Next Article in Journal
A Comparison of the Efficiency of Catalysts Based on Ni, Ni-Co and Ni-Mo in Pressure Pyrolysis of Biomass Leading to Hythane
Next Article in Special Issue
Recent Advances in Homogeneous/Heterogeneous Catalytic Hydrogenation and Dehydrogenation for Potential Liquid Organic Hydrogen Carrier (LOHC) Systems
Previous Article in Journal
Production of Chlorine Dioxide Using Hydrogen Peroxide and Chlorates
Previous Article in Special Issue
Poly(imidazolium) Carbosilane Dendrimers: Synthesis, Catalytic Activity in Redox Esterification of α,β-Unsaturated Aldehydes and Recycling via Organic Solvent Nanofiltration
 
 
Search for Articles:
Title / Keyword
Author / Affiliation / Email
Journal
Article Type
 
 
Advanced Search
 
Section
Special Issue
Volume
Issue
Number
Page
 
Journals
Catalysts
Volume 11
Issue 12
10.3390/catal11121479
catalysts-logo
Submit to this Journal Review for this Journal Propose a Special Issue
► Article Menu

Article Menu

share Share announcement Help format_quote Cite question_answer Discuss in SciProfiles thumb_up
...
Endorse textsms
...
Comment
first_page
settings
Order Article Reprints
Font Type:
Arial Georgia Verdana
Font Size:
Aa Aa Aa
Line Spacing:
Column Width:
Background:
Article

Chiral Quaternary Ammoniums Derived from Dehydroabietylamine: Synthesis and Application to Alkynylation of Isatin Derivatives Catalyzed by Silver

by
Guanyu Jiang
1,
Xinduo Sun
1,
Fanrui Zhou
1,
Kun Liang
1 and
Qian Chen
1,2,*
1
Key Laboratory of State Forestry and Grassland Administration on Highly-Efficient Utilization of Forestry Biomass Resources in Southwest China, College of Chemical Engineering, Southwest Forestry University, Kunming 650224, China
2
Key Laboratory of Forest Resources Conservation and Utilization in the Southwest Mountains of China Ministry of Education, College of Chemical Engineering, Southwest Forestry University, Kunming 650224, China
*
Author to whom correspondence should be addressed.
Catalysts 2021, 11(12), 1479; https://doi.org/10.3390/catal11121479
Submission received: 21 November 2021 / Revised: 26 November 2021 / Accepted: 29 November 2021 / Published: 3 December 2021
(This article belongs to the Special Issue Heterogeneous/Homogeneous Catalysis in Organic Synthesis – Recent Advances)
Browse Figures
Versions Notes

Abstract

:
Abietic acid and its derivatives have broadly been used in fine chemicals and are renewable resources. Its inherent chiral rigid tricyclic phenanthrene skeleton is unique. Its utilities in asymmetric catalysis remain to be explored. A series new amide-type chiral quaternary ammoniums bearing dehydroabietylamine were designed, and prepared by two convenient steps. Acylation of dehydroabietylamine with bromoacetyl chloride afforded amide holding bromoacetyl group in higher yields using triethyl amine as base. Subsequent quaternization reaction gave the desired amide-type chiral quaternary ammoniums. The new chiral quaternary ammoniums can be used as phase-transfer catalyst (PTC) for the transition metal-catalysed alkynylation of isatin derivatives.

1. Introduction

Rosin can be abundantly obtained from pine trees as a kind of unique sustainable and renewable biomass resource. Abietic acid is an essential component of rosin, which has an inherent rigid tricyclic diterpene structure with favorable biocompatibility [1]. Abietic acid and its derivatives are therefore used as raw materials for the preparation of many kinds of fine chemicals due to their rigid hydrophobic structure (Figure 1), such as a monomer of polymer or cross-linking agent [2,3,4,5,6,7,8,9,10,11,12,13,14], surfactants [15,16,17,18,19,20,21], and bioactive compounds [22,23,24,25,26,27]. As one of the important commercially available derivatives of abietic acid, dehydroabietylamine has been broadly used in the preparation of antitumor therapies [28,29,30,31], epoxy resin [32], and quaternary ammonium surfactants [33,34,35]. However, its potential application has still not been well developed as an optical active amine with a rigid tricyclic phenanthrene skeleton. Chiral thioureas and thiouronium salts containing dehydroabietylamine group are prepared and used for the physical separation of racemic mixtures [36,37]. Wang’s group developed a class of a chiral thioureas holding dehydroabietylamine group, which can be used as powerful chiral catalysts for many reactions [38,39,40,41,42,43,44], such as Michael addition, aza-Henry reaction, Mannich reaction, and Friedel–Crafts alkylation. A bifunctional squaramide catalyst was designed and utilized for efficient asymmetric Michael/cyclization cascade reaction [45].
Alkynes and their derivatives are important structural motifs in biologically significant pharmaceuticals and potential intermediates for many kinds of transformations. Alkynylation of aldehydes is one of the most efficient approaches for the preparation of optically active secondary propargylic alcohols [46,47,48]. In the early stages of this transformation, stoichiometric amounts of metal reagents such as organolithium, organomagnesium, and diorganozinc compounds were needed to increase the nucleophilicity of the alkyne. An efficient method for the catalytic asymmetric alkynylation of aldehydes was developed by Carreira’s pioneering work and carried forward by other groups [49,50,51,52,53,54,55,56,57,58,59,60,61,62,63,64,65,66,67]. Then, the formation of chiral tertiary alcohols was realized by enantioselective alkynylation of ketones, isatin derivatives and α-ketoesters [68,69,70,71,72,73,74,75,76,77,78,79,80,81,82]. Maruoka reported an interesting work on enantioselective alkynylation of isatin derivatives using a hybrid catalyst system consisting of chiral phase-transfer catalyst (PTC) and transition-metal catalyst [76]. Much great progress has been made in the counterion-mediated (chiral anion) enantioselective metal catalysis [83,84,85,86,87,88,89,90,91,92,93,94,95,96]. It should be noted that the example of transition metal catalysis on the condition of phase-transfer (chiral cation/ammonium) is very rare [97,98]. Following our interests to the addition of terminal alkyne and utility of chiral natural product [99,100], we had an interest to probe the possibility of quaternary ammonium containing dehydroabietylamine as chiral phase-transfer catalyst. Although the dehydroabietylamine has been broadly used for preparation of quaternary ammonium surfactants, the application of quaternary ammonium bearing dehydroabietylamine as chiral phase-transfer catalyst has been scarcely explored [33,34,35]. Herein, we report a practical synthesis of new chiral quaternary ammonium bearing dehydroabietylamine, using it as a phase-transfer catalyst for the transition-metal catalytic alkynylation of isatin derivatives.

2. Results and Discussion

2.1. Design and Synthesis of Chiral Dehydroabietylamine Quaternary Ammoniums

We envisaged that new chiral dehydroabietylamine quaternary ammonium derivatives should be conveniently prepared by short steps. Thus, five dehydroabietylamine quaternary ammoiums were derived from chain or cyclic tertiary amines (Figure 2).
The synthesis of dehydroabietylamine quaternary ammonium derivatives is shown in Scheme 1. Amidation reaction between bromoacetyl chloride 3 and commercially available dehydroabietylamine 2 produces bromide 4 in 85% yields using triethyl amine as base in CH2Cl2. The quaternization reaction bromide 4 with triethyl amine, 1-methylpiperidine, 1-methylpyrrolidine, N,N,N′,N′-tetramethyl-1,3-propanediamine, triethylene diamine (DABCO) gave the corresponding quaternary ammonium derivatives in high yields, respectively.

2.2. Metal-Catalysed Alkynylation of Isatin Derivatives in the Presence of Chiral Quaternary Ammoniums

Our investigation began with the addition of phenylacetylene 6a to isatin derivative 5a (Table 1). Initially, the reaction was carried out by using 5 mol % of AgOAc and 5.5 mol% 1a as catalyst and K2CO3 as base in THF. The desired product can be obtained in a 68% yield without enantioselectivity at 50 °C (Table 1, entry 1). Investigations into the effects of dehydroabietylamine quaternary ammonium derivatives suggested that marginal enantioselectivities were observed when 1d and 1e were used (Table 1, entries 2–5). The same enantioselectivity was obtained but the yield was slightly reduced when toluene was used as a solvent (Table 1, entry 6). Examination into the effects of metal catalyst precursors suggested that AgOAc was the best choice, although AgOTf, CuOTf and CuI were suitable catalysts for the present reaction (Table 1, entries 7–10). The reaction was very sluggish at room temperature (Table 1, entry 11). When 5b was used as substrate, the enantioselectivity was increased to 6%ee (Table 1, entries 12–13). When 5c was used as substrate, the screening of solvents suggested that the solvents have a distinct influence on catalytic activity (Table 1, entries 14–22). Mesitylene gave best result with respect to the enantioselectivity, whereas, THF, toluene, DMSO, and MeOH gave worse results (entries 14–16, 17–21). Investigations into the effects of bases suggested that all of the examined inorganic base carbonates were suitable bases for the present reaction (Table 1, entries 22–26). Finally, in the absence of AgOAc, no desired compound was observed, suggesting that metal catalyst played an important role in the transformation [101] (Table 1, entry 26).

2.3. Scope for Addition of Alkynes to Isatin Derivatives

Next, studies on the expansion of the substrate scopes were then carried out using the relative optimal reaction conditions (Table 1, entry 21). As shown in Scheme 2, the different substituents and substitution patterns of the isatin and aryl acetylene were all tolerated. The 1-n-Butyl-4-ethynylbenzene was successfully added to 5c to give the corresponding product 7cb in a moderate yield and 6%ee. The reaction of 5c with 1-ethynyl-4-methoxybenzene and 1-ethynyl-4-ethoxybenzene, holding a strong electron-donating substituent, gave the desired products 7cc and 7cd in good yield with 3%ee and 9%ee, respectively. Aryl acetylene-bearing, electron-withdrawing substituents, including fluoro- and chloro-groups, were tested for the present reaction, and the desired products (7ce and 7cf) were obtained in good to high yields with 2%ee and 3%ee. The reaction of isatin derivative 5d holding methyl with phenylacetylene 6a and 1-ethynyl-3-fluorobenzene 6f gave the desired products, 7da and 7df, in good yields with 3%ee. The alkynylation of isatin derivative 5e tolerating electron-donating substituents with phenylacetylene 6a, 1-ethyl-4-ethynylbenzene 6g, and 1-ethynyl-3-fluorobenzene 6f gave the desired products, 7ea, 7eg, and 7df, in moderate to good yields, respectively. Isatin derivatives (5f, 5g, and 5h) with electron-withdrawing substituents, including fluoro-, bromo-, and chloro-groups, smoothly reacted with aromatic alkynes containing a wide range of functionalities to give the corresponding products 7 in good to high yields. The results indicated that the electronic property and steric hindrance on the isatins or aromatic alkynes had a slight effect on the reaction.

