Opportunities Offered by Chiral η6-Arene/N-Arylsulfonyl-diamine-RuII Catalysts in the Asymmetric Transfer Hydrogenation of Ketones and Imines
Abstract
:1. Introduction
2. Original η6-Arene/N-sulfonyldiamine-RuII Catalysts
2.1. The Pioneering Works on η6-Arene/N-sulfonyldiamine-RuII Catalysts
2.2. ATH Catalyzed by 1 in Water
2.3. Attempts to Immobilize Unmodified Complexes 1
2.4. ATH Catalyzed by 1 in Ionic Liquids
3. Modifications of the η6-Arene/N-sulfonyldiamine-RuII Complexes
3.1. Modifications of 1 Facilitating ATH in Aqueous Media
3.2. ATH Conducted on Immobilized Catalysts Derived from 1
3.3. ATH Conducted on Dendrimeric Catalysts Derived from 1
3.4. ATH Conducted in Ionic Liquids Using Modified Catalysts 1
3.5. Biomimetic Modifications of 1
4. Mechanistic Considerations
4.1. ATH of Ketones Catalyzed by 1 in the Presence of Isopropanol and a Strong Base
4.2. ATH Catalyzed by 1 in the Presence of the HCOOH/Triethylamine Azeotrope
4.3. Mechanism of ATH Catalyzed by 1 in Water
4.4. ATH of Imines Catalyzed by 1 in the Presence of the HCOOH/Triethylamine Azeotrope
4.5. Molecular Modelling
5. Conclusions
Acknowledgements
References and Notes
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Sample Availability: Samples of the compounds are not available from the authors. |
Entry | Catalyst | Substrate | Product | S/C [a]; Time; Temp.; Conversion (%) | % ee (config) [b] | Ref. [c] |
---|---|---|---|---|---|---|
1 | (R,R)-1a | 200; 0.5 h; 28 °C; 100 | 97 (R) | [26] | ||
2 | (S,S)-1b | 200; 3 h; 28 °C; 99 | 95 (R) | [53] | ||
3 | (R,R)-1b [d] | 100; 20 h; 28 °C; > 99 | 97.7 (R) | [57] | ||
4 | (S,S)-1c | 200; 20 h; 28 °C; 99 | 98 (S) | [54] | ||
5 | (S,S)-1c [d] | 200; 15 h; r.t.; 99 | 97 (S) | [52] | ||
6 | (R,R)-1d | 200; 7 h; 28 °C; 99 | 96 (R) | [26] | ||
7 | (S,S)-1e | 200; 8 h; 28 °C; 99 | 84 (R) | [53] | ||
8 | (R,R)-1f | 200; 12 h; 28 °C; 99 | 92 (S) | [53] |
Entry | Catalyst config. | Solution | Time; Temp.; Conversion (%) | % ee (config) [b] | Ref. [c] |
---|---|---|---|---|---|
1 | (R,R) | H2O/HCOONa | 2 h; 40 °C; >99 | 94 % (R) | [59] |
2 | (R,R) | HCOOH/Et3N | 12 h; 40°C; 98 | 97 % (R) | [59] |
3 | (R,R) | H2O/HCOONa/CTAB [d] | 4 h; 28 °C; >99 | 95 % (R) | [62] |
4 | (S,S) | H2O/HCOONa/PEG | 15 h; 40 °C; >99 | 96 % (S) | [63] |
Entry | Catalyst config. | Substrate | Solution | S/C [a]; Time; Temp.; Conversion (%) | % ee (config) [b] | Ref. [c] |
---|---|---|---|---|---|---|
1 | (S,S) [d] | DHIQ [e] | HCOOH/Et3N; acetonitrile | 200; 7 h; r.t.; 99 | 89% (R) | [67] |
2 | (S,S) [f] | acetophenone | H2O/HCOONa; Et4N+Br | 100; 5 h; 30 °C; >99 | 93% (S) | [68] |
Entry | Ligand | Substrate | Solution | Time; Temp.; Conversion (%) | % ee (config) [b] | Ref. [c] |
---|---|---|---|---|---|---|
1 | (S,S)-2 | acetophenone | H2O/i-PrOH/t-BuOK | 48 h; 22 °C; 96 | 94 (S) | [91] |
2 | (R,R)-3 | acetophenone | H2O/HCOONa; SDS [d] | 24 h; 40 °C; >99 | 95 (R) | [93] |
3 | (R,R)-3 | α-bromo-acetophenone | H2O/CH2Cl2/HCOONa; SDS | 24 h; 28 °C; 87 (isol. yield) | 94 | [93] |
4 | (R,R)-3 | DHIQ [e] | H2O/HCOONa; CTAB [f] | 10 h; 28 °C; 97 (isol. yield) | 95 (S) | [94] |
5 | (S,S)-4 | acetophenone | H2O/HCOONa | 0.5 h