2.4. Mechanism for Ag-Catalysed Alkynylation of Isatin Derivatives

On the basis of the experimental results as well as literature’s working hypothesis [47,77], we propose the mechanism of the present Ag catalysed alkynylation of isatin derivatives, as shown in Scheme 3. We speculated that a silver alkynilide is formed by the coordination of terminal alkyne 6 with Ag(I) and deprotonation, which can produce a silver alkynilide ion pair intermediate A with chiral quaternary ammoniums catalyst (Q+Br−). The nucleophilic addition of the silver alkynilide intermediate A to isatin 5 affords the desired product 7. Comparison with Maruoka’s chiral quaternary ammoniums catalyst holding binaphthyl framework, a lower enantioselectivity was observed, which may be causeded by the asymmetric center of the catalyst being far away from the nitrogen atom. The future focus will be to further modify the structure of the chiral quaternary ammonium containing dehydroabietylamine to improve the enantioselectivity.

3. Materials and Methods

3.1. General Information

The 1H and 13C NMR data were acquired on a Bruker AV-400 and/or AV-600 MHz spectrometer (Billerica, MA, USA). HRMS data were obtained from Agilent 6520 Q-TOF LC/MS (Santa Clara, CA, USA). Commercial reagents were purchased and used without further purification. THF and toluene were distilled over benzophenone ketyl under nitrogen. DMF and MeOH were distilled over CaH2 under nitrogen. Dioxane was distilled over LiAlH4 under nitrogen.

3.2. General Procedure for the Synthesis of 2-Bromo-N-(((1R,4aS)-7-isopropyl-1,4a-dimethyl-1,2,3,4,4a,9,10,10a-octahydrophenanthren-1-yl) methyl) acetamide 4

To a solution of dehydroabietylamine (2.850 g, 10.0 mmol) and triethylamine (1.525 g, 15.0 mmol) in dry dichloromethane (20 mL) at 0 °C under nitrogen atmosphere, was added dropwise a solution of bromoacetyl chloride (2.340 g, 15.0 mmol) in dry dichloromethane (10 mL). After the completion of addition, the reaction mixture was stirred at room temperature overnight and poured into saturated NaHCO3 solution. The aqueous layer was extracted with dichloromethane (2 × 25 mL) and the combined organic phases were washed with brine solution, dried over anhydrous Na2SO4 and filtered. The solvent was removed under reduced pressure, and the residue was purified through silica gel column chromatography to give the product 4, 3.440 g, 85%. 1H NMR (400 MHz, CDCl3) δ 7.17 (d, J = 8.0 Hz, 1H), 7.00 (d, J = 8.0 Hz, 1H), 6.89 (s, 1H), 6.63–6.55 (s, amide rotomer,1H), 4.05 (s, 1H), 3.89 (s, 1H), 3.26–3.20 (m, 1H), 3.17–3.15 (m, 1H), 2.92–2.89 (m, 1H), 2.85–2.81 (m, 2H), 2.30 (d, J = 8.0 Hz, 1H), 1.76–1.70 (m, 5H), 1.45–1.40 (m, 3H), 1.28–1.22 (m, 9H), 0.96 (s, 3H). 13C NMR (101 MHz, CDCl3) δ 165.8, 165.2, 146.9, 145.7, 134.7, 127.0, 124.2, 123.9, 50.7, 50.2, 45.7, 45.6, 42.9, 38.3, 37.53, 37.47, 36.2, 33.4, 30.4, 29.8, 25.4, 24.0, 23.97, 19.1, 18.63, 18.59, 18.57. HRMS-ESI (m/z): Calcd for C22H33BrN2O+ [M+H]+: 406.1740, Found: 406.1728 (see the Supplementary Materials).

3.3. General Procedure for the Synthesis of Chiral Dehydroabietylamine Quaternary Ammoniums 1

To a reaction tube were added above bromide 4 (445 mg, 1.1 mmol), CH3CN (3 mL), and tertial amine (1 mmol 1a, 1b, 1c; 0.5 mmol 1d, 1e). The mixture was stirred at 60 °C overnight. After being cooled to room temperature, AcOEt (10 mL) was added and the resulting solid was washed with AcOEt several times to give the quaternary ammonium salt.

3.3.1. N, N, N-Triethyl-2-((((1R,4aS)-7-isopropyl-1,4a-dimethyl-1,2,3,4,4a,9,10,10a- octahydrophenanthren-1-yl) methyl) amino)-2-oxoethan-1-aminium bromide (1a)

A colorless powder, m.p. 217–219 °C. 1H NMR (400 MHz, CDCl3) δ 9.16 (s,1H), 7.15 (d, J = 8.1 Hz, 1H), 6.97 (d, J = 8.1 Hz, 1H), 6.86 (s,1H), 4.63 (d, J = 15.2 Hz, 1H), 4.55 (d, J = 15.2 Hz, 1H), 3.54 (q, J = 7.1 Hz, 6H), 3.30 (dd, J = 13.2 and 7.1 Hz, 1H), 3.08 (dd, J = 13.4 and 5.5 Hz, 1H), 2.91–2.79 (m, 3H), 2.26 (d, J = 12.7 Hz, 1H), 1.97 (s, 3H), 1.93–1.91 (m, 1H), 1.74–1.69 (m, 3H), 1.55–1.41 (m, 4H), 1.37 (t, J = 6.9 Hz, 9H), 1.20 (d, J = 6.9 Hz, 6H), 0.97 (s, 3H). 13C NMR (101 MHz, CDCl3) δ 163.4, 147.4, 145.5, 134.8, 126.8, 124.1, 123.7, 27.2, 54.8, 50.4, 45.4, 38.3, 37.9, 37.4, 36.4, 35.4, 30.0, 25.3, 24.1, 19.1, 18.6, 18.5, and 8.2. HRMS-ESI (m/z): Calcd for C28H47N2O3+ [M-Br]+: 427.3683, Found: 427.3681.

3.3.2. 1-(2-((((1R,4aS)-7-Isopropyl-1,4a-dimethyl-1,2,3,4,4a,9,10,10a- octahydrophenanthren-1-yl)methyl)amino)-2-oxoethyl)-1-methylpiperidin-1-ium bromide (1b)

A colorless powder, m.p. 278–280 °C. The 1H NMR (600 MHz, CDCl3), δ 9.09 (s,1H), 7.15 (d, J = 8.2 Hz, 1H), 6.97 (d, J = 8.2 Hz, 1H), 6.87 (s,1H), 4.77 (d, J = 13.5 Hz, 1H), 4.70 (d, J = 13.5 Hz, 1H), 3.94–3.90 (m, 2H), 3.42–3.30 (m, 5H), 3.14–3.10 (m, 1H), 2.91–2.90 (m, 2H), 2.82–2.79 (m, 1H), 2.26 (d, J = 12.6 Hz, 1H), 1.96–1.90 (m, 3H), 1.93–1.91(m, 1H), 1.84–1.65(m, 10H), 1.58 (d, J = 13.2 Hz, 1H), 1.47–1.34 (m, 3H), 1.20 (d, J = 6.9 Hz, 6H), 0.97 (s, 3H). The 13C NMR (151 MHz, CDCl3) δ 163.2, 147.3, 145.5, 134.8, 126.8, 124.1, 123.8, 62.7, 62.5, 50.5, 45.5, 38.3, 37.8, 37.4, 36.3, 33.4, 30.1, 25.3, 24.0, 20.9, 20.1, 19.1, 18.6, and 18.5. HRMS-ESI(m/z): Calcd for C28H45N2O3+ [M-Br]+: 425.3526, Found: 425.3536.

3.3.3. 1-(2-((((1R,4aS)-7-Isopropyl-1,4a-dimethyl-1,2,3,4,4a,9,10,10a- octahydrophenanthren-1-yl)methyl)amino)-2-oxoethyl)-1-methylpyrrolidin-1-ium bromide (1c)

A colorless powder, m.p. 215–217 °C. The 1H NMR (600 MHz, CDCl3), δ 8.95 (s,1H), 7.15 (d, J = 8.4 Hz, 1H), 6.97 (d, J = 8.4 Hz, 1H), 6.87 (s,1H), 4.77 (d, J = 15.2 Hz, 1H), 4.76 (d, J = 15.2 Hz, 1H), 3.99–3.94 (m, 2H), 3.67–3.66 (m, 1H), 3.56–3.54 (m, 1H), 3.30 (s, 3H), 3.26 (dd, J = 12.6 and 4.8 Hz, 1H), 3.17 (dd, J = 13.2 and 5.4 Hz, 1H), 2.91–2.90 (m, 2H), 2.81–2.79 (m, 1H), 2.29–2.26 (m, 3H), 2.13–2.09 (m, 2H), 1.85 (s, 3H), 1.64–1.61 (m, 3H), 1.55 (d, J = 11.4 Hz, 1H), 1.41–1.25 (m, 3H), 1.20 (d, J = 7.2 Hz, 6H), 0.97 (s, 3H). The 13C NMR (151 MHz, CDCl3) δ 163.7, 147.3, 145.5, 134.9, 126.8, 124.2, 123.8, 65.4, 63.5, 50.4, 49.9, 45.5, 38.3, 37.9, 37.4, 36.4, 33.4, 30.1, 25.4, 24.0, 21.5, 19.1, 18.6, and 18.5. HRMS-ESI(m/z): Calcd for C27H43N2O3+ [M-Br]+: 411.3370, Found: 411.3380.

3.3.4. N1,N3-Bis(2-((((1R,4aS)-7-isopropyl-1,4a-dimethyl-1,2,3,4,4a,9,10,10a- octahydrophenanthren-1-yl)methyl)amino)-2-oxoethyl)-N1,N1,N3,N3-tetramethylpropane-1,3-diaminium bromide (1d)

A colorless powder, m.p. 299–301°C. The 1H NMR (600 MHz, CDCl3,) δ 8.43 (s, 2H), 7.15 (d, J = 7.8 Hz, 2H), 6.99 (d, J = 8.4 Hz, 2H), 6.88 (s, 2H), 4.61 (d, J = 14.4 Hz, 2H), 4.31 (t, J = 7.2 Hz, 1H), 3.96–3.94 (m, 2H), 3.76–3.74 (m, 2H), 3.54–3.36 (m, 18H), 3.06–3.05 (m, 2H), 2.91–2.90 (m, 3H), 2.83–2.77 (m, 6H), 2.26 (d, J = 12.3 Hz, 2H), 2.04 (d, J = 5.4 Hz, 2H), 1.96–1.92 (m, 6H), 1.46–1.45 (m, 6H), 1.29–1.18 (m, 12H), 0.97–0.94 (m, 10H). The 13C NMR (151 MHz, CDCl3) δ 162.7, 147.2, 145.8, 134.7, 131.0, 128.9, 127.0, 124.3, 124.1, 65.6, 62.8, 57.5, 53.5, 52.7, 50.5, 45.5, 38.3, 37.8, 37.5, 33.4, 30.5, 30.4, 29.7, 25.5, 24.1, 23.9, 19.1, 18.7, and 18.4. HRMS-ESI(m/z): Calcd for C51H82N4O22+ [M-2Br]2+: 782.6427, Found: 782.6427

3.3.5. 1,4-Bis(2-((((1R,4aS)-7-isopropyl-1,4a-dimethyl-1,2,3,4,4a,9,10,10a- octahydrophenanthren-1-yl)methyl)amino)-2-oxoethyl)-1,4-diazabicyclo[2.2.2]octane-1,4-diium bromide (1e)

A colorless powder, m.p. 327–329 °C. The 1H NMR (400 MHz, DMSO-d6) δ 8.51 (s, 2H), 7.15 (d, J = 8.0 Hz, 2H), 6.95 (d, J = 8.0 Hz, 2H), 6.85 (s, 2H), 4.44 (dd, J = 24.4 and 15.6 Hz, 4H), 4.14(s, 12H), 3.20–3.16 (m, 2H), 2.98–2.93 (m, 2H), 2.80–2.75 (m, 6H), 2.27 (d, J = 8.0 Hz, 2H), 1.76–1.59 (m, 8H), 1.38–1.33 (m, 8H), 1.16–1.13 (m, 18H), 0.89 (s, 6H). The 13C NMR (101 MHz, DMSO-d6) δ 163.2, 147.4, 145.4, 134.9, 126.9, 124.6, 124.0, 62.2, 51.6, 49.3, 44.6, 38.3, 37.7, 37.5, 36.0, 33.4, 30.0, 25.7, 24.4, 19.2, 18.8, and 18.7. HRMS-ESI(m/z): Calcd for C50H76N4O22+ [M-2Br]2+: 764.5957, Found: 764.5955.

3.4. General Procedure for Addition of Alkynes to Isatin Derivatives

Under an atmosphere of N2, a reaction tube was charged with isatin (0.20 mmol), AgOAc (0.01 mmol), quaternary ammonium salt (0.011 mmol), base (0.40 mmol). Then, mesitylene (2.0 mL) and alkyne (0.40 mmol) were added successively to the tube. The mixture was stirred at given temperature for 12 h. The mixture was directly purified through silica gel column chromatography to give the product 7.

3.4.1. (S)-1-Benzyl-3-hydroxy-3-(phenylethynyl)indolin-2-one 7aa

Silica gel column chromatography (hexane/AcOEt = 5/1) gave 7aa as a colorless solid, m.p. 179–181 °C. The 1H NMR (400 MHz, CDCl3), δ 7.63 (d, J = 8.0 Hz, 1H), 7.47 (d, J = 8.0 Hz, 2H), 7.32-7.23 (m, 9H), 7.14 (d, J = 8.0 Hz, 1Hz), 6.73 (d, J = 8.0 Hz, 1H), 4.94 (s, 2H), 3.49 (s, 1H). The 13C NMR (101 MHz, CDCl3) δ 174.04, 142.20, 134.99, 132.11, 130.47, 129.10, 128.93, 128.77, 128.27, 127.84, 127.18, 124.82, 123.80, 121.57, 109.96, 86.62, 85.39, 69.62, amd 44.12. HRMS-ESI(m/z): Calcd for C23H18NO2+ [M+H]+: 340.1332, Found: 340.1373.

3.4.2. (S)-1-Benzhydryl-3-hydroxy-3-(phenylethynyl)indolin-2-one 7ba

Silica gel column chromatography (hexane/AcOEt = 5/1) gave 7ba as a colorless solid, m.p. 189–191 °C. The 1H NMR (400 MHz, CDCl3), δ 7.61 (d, J = 4.0 Hz, 1H), 7.48 (d, J = 8.0 Hz, 2H), 7.37-7.28(m,13H), 7.11 (t, J = 4.0 Hz, 2H), 6.98(s, 1H), 6.51 (d, J = 4.0 Hz, 1H), 3.09 (s, 1H). the 13C NMR (101 MHz, CDCl3) δ 174.32, 141.87, 137.10, 136.97, 132.14, 129.91, 129.02, 128.71, 128.67, 128.51, 128.36, 128.24, 127.97, 124.79, 123.50, 121.66, 112.03, 86.57, 86.51, 69.33, and 58.50. HRMS-ESI(m/z): Calcd for C29H21NNaO2+ [M+Na]+: 438.1465, Found: 438.1469.

3.4.3. (S)-3-Hydroxy-3-(phenylethynyl)-1-tritylindolin-2-one 7ca

Silica gel column chromatography (hexane/AcOEt = 5/1) gave 7ca as a yellow solid, m.p. 219-222 °C. The 1H NMR (400 MHz, CDCl3), δ 7.54 (d, J = 4.0 Hz, 1H), 7.48 (d, J = 4.0 Hz, 8H), 7.32-7.28 (m, 3H), 7.26 (t, J = 8.0 Hz, 6H), 7.20 (t, J = 4.0 Hz, 3H), 7.00 (d, J = 8.0 Hz, 1H), 6.98 (dd, J = 4.0 Hz and 16.0 Hz, 1H), 6.29 (d, J = 4.0 Hz, 1H), 3.61 (s, 1H). The 13C NMR (101 MHz, CDCl3) δ 174.57, 141.54, 140.52, 131.02, 128.14, 127.97, 127.95, 127.72, 127.27, 126.77, 126.02, 122.84, 122.05, 115.16, 85.13, 84.86, 73.27, and 68.68. HRMS-ESI(m/z): Calcd for C35H25NNaO2+ [M+Na]+: 514.1778, Found: 514.1747.

3.4.4. (S)-3-((4-Butylphenyl)ethynyl)-3-hydroxy-1-tritylindolin-2-one 7cb

Silica gel column chromatography (hexane/AcOEt = 5/1) gave 7cb as a yellow solid, m.p. 225–227 °C. The 1H NMR (400 MHz, CDCl3), δ 7.57 (d, J = 4.0 Hz, 1H), 7.51 (d, J = 8.0 Hz, 6H), 7.43 (d, J= 8.0 Hz, 2H), 7.31-7.22 (m, 12H), 7.18 (d, J = 12.0 Hz, 2H), 7.03 (t, J = 4.0 Hz, 1H), 6.32 (d, J = 8.0 Hz, 1H), 3.29 (s, 1H), 2.65 (t, J = 8.0 Hz, 3H), 1.62 (m, J = 8.0 Hz, 2H), 1.39 (q, J = 8.0 Hz, 2H), 0.96 (t, J = 4.0 Hz, 3H). The 13C NMR (101 MHz, CDCl3) δ 175.64, 144.31, 1442.58, 141.58, 132.00, 129.19, 129.00, 128.73, 128.45, 127.81, 127.06, 123.82, 123.07, 118.84, 116.19, 86.19, 85.44, 74.27, 69.73, 35.61, 33.34, 22.28, and 13.92. HRMS-ESI(m/z): Calcd for C39H33NNaO2+ [M+Na]+: 570.2404, Found: 570.2428.

3.4.5. (S)-3-Hydroxy-3-((4-methoxyphenyl)ethynyl)-1-tritylindolin-2-one 7cc

Silica gel column chromatography (hexane/AcOEt = 5/1) gave 7cc as a light yellow solid, m.p. 205–208 °C. The 1H NMR (400 MHz, CDCl3), δ 7.49 (d, J = 4.0 Hz, 2H), 7.47-7.27 (m, 8H), 7.26-7.21(m, 12H), 7.01 (s, 1H), 6.86 (d, J = 8.0 Hz, 2H), 6.29 (d, J = 8.0 Hz, 1H), 3.82 (s, 3H), 3.26 (s, 1H). The 13C NMR (101 MHz, CDCl3) δ 175.01, 160.16, 142.59, 141.59, 133.64, 129.20, 128.71, 127.81, 127.07, 123.81, 123.06, 116.19, 113.95, 113.76, 86.05, 84.80, 74.28, 69.75, and 55.32. HRMS-ESI(m/z): Calcd for C36H27NNaO3+ [M+Na]+: 544.1883, Found: 544.1875.

3.4.6. (S)-3-((4-Ethoxyphenyl)ethynyl)-3-hydroxy-1-tritylindolin-2-one 7cd

Silica gel column chromatography (hexane/AcOEt = 5/1) gave 7cd as a yellow solid, m.p. 210–213 °C. The 1H NMR (400 MHz, CDCl3), δ 7.55-7.40 (m, 10H), 7.29-7.20 (m, 9H), 7.01 (q, J = 4.0 Hz, 2H), 6.84 (d, J = 8.0 Hz, 1H), 6.29 (d, J = 8.0 Hz, 1H), 4.05 (q, J = 8.0 Hz, 2H), 3.26 (s, 1H), 1.57 (t, J =5.2 Hz, 3H). The 13C NMR (101 MHz, CDCl3) δ 170.43, 154.33, 137.34, 136.36, 128.40, 123.97, 123.85, 123.46, 122.57, 121.83, 118.57, 117.82, 110.95, 109.19, 108.31, 80.91, 79.49, 69.04, 64.52, 58.30, and 9.46. HRMS-ESI(m/z): Calcd for C37H29NNaO3+ [M+Na]+: 558.2040, Found: 558.2047.

3.4.7. (S)-3-((3-Chlorophenyl)ethynyl)-3-hydroxy-1-tritylindolin-2-one 7ce

Silica gel column chromatography (hexane/AcOEt = 5/1) gave 7ce as a light yellow solid, m.p. 214–217 °C. The 1H NMR (400 MHz, CDCl3), δ 7.54 (d, J = 8.0 Hz, 1H), 7.47-7.45 (m, 7H), 7.35 (t, J = 8.0 Hz, 2H), 7.40-7.23 (m, 10H), 7.02 (t, J = 8.0 Hz, 1H), 6.96 (t, J = 8.0 Hz, 1H), 6.34 (d, J = 8.0 Hz, 1H), 3.33 (s,1H). The 13C NMR (101 MHz, CDCl3) δ175.39, 141.50, 134.21, 131.95, 130.19, 129.60, 129.38, 129.21, 128.98, 127.85, 127.15, 123.92, 123.21, 116.16, 90.47, 84.43, 74.48, and 69.65. HRMS-ESI(m/z): Calcd for C35H24ClNNaO2+ [M+Na]+: 548.1388, Found: 548.1381.

3.4.8. (S)-3-((3-Fluorophenyl)ethynyl)-3-hydroxy-1-tritylindolin-2-one 7cf

Silica gel column chromatography (hexane/AcOEt = 5/1) gave 7cf as a light yellow solid, m.p. 212–214 °C. The 1H NMR (400 MHz, CDCl3), δ 7.55 (d, J = 8.0 Hz, 1H), 7.47 (d, J = 4.0 Hz, 6H), 7.29-7.17 (m, 12H), 7.07-6.96 (m, 3H), 6.31 (d, J = 8.0 Hz, 1H), 3.30 (s, 1H). The 13C NMR (101 MHz, CDCl3) δ 175.32, 142.67, 141.47, 129.95, 129.19, 128.96, 128.56, 127.98, 127.84, 127.14, 123.90, 123.19, 118.95, 118.80, 116.56, 116.41, 116.34, 86.98, 84.57, 74.43, and 69.63. HRMS-ESI(m/z): Calcd for C35H24FNNaO2+ [M+Na]+: 532.1683, Found: 532.1687.

3.4.9. (S)-3-Hydroxy-5-methyl-3-(phenylethynyl)-1-tritylindolin-2-one 7da

Silica gel column chromatography (hexane/AcOEt = 5/1) gave 7da as a yellow solid, m.p. 213–215 °C. The 1H NMR (400 MHz, CDCl3), δ 7.48-7.46 (m, 7H), 7.37-7.33 (m, 3H), 7.28-7.24 (m, 8H), 7.23-7.20 (m, 3H), 6.75 (d, J = 8.0 Hz, 1H), 6.16 (d, J = 8.0 Hz, 1H), 3.29 (s, 1H), 2.26 (s, 3H). The 13C NMR (101 MHz, CDCl3) δ 175.55, 141.65, 140.17, 132.86, 132.10, 129.32, 129.23, 129.03, 128.80, 128.34, 127.81, 127.08, 124.51, 116.04, 86.28, 85.84, 74.29, 69.80, and 20.81. HRMS-ESI(m/z): Calcd for C36H27NNaO2+ [M+Na]+: 528.1734, Found: 528.1738.

3.4.10. (S)-3-((3-Fluorophenyl)ethynyl)-3-hydroxy-5-methyl-1-tritylindolin-2-one 7df

Silica gel column chromatography (hexane/AcOEt = 5/1) gave 7df as a yellow solid, m.p. 223–225 °C. 1H NMR (400.0 MHz, CDCl3), δ 7.46-7.43 (m, 7H), 7.28-7.10 (m, 12H), 7.07 (s, 1H), 6.76 (d, J = 8.0 Hz, 1H), 6.17 (d, J = 8.0 Hz, 1H), 3.30 (s, 1H), 2.26 (s, 3H). The 13C NMR (101 MHz, CDCl3) δ 175.32, 141.57, 140.22, 129.47, 129.25, 129.22, 17.92, 127.82, 127.30, 127.12, 124.54, 118.97, 116.53, 116.14, 88.45, 87.17, 74.38, 69.71, and 20.79. HRMS-ESI(m/z): Calcd for C36H26FNNaO2+ [M+Na]+: 546.1840, Found: 546.1840.

3.4.11. (S)-3-Hydroxy-5-methoxy-3-(phenylethynyl)-1-tritylindolin-2-one 7ea

Silica gel column chromatography (hexane/AcOEt = 5/1) gave 7ea as a light yellow solid, m.p. 223–225°C. The 1H NMR (400 MHz, CDCl3), δ 7.50-7.45 (m, 8H), 7.35-7.28 (m, 3H), 7.28 -7.20 (m, 9H), 7.14 (d, J = 4.0 Hz, 1H), 6.49 (d, J = 8.0 Hz, 1H), 6.18 (d, J = 8.0 Hz, 1H), 3.74 (s, 3H), 3.34 (s, 1H). The 13C NMR (101 MHz, CDCl3) δ 174.36, 157.81, 141.63, 135.72, 132.09, 131.46, 129.96, 129.24, 128.33, 127.81, 127.61, 127.09, 126.43, 109.72, 108.17, 88.57, 84.94, 69.97, 69.76, and 55.62. HRMS-ESI(m/z): Calcd for C36H27NNaO3+ [M+Na]+: 544.1883, Found: 544.1879.

3.4.12. (S)-3-((4-Ethylphenyl)ethynyl)-3-hydroxy-5-methoxy-1-tritylindolin-2-one 7eg

Silica gel column chromatography (hexane/AcOEt = 5/1) gave 7eg as a deep yellow solid, m.p. 198–200 °C. The 1H NMR (400 MHz, CDCl3), δ 7.47-7.45 (m, 6H), 7.41 (d, J = 8.0 Hz, 2H), 7.28-7.25 (m, 6H), 7.23-7.20 (m, 3H), 7.16 (d, J = 8.0 Hz, 2H), 7.13 (d, J = 4.0 Hz, 1H), 6.48 (dd, J = 8.0 Hz and 4.0 Hz, 1H), 6.17 (d, J = 4.0 Hz, 1H), 3.74 (s, 3H), 3.30 (s, 1H), 2.66 (q, J = 4.0 Hz, 2H), 1.25 (t, J= 4.0 Hz, 3H). The 13C NMR (101 MHz, CDCl3) δ 179.45, 147.86, 141.65, 134.70, 132.11, 130.05, 129.23, 127.91, 127.80, 127.06, 116.98, 114.30, 109.67, 86.52, 83.97, 74.27, 69.99, 55.62, 28.86, and 15.30. HRMS-ESI(m/z): Calcd for C38H31NNaO3+ [M+Na]+: 572.2196, Found: 572.2199.

3.4.13. (S)-3-((3-Fluorophenyl)ethynyl)-3-hydroxy-5-methoxy-1-tritylindolin-2-one 7ef

Silica gel column chromatography (hexane/AcOEt = 4/1) gave 7ef as a yellow solid, m.p. 215–217 °C. The 1H NMR (400 MHz, CDCl3), δ 7.46 (d, J = 4.0 Hz, 7H), 7.31-7.07 (m, 18H), 6.51 (d, J = 8.0 Hz, 1H), 6.20 (d, J = 8.0 Hz, 1H), 3.74 (s, 3H), 3.36 (s, 1H). The 13C NMR (101 MHz, CDCl3) δ 175.11, 155.96, 141.54, 135.72, 129.97, 129.63, 129.22, 128.01, 127.84, 127.15, 118.97, 118.82, 117.15, 114.48, 109.73, 87.05, 74.41, 69.89, and 55.63. HRMS-ESI(m/z): Calcd for C36H26FNNaO3+ [M+Na]+: 562.1789, Found: 562.1779.

3.4.14. (S)-5-Fluoro-3-hydroxy-3-(phenylethynyl)-1-tritylindolin-2-one 7fa

Silica gel column chromatography (hexane/AcOEt = 4/1) gave 7fa as a yellow solid, m.p. 240–242 °C. The 1H NMR (400 MHz, CDCl3), δ 7.50-7.44 (m, 8H), 7.37-7.21(m, 13H), 6.65 (d, J = 8.0 Hz, 1H), 6.23 (d, J = 8.0 Hz, 1H), 3.41 (s, 1H). The 13C NMR (101 MHz, CDCl3) δ 175.32, 142.67, 141.47, 129.95, 129.19, 128.96, 128.56, 127.98, 127.84, 127.14, 123.90, 123.19, 118.95, 118.80, 116.56, 116.41, 116.34, 86.98, 84.57, 74.43, and 69.63. HRMS-ESI(m/z): Calcd for C35H24FNNaO2+ [M+Na]+: 532.1683, Found: 532.1685.

3.4.15. (S)-3-((4-Ethylphenyl)ethynyl)-5-fluoro-3-hydroxy-1-tritylindolin-2-one 7fg

Silica gel column chromatography (hexane/AcOEt = 5/1) gave 7fg as a deep yellow solid, m.p. 215–217 °C. The 1H NMR (400 MHz, CDCl3), δ 7.49-7.44 (m, 8H), 7.32-7.24 (m, 10H), 7.20(d, J = 8.0 Hz, 2H), 6.70-6.66 (m, 1H), 6.23 (dd, J = 8.0 Hz and 4.0 Hz, 1H), 3.40 (s, 1H), 2.68 (q, J = 4.0 Hz, 2H), 1.24 (t, J = 4.0 Hz, 3H). The 13C NMR (101 MHz, CDCl3) δ 175.43, 158.04, 145.80, 141.39, 138.40, 135.28, 132.13, 129.19, 127.97, 127.89, 127.21, 120.95, 118.67, 117.05, 111.58, 86.62, 84.93, 74.46, 69.71, 28.88, and 15.30. HRMS-ESI(m/z): Calcd for C37H28FNNaO2+ [M+Na]+: 560.1996, Found: 560.1992.

3.4.16. (S)-3-((4-Butylphenyl)ethynyl)-5-fluoro-3-hydroxy-1-tritylindolin-2-one 7fb

Silica gel column chromatography (hexane/AcOEt = 5/1) gave 7fb as a deep yellow solid, m.p. 230–232 °C. The 1H NMR (400 MHz, CDCl3), δ 7.52 (d, J = 8.0 Hz, 6H), 7.46 (d, J = 4.0 Hz, 2H), 7.33-7.25 (m, 10H), 7.21 (d, J =8.0 Hz, 2H), 6.70-6.67 (m, 1H), 6.28(dd, J =8.0 Hz and 4Hz, 1H), 3.55 (s, 1H), 2.68 (t, J = 4.0 Hz, 2H), 1.68-1.61 (m, 2H), 1.42 (q, J = 4.0 Hz, 2H), 0.99 (t, J = 4.0 Hz, 3H). The 13C NMR (101 MHz, CDCl3) δ 175.48, 160.00, 158.06, 144.51, 141.43, 138.41, 132.09, 129.22, 128.52, 127.92, 127.22, 118.68, 117.07, 115.36, 115.18, 111.81, 111.61, 86.67, 85.01, 74.50, 69.75, 35.65, 33.36, 22.31, and 13.95. HRMS-ESI(m/z): Calcd for C39H32FNNaO2+ [M+Na]+: 588.2309, Found: 588.2316.

3.4.17. (S)-3-((4-Ethoxyphenyl)ethynyl)-5-fluoro-3-hydroxy-1-tritylindolin-2-one 7fd

Silica gel column chromatography (hexane/AcOEt = 5/1) gave 7fd as a deep yellow solid, m.p. 200–202 °C. The 1H NMR (400 MHz, CDCl3), δ 7.45 (d, J = 4.0 Hz, 6H), 7.41 (d, J = 4.0 Hz, 2H), 7.28-7.20 (m, 10H), 6.86 (d, J = 8.0 Hz, 2H), 6.66 (td, J = 8.0 Hz and 4.0 Hz, 1H), 6.20 (dd, J = 8.0 Hz and 4.0 Hz, 1H), 4.04 (q, J = 8.0 Hz, 2H), 3.37 (br, 1H), 1.42 (t, J = 8.0 Hz, 3H). The 13C NMR (101 MHz, CDCl3) δ 175.48, 160.30, 159.81, 158.19, 141.37, 138.39, 133.70, 130.64, 129.19, 127.90, 127.21, 117.12, 117.07, 115.35, 115.19, 114.03, 113.50, 111.74, 115.35, 115.19, 114.03, 113.50, 111.74, 111.58, 86.51, 84.28, 74.44, 69.73, 63.58, and 14.72. HRMS-ESI(m/z): Calcd for C37H28FNNaO3+ [M+H]+: 576.1945, Found: 576.1949.

3.4.18. (S)-3-((3-Chlorophenyl)ethynyl)-5-fluoro-3-hydroxy-1-tritylindolin-2-one 7fe

Silica gel column chromatography (hexane/AcOEt = 5/1) gave 7fe as a yellow solid, m.p. 201–203 °C. The 1H NMR (400 MHz, CDCl3), δ 7.48(s, 1H), 7.44-7.35 (m, 6H), 7.36 (t, J = 4.0 Hz, 2H), 7.29 -7.22 (m, 11H), 6.67 (t, J = 4.0 Hz, 1H), 6.24 (t, J = 4.0 Hz, 1H), 3.36 (s, 1H). The 13C NMR (101 MHz, CDCl3) δ 141.25, 138.48, 130.22, 129.67, 129.57, 129.17, 127.93, 122.29, 122.11, 117.59, 117.26, 115.64, 115.49, 111.83, 111.66, 86.69, 84.83, 74.60, and 69.58. HRMS-ESI(m/z): Calcd for C35H23ClFNNaO2+ [M+Na]+: 566.1294, Found: 566.1278.

3.4.19. (S)-3-((4-Chlorophenyl)ethynyl)-5-fluoro-3-hydroxy-1-tritylindolin-2-one 7fh

Silica gel column chromatography (hexane/AcOEt = 5/1) gave 7fh as a yellow solid, m.p. 219–221 °C. The 1H NMR (400 MHz, CDCl3), δ 7.48-7.35 (m, 7H), 7.28 (t, J = 4.0 Hz, 2H), 7.26-7.21 (m, 11H), 6.68 (dd, J = 8.0 Hz and 4.0 Hz, 1H), 6.24 (dd, J = 4.0 Hz and 4.0 Hz, 1H), 3.40 (s, 1H). The 13C NMR (101 MHz, CDCl3) δ 175.19, 159.83, 158.22, 141.27, 138.48, 135.42, 133.35, 130.18, 129.18, 128.80, 127.98, 127.28, 126.91, 119.96, 117.29, 115.60, 115.45, 111.83, 111.66, 86.48, 85.23, 74.59, and 69.63. HRMS-ESI(m/z): Calcd for C35H23ClFNNaO2+ [M+Na]+: 566.1294, Found: 566.1283.

3.4.20. (S)-5-Fluoro-3-((3-fluorophenyl)ethynyl)-3-hydroxy-1-tritylindolin-2-one 7ff

Silica gel column chromatography (hexane/AcOEt = 5/1) gave 7ff as a yellow solid, m.p. 211–213 °C. The 1H NMR (400 MHz, CDCl3), δ 7.45 (d, J = 8.0 Hz, 6H), 7.32-7.22 (m, 12H), 7.18 (d, J = 4.0 Hz, 1H), 7.09 (t, J = 4.0 Hz, 1H), 6.68 (t, J = 8.0 Hz, 1H), 6.24 (dd, J = 8.0 Hz and 4.0 Hz, 1Hz), 3.42 (s, 1H). The 13C NMR (101 MHz, CDCl3) δ 175.14, 163.08, 161.44, 159.84, 158.22, 141.26, 138.48, 130.09, 130.03, 129.17, 128.03, 128.01, 127.93, 122.28, 119.00, 118.85, 117.30, 117.25, 116.76, 116.62, 115.63, 115.47, 111.84, 111.68, 86.42, 84.99, 74.59, and 69.59. HRMS-ESI(m/z): Calcd for C35H23F2NNaO2+ [M+H]+: 550.1589, Found: 550.1582.

3.4.21. (S)-6-Bromo-3-hydroxy-3-(phenylethynyl)-1-tritylindolin-2-one 7ga

Silica gel column chromatography (hexane/AcOEt = 3/1) gave 7ga as a light yellow solid, m.p. 230–232 °C. The 1H NMR (400 MHz, CDCl3), δ 7.48-7.15 (m, 21H), 7.15 (dd, J = 8.0 and 1.4 Hz, 1H), 6.35 (d, J = 1.4 Hz, 1H), 3.38 (s, 1H). The 13C NMR (101 MHz, CDCl3) δ 193.74, 159.54, 147.65, 143.86, 141.16, 132.08, 129.22, 129.14, 128.39, 127.96, 127.33, 126.09, 125.10, 122.57, 121.52, 119.30, 87.97, 85.51, 74.65, and 69.28. HRMS-ESI(m/z): Calcd for C35H24BrNNaO2+ [M+H]+: 592.0883, Found: 592.0890.

3.4.22. (S)-4-Chloro-3-hydroxy-3-(phenylethynyl)-1-tritylindolin-2-one 7ha

Silica gel column chromatography (hexane/AcOEt = 5/1) gave 7ha as a light yellow solid, m.p. 212–214 °C. The 1H NMR (400 MHz, CDCl3), δ 7.52 (dd, J = 8.0Hz and 4.0 Hz, 2H), 7.45 (d, J = 8.0 Hz, 6H), 7.35-7.23 (m, 12H), 6.98 (t, J = 8.0 Hz, 1H), 6.89 (t, J = 8.0 Hz, 1H), 6.23 (d, J = 8.0 Hz, 1H), 3.37 (s, 1H). The 13C NMR (101 MHz, CDCl3) δ 174.25, 144.35, 141.27, 132.29, 131.23, 129.56, 129.25, 129.19, 128.38, 127.94, 127.30, 125.69, 124.04, 121.73, 114.82, 86.18, 84.16, 74.81, and 69.63. HRMS-ESI(m/z): Calcd for C35H24ClNNaO2+ [M+Na]+: 548.1388, Found: 548.1384.

4. Conclusions

In summary, a series of new amide-type chiral quaternary ammoniums bearing dehydroabietylamine were prepared by acylation of dehydroabietylamine with bromoacetyl chloride in higher yields using triethyl amine as base and subsequent quaternization reaction with tertial amines and/or tertial diamines. To some extent enantioselectivities were observed when using them as phase-transfer catalyst for the transition-metal catalytic alkynylation of isatin derivatives. Their chiral recognition ability or application in the others’ asymmetric transformation will be examined.

Supplementary Materials

The following are available online at https://www.mdpi.com/article/10.3390/catal11121479/s1, The 1H NMR and 13C NMR of compounds 1, 4, 7; HPLC chart of compounds 7.

Author Contributions

Conceptualization, Q.C.; methodology, K.L.; formal analysis, K.L.; F.Z.; investigation, G.J.; X.S.; writing—original draft preparation, Q.C.; writing—review and editing, Q.C.; F.Z.; supervision, Q.C.; project administration, Q.C.; funding acquisition, Q.C. All authors have read and agreed to the published version of the manuscript.

Funding

This research was funded by the National Natural Science Foundation of China (grant number 32160351 and 31860241), the Key Laboratory of State Forestry and Grassland Adminstration on Highly-Efficient Utilization of Forestry Biomass Resources in Southwest China, Southwest Forestry University (grant number 2019-KF08), and the Key Laboratory of Forest Resources Conservation and Utilization in the Southwest Mountains of China Ministry of Education.

Acknowledgments

We thank Shiqing Dong for experimental assistant.

Conflicts of Interest

The authors declare no conflict of interest.

References

  1. Silvestre, A.J.D.; Gandini, A. Monomers, Polymers and Composites from Renewable Resources; Belgacem, M.N., Gandini, A., Eds.; Elsevier: Amsterdam, The Netherlands, 2008; Chapter 4; ISBN 978-0-08-045316-3. [Google Scholar]
  2. Yang, X.; Li, Q.; Li, Z.; Xu, X.; Liu, H.; Shang, S.; Song, Z. Preparation and characterization of room-temperature vulcanized silicone rubber using acrylpimaric acid-modified aminopropyltriethoxysilane as a crosslinking agent. ACS Sustain. Chem. Eng. 2019, 7, 4964–4974. [Google Scholar] [CrossRef]
  3. Liu, S.; Li, Z.; Diao, K.; Huang, W.; Wang, J.; Deng, W.; Lei, F.; Goodman, B.A. Direct identification of Cu(II) species adsorbed on rosin-derived resins using electron paramagnetic resonance (EPR) spectroscopy. Chemosphere 2018, 210, 789–794. [Google Scholar] [CrossRef] [PubMed]
  4. Liu, S.; Wang, J.; Huang, W.; Tan, X.; Dong, H.; Goodman, B.A.; Du, H.; Lei, F.; Diao, K. Adsorption of phenolic compounds from water by a novel ethylenediamine rosin-based resin: Interaction models and adsorption mechanisms. Chemosphere 2019, 214, 821–829. [Google Scholar] [CrossRef]
  5. Liu, X.; Zhang, R.; Li, T.; Zhu, P.; Zhuang, Q. Novel Fully Biobased Benzoxazines from Rosin: Synthesis and Properties. ACS Sustain. Chem. Eng. 2017, 5, 10682–10692. [Google Scholar] [CrossRef]
  6. Mantzaridis, C.; Brocas, A.-L.; Llevot, A.; Cendejas, G.; Auvergne, R.; Caillol, S.; Carlotti, S.; Cramail, H. Rosin acid oligomers as precursors of DGEBA-free epoxy resins. Green Chem. 2013, 15, 3091–3098. [Google Scholar] [CrossRef]
  7. Wilbon, P.A.; Zheng, Y.; Yao, K.; Tang, C. Renewable Rosin Acid-Degradable Caprolactone Block Copolymers by Atom Transfer Radical Polymerization and Ring-Opening Polymerization. Macromolecules 2010, 43, 8747–8754. [Google Scholar] [CrossRef]
  8. Zhang, L.; Jiang, Y.; Xiong, Z.; Liu, X.; Na, H.; Zhang, R.; Zhu, J. Highly recoverable rosin-based shape memory polyurethanes. J. Mater. Chem. A 2013, 1, 3263–3267. [Google Scholar] [CrossRef]
  9. Li, Q.; Huang, X.; Liu, H.; Shang, S.; Song, Z.; Song, J. Properties Enhancement of Room Temperature Vulcanized Silicone Rubber by Rosin Modified Aminopropyltriethoxysilane as a Cross-linking Agent. ACS Sustain. Chem. Eng. 2017, 5, 10002–10010. [Google Scholar] [CrossRef]
  10. Sacripante, G.G.; Zhou, K.; Farooque, M. Sustainable Polyester Resins Derived from Rosins. Macromolecules 2015, 48, 6876–6881. [Google Scholar] [CrossRef]
  11. Li, R.; Zhang, P.; Liu, T.; Muhunthan, B.; Xin, J.; Zhang, J. Use of Hempseed-Oil-Derived Polyacid and Rosin-Derived Anhydride Acid as Cocuring Agents for Epoxy Materials. ACS Sustain. Chem. Eng. 2018, 6, 4016–4025. [Google Scholar] [CrossRef]
  12. Zheng, Y.; Yao, K.; Lee, J.; Chandler, D.; Wang, J.; Wang, C.; Chu, F.; Tang, C. Well-Defined Renewable Polymers Derived from Gum Rosin. Macromolecules 2010, 43, 5922–5924. [Google Scholar] [CrossRef]
  13. Yan, X.; Zhai, Z.; Song, Z.; Shang, S.; Rao, X. Synthesis and properties of polyester-based polymeric surfactants from diterpenic rosin. Ind. Crop. Prod. 2017, 108, 371–378. [Google Scholar] [CrossRef]
  14. Ding, W.; Wang, S.; Yao, K.; Ganewatta, M.S.; Tang, C.; Robertson, M.L. Physical Behavior of Triblock Copolymer Thermoplastic Elastomers Containing Sustainable Rosin-Derived Polymethacrylate End Blocks. ACS Sustain. Chem. Eng. 2017, 5, 11470–11480. [Google Scholar] [CrossRef]
  15. Zhai, Z.; Ye, S.; Yan, X.; Song, Z.; Shang, S.; Rao, X.; Song, J. pH-Responsive Wormlike Micelles Formed by an Anionic Surfactant Derived from Rosin. J. Agric. Food Chem. 2020, 68, 10063–10070. [Google Scholar] [CrossRef] [PubMed]
  16. Yan, X.; Zhai, Z.; Xu, J.; Song, Z.; Shang, S.; Rao, X. CO2-Responsive Pickering Emulsions Stabilized by a Bio-based Rigid Surfactant with Nanosilica. J. Agric. Food Chem. 2018, 66, 10769–10776. [Google Scholar] [CrossRef]
  17. Zhai, Z.; Xu, J.; Yan, X.; Song, Z.; Shang, S.; Rao, X. pH-responsive foams based on a transition between a bola surfactant and a traditional surfactant. J. Mol. Liq. 2020, 298, 111968. [Google Scholar] [CrossRef]
  18. Wang, D.; Chen, H.; Song, B.; Yan, T.; Zhai, Z.; Pei, X.; Cui, Z. Supramolecular Hydrogels with Chiral Nanofibril Structures Formed from β-Cyclodextrin and a Rosin-Based Amino Acid Surfactant. J. Agric. Food Chem. 2020, 68, 10056–10062. [Google Scholar] [CrossRef] [PubMed]
  19. Yan, T.; Song, B.; Du, D.; Cui, Z.; Pei, X. Rosin-based chiral wormlike Micelles: Rheological behavior and its application in preparing ultrasmall gold nanoparticles. J. Colloid Interface Sci. 2020, 579, 61–70. [Google Scholar] [CrossRef] [PubMed]
  20. Chen, J.; Song, B.; Pei, X.; Cui, Z.; Xie, D. Rheological Behavior of Environmentally Friendly Viscoelastic Solutions Formed by a Rosin-Based Anionic Surfactant. J. Agric. Food Chem. 2019, 67, 2004–2011. [Google Scholar] [CrossRef]
  21. Klejdysz, T.; Łęgosz, B.; Czuryszkiewicz, D.; Czerniak, K.; Pernak, J. Biobased Ionic Liquids with Abietate Anion. ACS Sustain. Chem. Eng. 2016, 4, 6543–6550. [Google Scholar] [CrossRef]
  22. Gao, Y.; Li, L.; Chen, H.; Li, J.; Song, Z.; Shang, S.; Song, J.; Wang, Z.; Xiao, G. High value-added application of rosin as a potential renewable source for the synthesis of acrylopimaric acid-based botanical herbicides. Ind. Crop. Prod. 2015, 78, 131–140. [Google Scholar] [CrossRef]
  23. Gao, Y.; Li, J.; Song, Z.; Song, J.; Shang, S.; Xiao, G.; Wang, Z.; Rao, X. Turning renewable resources into value-added products: Development of rosin-based insecticide candidates. Ind. Crop. Prod. 2015, 76, 660–671. [Google Scholar] [CrossRef]
  24. Wang, H.; Nguyen, T.T.H.; Li, S.; Liang, T.; Zhang, Y.; Li, J. Quantitative structure–activity relationship of antifungal activity of rosin derivatives. Bioorg. Med. Chem. Lett. 2015, 25, 347–354. [Google Scholar] [CrossRef] [PubMed]
  25. Yao, G.; Ye, M.; Huang, R.; Li, Y.; Zhu, Y.; Pan, Y.; Liao, Z.-X.; Wang, H. Synthesis and antitumor activity evaluation of maleopimaric acid N-aryl imide atropisomers. Bioorg. Med. Chem. Lett. 2013, 23, 6755–6758. [Google Scholar] [CrossRef]
  26. Xing, Y.; Zhang, W.; Song, J.; Zhang, Y.; Jiang, X.; Wang, R. Anticancer effects of a novel class rosin-derivatives with different mechanisms. Bioorg. Med. Chem. Lett. 2013, 23, 3868–3872. [Google Scholar] [CrossRef] [PubMed]
  27. Gu, W.; Qiao, C.; Wang, S.-F.; Hao, Y.; Miao, T.-T. Synthesis and biological evaluation of novel N-substituted 1H-dibenzo[a,c]carbazole derivatives of dehydroabietic acid as potential antimicrobial agents. Bioorg. Med. Chem. Lett. 2014, 24, 328–331. [Google Scholar] [CrossRef]
  28. Gowda, R.; Madhunapantula, S.V.; Kuzu, O.F.; Sharma, A.; Robertson, G.P. Targeting Multiple Key Signaling Pathways in Melanoma Using Leelamine. Mol. Cancer Ther. 2014, 13, 1679–1689. [Google Scholar] [CrossRef] [PubMed] [Green Version]
  29. Kuzu, O.F.; Gowda, R.; Sharma, A.; Robertson, G.P. Leelamine Mediates Cancer Cell Death through Inhibition of Intracellular Cholesterol Transport. Mol. Cancer Ther. 2014, 13, 1690–1703. [Google Scholar] [CrossRef] [Green Version]
  30. Gowda, R.; Madhunapantula, S.V.; Sharma, A.; Kuzu, O.F.; Robertson, G.P. Nanolipolee-007, a Novel Nanoparticle-Based Drug Containing Leelamine for the Treatment of Melanoma. Mol. Cancer Ther. 2014, 13, 2328–2340. [Google Scholar] [CrossRef] [Green Version]
  31. Singh, K.B.; Ji, X.; Singh, S.V. Therapeutic Potential of Leelamine, a Novel Inhibitor of Androgen Receptor and Castration-Resistant Prostate Cancer. Mol. Cancer Ther. 2018, 17, 2079–2090. [Google Scholar] [CrossRef] [Green Version]
  32. Li, C.; Liu, X.; Zhu, J.; Zhang, C.; Guo, J. Synthesis, Characterization of a Rosin-based Epoxy Monomer and its Comparison with a Petroleum-based Counterpart. J. Macromol. Sci. A 2013, 50, 321–329. [Google Scholar] [CrossRef]
  33. Wang, P.; Chen, S.X.; Zhao, Z.D.; Wang, Z.; Fan, G. Synthesis of ordered porous SiO2 with pores on the border between the micropore and mesopore regions using rosin-based quaternary ammonium salt. RSC Adv. 2015, 5, 11223–11228. [Google Scholar] [CrossRef]
  34. Song, F.; Wang, P.; Chen, S.; Wang, Z.; Fan, G. Ordered lamellar supermicroporous titania templating by rosin-derived quaternary ammonium salt. PLoS ONE 2017, 12, e0180178. [Google Scholar] [CrossRef] [Green Version]
  35. Wang, P.; Zhao, Z.D.; He, L.Z.; Bi, L.W.; Chen, Y.X. Fabrication of Mesoporous ZrO2 by Using Rosin-Based Quaternary Ammonium Salt. Adv. Mater. Res. 2011, 239–242, 3257–3261. [Google Scholar] [CrossRef]
  36. Foreiter, M.B.; Gunaratne, H.Q.N.; Nockemann, P.; Seddon, K.R.; Stevenson, P.J.; Wassell, D.F. Chiral thiouronium salts: Synthesis, characterisation and application in NMR enantio-discrimination of chiral oxoanions. New J. Chem. 2013, 37, 515–533. [Google Scholar] [CrossRef] [Green Version]
  37. Narayanaperumal, S.; Rivera, D.G.; Silva, R.C.; Paixão, M.W. Terpene-Derived Bifunctional Thioureas in Asymmetric Organocatalysis. ChemCatChem 2013, 5, 2756–2773. [Google Scholar] [CrossRef]
  38. Jiang, X.; Fu, D.; Zhang, G.; Cao, Y.; Liu, L.; Song, J.; Wang, R. Highly diastereo- and enantioselective Mannich reaction of lactones with N-Boc-aldimines catalyzed by bifunctional rosin-derived amine thiourea catalysts. Chem. Commun. 2010, 46, 4294–4296. [Google Scholar] [CrossRef]
  39. Jiang, X.; Zhang, Y.; Chan, A.S.C.; Wang, R. Highly Enantioselective Synthesis of γ-Nitro Heteroaromatic Ketones in a Doubly Stereocontrolled Manner Catalyzed by Bifunctional Thiourea Catalysts Based on Dehydroabietic Amine: A Doubly Stereocontrolled Approach to Pyrrolidine Carboxylic Acids. Org. Lett. 2009, 11, 153–156. [Google Scholar] [CrossRef] [PubMed]
  40. Jiang, X.; Cao, Y.; Wang, Y.; Liu, L.; Shen, F.; Wang, R. A Unique Approach to the Concise Synthesis of Highly Optically Active Spirooxazolines and the Discovery of a More Potent Oxindole-Type Phytoalexin Analogue. J. Am. Chem. Soc. 2010, 132, 15328–15333. [Google Scholar] [CrossRef]
  41. Jiang, X.; Zhang, G.; Fu, D.; Cao, Y.; Shen, F.; Wang, R. Direct Organocatalytic Asymmetric Aldol Reaction of α-Isothiocyanato Imides to α-Ketoesters under Low Ligand Loading: A Doubly Stereocontrolled Approach to Cyclic Thiocarbamates Bearing Chiral Quaternary Stereocenters. Org. Lett. 2010, 12, 1544–1547. [Google Scholar] [CrossRef]
  42. Cao, Y.; Jiang, X.; Liu, L.; Shen, F.; Zhang, F.; Wang, R. Enantioselective Michael/Cyclization Reaction Sequence: Scaffold-Inspired Synthesis of Spirooxindoles with Multiple Stereocenters. Angew. Chem. Int. Ed. 2011, 50, 9124–9127. [Google Scholar] [CrossRef]
  43. Zhang, G.; Zhang, Y.; Jiang, X.; Yan, W.; Wang, R. Highly Enantioslective Synthesis of Multisubstituted Polyfunctional Dihydropyrrole via an Organocatalytic Tandem Michael/Cyclization Sequence. Org. Lett. 2011, 13, 3806–3809. [Google Scholar] [CrossRef] [PubMed]
  44. Jiang, X.; Wu, L.; Xing, Y.; Wang, L.; Wang, S.; Chen, Z.; Wang, R. Highly enantioselective Friedel–Crafts alkylation reaction catalyzed by rosin-derived tertiary amine–thiourea: Synthesis of modified chromanes with anticancer potency. Chem. Commun. 2012, 48, 446–448. [Google Scholar] [CrossRef] [PubMed]
  45. Lin, N.; Long, X.W.; Chen, Q.; Zhu, W.R.; Wang, B.C.; Chen, K.B.; Jiang, C.W.; Weng, J.; Lu, G. Highly efficient construction of chiral dispirocyclic oxindole/thiobutyrolactam/chromanone complexes through Michael/cyclization cascade reactions with a rosin-based squaramide catalyst. Tetrahedron 2018, 74, 3734–3741. [Google Scholar] [CrossRef]
  46. Frantz, D.E.; Fässler, R.; Tomooka, C.S.; Carreira, E.M. The Discovery of Novel Reactivity in the Development of C−C Bond-Forming Reactions:  In Situ Generation of Zinc Acetylides with ZnII/R3N. Acc. Chem. Res. 2000, 33, 373–381. [Google Scholar] [CrossRef] [PubMed]
  47. Trost, B.M.; Weiss, A.H. The Enantioselective Addition of Alkyne Nucleophiles to Carbonyl Groups. Adv. Synth. Catal. 2009, 351, 963–983. [Google Scholar] [CrossRef]
  48. Turlington, M.; Pu, L. Asymmetric Alkyne Addition to Aldehydes Catalyzed by BINOL and Its Derivatives. SynLett 2012, 5, 649–684. [Google Scholar] [CrossRef]
  49. Frantz, D.E.; Fässler, R.; Carreira, E.M. For selective examples for the addition of alkynes to aldehydes: Facile Enantioselective Synthesis of Propargylic Alcohols by Direct Addition of Terminal Alkynes to Aldehydes. J. Am. Chem. Soc. 2000, 122, 1806–1807. [Google Scholar] [CrossRef]
  50. Anand, N.K.; Carreira, E.M. A Simple, Mild, Catalytic, Enantioselective Addition of Terminal Acetylenes to Aldehydes. J. Am. Chem. Soc. 2001, 123, 9687–9688. [Google Scholar] [CrossRef]
  51. El-Sayed, E.; Anand, N.K.; Carreira, E.M. Asymmetric Synthesis of γ-Hydroxy α,β-Unsaturated Aldehydes via Enantioselective Direct Addition of Propargyl Acetate to Aldehydes. Org. Lett. 2001, 3, 3017–3020. [Google Scholar] [CrossRef]
  52. Gao, G.; Wang, Q.; Yu, X.-Q.; Xie, R.-G.; Pu, L. Highly Enantioselective Synthesis of γ-Hydroxy-α,β-acetylenic Esters by Asymmetric Alkyne Addition to Aldehydes. Angew. Chem. Int. Ed. 2006, 45, 122–125. [Google Scholar] [CrossRef]
  53. Gao, G.; Moore, D.; Xie, R.-G.; Pu, L. Highly Enantioselective Phenylacetylene Additions to Both Aliphatic and Aromatic Aldehydes. Org. Lett. 2002, 4, 4143–4146. [Google Scholar] [CrossRef] [PubMed]
  54. Trost, B.M.; Weiss, A.H.; Jacobi von Wangelin, A. Dinuclear Zn-Catalyzed Asymmetric Alkynylation of Unsaturated Aldehydes. J. Am. Chem. Soc. 2006, 128, 8–9. [Google Scholar] [CrossRef] [Green Version]
  55. Yamashita, M.; Yamada, K.; Tomioka, K. Catalytic Asymmetric Addition of Terminal Alkynes to Aldehydes Mediated by (1R,2R)-2-(Dimethylamino)- 1,2-diphenylethanol. Adv. Synth. Catal. 2005, 347, 1649–1652. [Google Scholar] [CrossRef]
  56. Emmerson, D.P.G.; Hems, W.P.; Davis, B. Carbohydrate-Derived Amino-Alcohol Ligands for Asymmetric Alkynylation of Aldehydes. Org. Lett. 2006, 8, 207–210. [Google Scholar] [CrossRef]
  57. Dahmen, S. Enantioselective Alkynylation of Aldehydes Catalyzed by [2.2]Paracyclophane-Based Ligands. Org. Lett. 2004, 6, 2113–2116. [Google Scholar] [CrossRef] [PubMed]
  58. Xu, Z.; Wang, R.; Xu, J.; Da, C.; Yan, W.; Chen, C. Highly Enantioselective Addition of Phenylacetylene to Aldehydes Catalyzed by a β-Sulfonamide Alcohol–Titanium Complex. Angew. Chem. Int. Ed. 2003, 42, 5747–5749. [Google Scholar] [CrossRef] [PubMed]
  59. Boyall, D.; Frantz, D.F.; Carreira, E.M. Efficient Enantioselective Additions of Terminal Alkynes and Aldehydes under Operationally Convenient Conditions. Org. Lett. 2002, 4, 2605–2606. [Google Scholar] [CrossRef]
  60. Asano, Y.; Hara, K.; Ito, H.; Sawamura, M. Enantioselective Addition of Terminal Alkynes to Aldehydes Catalyzed by a Cu(I)−TRAP Complex. Org. Lett. 2007, 9, 3901–3904. [Google Scholar] [CrossRef]
  61. Molina, Y.S.; Ruchti, J.; Carreira, E.M. Enantioselective Addition of Alkynes to α,α-Dichlorinated Aldehydes. Org. Lett. 2017, 19, 743–745. [Google Scholar] [CrossRef]
  62. Lin, L.; Jiang, X.; Liu, W.; Qiu, L.; Xu, Z.; Xu, J.; Chan, A.S.C.; Wang, R. Highly Enantioselective Synthesis of γ-Hydroxy-α,β-acetylenic Esters Catalyzed by a β-Sulfonamide Alcohol. Org. Lett. 2007, 9, 2329–2332. [Google Scholar] [CrossRef] [PubMed]
  63. Luo, S.; Zhang, X.; Zheng, Y.; Harms, K.; Zhang, L.; Meggers, E. Enantioselective Alkynylation of Aromatic Aldehydes Catalyzed by a Sterically Highly Demanding Chiral-at-Rhodium Lewis Acid. J. Org. Chem. 2017, 82, 8995–9005. [Google Scholar] [CrossRef]
  64. Li, Z.-B.; Liu, T.-D.; Pu, L. Chiral Macrocycle-Catalyzed Highly Enantioselective Phenylacetylene Addition to Aliphatic and Vinyl Aldehydes. J. Org. Chem. 2007, 72, 4340–4343. [Google Scholar] [CrossRef]
  65. Wolf, C.; Liu, S. Bisoxazolidine-Catalyzed Enantioselective Alkynylation of Aldehydes. J. Am. Chem. Soc. 2006, 128, 10996–10997. [Google Scholar] [CrossRef]
  66. Takita, R.; Yakura, K.; Ohshima, T.; Shibasaki, M. Asymmetric Alkynylation of Aldehydes Catalyzed by an In(III)/BINOL Complex. J. Am. Chem. Soc. 2005, 127, 13760–13761. [Google Scholar] [CrossRef]
  67. Li, Z.; Pu, L. BINOL−Salen-Catalyzed Highly Enantioselective Alkyne Additions to Aromatic Aldehydes. Org. Lett. 2004, 6, 1065–1068. [Google Scholar] [CrossRef]
  68. FPark, D.; Jette, C.I.; Kim, J.; Jung, W.-O.; Lee, Y.; Park, J.; Kang, S.; Han, M.S.; Stoltz, B.M.; Hong, S. Enantioselective Alkynylation of Trifluoromethyl Ketones Catalyzed by Cation-Binding Salen Nickel Complexes. Angew. Chem. Int. Ed. 2020, 59, 775–779. [Google Scholar] [CrossRef] [Green Version]
  69. Chinkov, N.; Warm, A.; Carreira, E.M. Asymmetric Autocatalysis Enables an Improved Synthesis of Efavirenz. Angew. Chem. Int. Ed. 2011, 50, 2957–2961. [Google Scholar] [CrossRef]
  70. Zhou, Y.; Wang, R.; Xu, Z.; Yan, W.; Liu, L.; Kang, Y.; Han, Z. Highly Enantioselective Phenylacetylene Additions to Ketones Catalyzed by (S)-BINOL−Ti Complex. Org. Lett. 2004, 6, 4147–4149. [Google Scholar] [CrossRef] [PubMed]
  71. Cozzi, P.G. Enantioselective Alkynylation of Ketones Catalyzed by Zn(Salen) Complexes. Angew. Chem. Int. Ed. 2003, 42, 2895–2898. [Google Scholar] [CrossRef] [PubMed]
  72. Chen, C.; Hong, L.; Xu, Z.-Q.; Liu, L.; Wang, R. Low Ligand Loading, Highly Enantioselective Addition of Phenylacetylene to Aromatic Ketones Catalyzed by Schiff-Base Amino Alcohols. Org. Lett. 2006, 8, 2277–2280. [Google Scholar] [CrossRef]
  73. Motoki, R.; Kanai, M.; Shibasaki, M. Copper(I) Alkoxide-Catalyzed Alkynylation of Trifluoromethyl Ketones. Org. Lett. 2007, 9, 2997–3000. [Google Scholar] [CrossRef]
  74. Liu, L.; Wang, R.; Kang, Y.-F.; Chen, C.; Xu, Z.-Q.; Zhou, Y.-F.; Ni, M.; Cai, H.-Q.; Gong, M.-Z. Highly Enantioselective Phenylacetylene Addition to Aromatic Ketones Catalyzed by Cinchona Alkaloid−Aluminum Complexes. J. Org. Chem. 2005, 70, 1084–1086. [Google Scholar] [CrossRef]
  75. Lu, G.; Li, X.; Jia, X.; Chan, W.L.; Chan, A.S.C. Enantioselective Alkynylation of Aromatic Ketones Catalyzed by Chiral Camphorsulfonamide Ligands. Angew. Chem. Int. Ed. 2003, 42, 5057–5058. [Google Scholar] [CrossRef] [PubMed]
  76. Paria, S.; Lee, H.-J.; Maruoka, K. Enantioselective Alkynylation of Isatin Derivatives Using a Chiral Phase-Transfer/Transition-Metal Hybrid Catalyst System. ACS Catal. 2019, 9, 2395–2399. [Google Scholar] [CrossRef]
  77. Chen, Q.; Tang, Y.; Huang, T.; Liu, X.; Lin, L.; Feng, X. Copper/Guanidine-Catalyzed Asymmetric Alkynylation of Isatins. Angew. Chem. Int. Ed. 2016, 55, 5286–5289. [Google Scholar] [CrossRef]
  78. Xu, N.; Gu, D.-W.; Zi, J.; Wu, X.-Y.; Guo, X.-X. Enantioselective Synthesis of 3-Alkynyl-3-hydroxyindolin-2-ones by Copper-Catalyzed Asymmetric Addition of Terminal Alkynes to Isatins. Org. Lett. 2016, 18, 2439–2442. [Google Scholar] [CrossRef] [PubMed]
  79. Zavesky, B.P.; Johnson, J.S. Direct Zinc(II)-Catalyzed Enantioconvergent Additions of Terminal Alkynes to α-Keto Esters. Angew. Chem. Int. Ed. 2017, 56, 8805–8808. [Google Scholar] [CrossRef]
  80. Jiang, B.; Chen, Z.; Tang, X. Highly Enantioselective Alkynylation of α-Keto Ester:  An Efficient Method for Constructing a Chiral Tertiary Carbon Center. Org. Lett. 2002, 4, 3451–3453. [Google Scholar] [CrossRef]
  81. Lu, J.; Luo, L.-S.; Sha, F.; Li, Q.; Wu, X.-Y. Copper-catalyzed enantioselective alkynylation of pyrazole-4,5-diones with terminal alkynes. Chem. Commun. 2019, 55, 11603–11606. [Google Scholar] [CrossRef]
  82. Ohshima, T.; Kawabata, T.; Takeuchi, Y.; Kakinuma, T.; Iwasaki, T.; Yonezawa, T.; Murakami, H.; Nishiyama, H.; Mashima, K. C1-Symmetric Rh/Phebox-Catalyzed Asymmetric Alkynylation of α-Ketoesters. Angew. Chem. Int. Ed. 2011, 50, 6296–6300. [Google Scholar] [CrossRef]
  83. Parmar, D.; Sugiono, E.; Raja, S.; Rueping, M. Complete Field Guide to Asymmetric BINOL-Phosphate Derived Brønsted Acid and Metal Catalysis: History and Classification by Mode of Activation; Brønsted Acidity, Hydrogen Bonding, Ion Pairing, and Metal Phosphates. Chem. Rev. 2014, 114, 9047–9153. [Google Scholar] [CrossRef]
  84. Mahlau, M.; List, B. Asymmetric counteranion-directed catalysis: Concept, definition, and applications. Angew. Chem. Int. Ed. 2013, 52, 518–533. [Google Scholar] [CrossRef]
  85. Brak, K.; Jacobsen, E.N. Asymmetric Ion-Pairing Catalysis. Angew. Chem. Int. Ed. 2013, 52, 534–561. [Google Scholar] [CrossRef] [Green Version]
  86. Hashmi, A.S.K. Raising the gold standard. Nature 2007, 449, 292–293. [Google Scholar] [CrossRef]
  87. Dorta, R.; Shimon, L.; David Milstein, D. Rhodium complexes with chiral counterions: Achiral catalysts in chiral matrices. J. Organomet. Chem. 2004, 689, 751–758. [Google Scholar] [CrossRef]
  88. Hamilton, G.L.; Kang, E.J.; Mba, M.; Toste, F.D. A Powerful Chiral Counterion Strategy for Asymmetric Transition Metal Catalysis. Science 2007, 317, 496–499. [Google Scholar] [CrossRef] [Green Version]
  89. Rueping, M.; Antonchick, A.P.; Brinkmann, C. Dual Catalysis: A Combined Enantioselective Brønsted Acid and Metal-Catalyzed Reaction—Metal Catalysis with Chiral Counterions. Angew. Chem. Int. Ed. 2007, 46, 6903–6906. [Google Scholar] [CrossRef] [PubMed]
  90. Rauniyar, V.; Lackner, A.D.; Hamilton, G.L.; Toste, F.D. Asymmetric Electrophilic Fluorination Using an Anionic Chiral Phase-Transfer Catalyst. Science 2011, 334, 1681–1684. [Google Scholar] [CrossRef] [PubMed]
  91. Hamilton, G.L.; Kanai, T.; Toste, F.D. Chiral Anion-Mediated Asymmetric Ring Opening of meso-Aziridinium and Episulfonium Ions. J. Am. Chem. Soc. 2008, 130, 14984–14986. [Google Scholar] [CrossRef] [Green Version]
  92. Li, C.; Wang, C.; Villa-Marcos, B.; Xiao, J. Chiral Counteranion-Aided Asymmetric Hydrogenation of Acyclic Imines. J. Am. Chem. Soc. 2008, 130, 14450–14451. [Google Scholar] [CrossRef]
  93. Aikawa, K.; Kojima, M.; Mikami, K. Axial Chirality Control of Gold(biphep) Complexes by Chiral Anions: Application to Asymmetric Catalysis. Angew. Chem. Int. Ed. 2009, 48, 6073–6077. [Google Scholar] [CrossRef]
  94. Li, C.; Villa-Marcos, B.; Xiao, J. Metal−Brønsted Acid Cooperative Catalysis for Asymmetric Reductive Amination. J. Am. Chem. Soc. 2009, 131, 6967–6969. [Google Scholar] [CrossRef] [PubMed]
  95. Lu, Y.; Johnstone, T.C.; Arndtsen, B.A. Hydrogen-Bonding Asymmetric Metal Catalysis with α-Amino Acids: A Simple and Tunable Approach to High Enantioinduction. J. Am. Chem. Soc. 2009, 131, 11284–11285. [Google Scholar] [CrossRef] [PubMed]
  96. Zhu, Y.; He, W.; Wang, W.; Pitsch, C.E.; Wang, X.; Wang, X. Enantioselective Tandem Cyclization of Alkyne-Tethered Indoles Using Cooperative Silver(I)/Chiral Phosphoric Acid Catalysis. Angew. Chem. Int. Ed. 2017, 56, 12206–12209. [Google Scholar] [CrossRef] [PubMed]
  97. Ye, X.; Tan, C.-H. Enantioselective transition metal catalysis directed by chiral cations. Chem. Sci. 2021, 12, 533–539. [Google Scholar] [CrossRef]
  98. Genov, G.R.; James, L.; Douthwaite, J.L.; Lahdenperä, A.S.K.; Gibson, D.C.; Phipps, R.J. Enantioselective remote C–H activation directed by a chiral cation. Science 2020, 367, 1246–1251. [Google Scholar] [CrossRef] [Green Version]
  99. Chen, Q.; Luo, M.; Guo, F.; Liang, K.; Gao, G. An Addition of Terminal Alkynes to Phthalazin-2-Ium Bromide Catalyzed by Copper. Adv. Synth. Catal. 2020, 362, 2332–2336. [Google Scholar] [CrossRef]
  100. Chen, Q.; Li, L.; Zhou, G.; Ma, X.; Zhang, L.; Guo, F.; Luo, Y.; Xia, W. Chiral Phosphorus–Olefin Ligands for the RhI-Catalyzed Asymmetric Addition of Aryl Boronic Acids to Electron-Deficient Olefins. Chem. Asian J. 2016, 11, 1518–1522. [Google Scholar] [CrossRef]
  101. Hashmi, A.S.K. Silver in Organic Chemistry; Harmata, M., Ed.; John Wiley and Sons, Inc.: Hoboken, NJ, USA, 2010; pp. 357–379, Chapter 12; ISBN 9780470466117. [Google Scholar]
Catalysts 11 01479 g001 550
Figure 1. Structure of natural abietic acid and commercially available dehydroabietylamine.
Figure 1. Structure of natural abietic acid and commercially available dehydroabietylamine.
Catalysts 11 01479 g001
Catalysts 11 01479 g002 550
Figure 2. Structure of quaternary ammonium salt derived from commercially available dehydroabietylamine.
Figure 2. Structure of quaternary ammonium salt derived from commercially available dehydroabietylamine.
Catalysts 11 01479 g002
Catalysts 11 01479 sch001 550
Scheme 1. Synthesis of chiral dehydroabietylamine quaternary ammonium derivatives.
Scheme 1. Synthesis of chiral dehydroabietylamine quaternary ammonium derivatives.
Catalysts 11 01479 sch001
Catalysts 11 01479 sch002a 550Catalysts 11 01479 sch002b 550
Scheme 2. Substrate scope of the alkynylation reaction (a–c). (a) Reaction condition: Isatin 5 (0.2 mmol), arylacetylene 6 (0.4 mmol), base (0.4 mmol), 5 mol % of AgOAc, 5.5 mol% 1e, solvent (2 mL) at given temperature for 12 h. (b) Isolated yield. (c) The ee was determined by chiral HPLC analysis.
Scheme 2. Substrate scope of the alkynylation reaction (a–c). (a) Reaction condition: Isatin 5 (0.2 mmol), arylacetylene 6 (0.4 mmol), base (0.4 mmol), 5 mol % of AgOAc, 5.5 mol% 1e, solvent (2 mL) at given temperature for 12 h. (b) Isolated yield. (c) The ee was determined by chiral HPLC analysis.
Catalysts 11 01479 sch002aCatalysts 11 01479 sch002b
Catalysts 11 01479 sch003 550
Scheme 3. Proposed mechanism for Ag−catalysed alkynylation in the presence of chiral quaternary ammoniums.
Scheme 3. Proposed mechanism for Ag−catalysed alkynylation in the presence of chiral quaternary ammoniums.
Catalysts 11 01479 sch003
Table
Table 1. Optimization of the reaction conditions (a).
Table 1. Optimization of the reaction conditions (a).
Catalysts 11 01479 i001
Entry5M Cat.
(5 mol%)		PTC
(5.5%)		BaseSolventTime (h)T (°C)Yield (%) (b)Ee (%) (c)
15aAgOAc1aK2CO3THF1250680
25aAgOAc1bK2CO3THF1250620
35aAgOAc1cK2CO3THF1250480
45aAgOAc1dK2CO3THF1250732
55aAgOAc1eK2CO3THF1250793
65aAgOAc1eK2CO3toluene1250654
75aAgTFA1eK2CO3THF1250702
85aAgOTf1eK2CO3THF1250684
95aCuOTf1eK2CO3THF1250652
105aCuI1eK2CO3THF1250561
115aAgOAc1eK2CO3THF12rttrace
125bAgOAc1eK2CO3THF1250712
135bAgOAc1eK2CO3toluene1250686
145cAgOAc1eK2CO3THF1250trace
155cAgOAc1eK2CO3toluene1250trace
165cAgOAc1eK2CO3DMSO1250trace
175cAgOAc1eK2CO3CH3CN1250705
185cAgOAc1eK2CO3DMF1250383
195cAgOAc1eK2CO3CH2Cl21235282
205cAgOAc1eK2CO3dioxane1250231
215cAgOAc1eK2CO3MeOH1250trace
225cAgOAc1eK2CO3Mesitylene1260689
235cAgOAc1eNEt3Mesitylene1260413
245cAgOAc1eNa2CO3Mesitylene1260658
255cAgOAc1eLi2CO3Mesitylene1260626
265cAgOAc1eCs2CO3Mesitylene1260583
275c 1eCs2CO3Mesitylene1260trace
(a) Reaction condition: Isatin 5 (0.2 mmol), phenylacetylene 6a (0.4 mmol), base (0.4 mmol), 5 mol % of metal catalyst, 5.5 mol% PTC, solvent (2 mL) at given temperature for 12 h. (b) Isolated yield. (c) The ee was determined by chiral HPLC analysis.
Publisher’s Note: MDPI stays neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Share and Cite

MDPI and ACS Style

Jiang, G.; Sun, X.; Zhou, F.; Liang, K.; Chen, Q. Chiral Quaternary Ammoniums Derived from Dehydroabietylamine: Synthesis and Application to Alkynylation of Isatin Derivatives Catalyzed by Silver. Catalysts 2021, 11, 1479. https://doi.org/10.3390/catal11121479

AMA Style

Jiang G, Sun X, Zhou F, Liang K, Chen Q. Chiral Quaternary Ammoniums Derived from Dehydroabietylamine: Synthesis and Application to Alkynylation of Isatin Derivatives Catalyzed by Silver. Catalysts. 2021; 11(12):1479. https://doi.org/10.3390/catal11121479

Chicago/Turabian Style

Jiang, Guanyu, Xinduo Sun, Fanrui Zhou, Kun Liang, and Qian Chen. 2021. "Chiral Quaternary Ammoniums Derived from Dehydroabietylamine: Synthesis and Application to Alkynylation of Isatin Derivatives Catalyzed by Silver" Catalysts 11, no. 12: 1479. https://doi.org/10.3390/catal11121479

Note that from the first issue of 2016, this journal uses article numbers instead of page numbers. See further details here.

Article Metrics

Back to TopTop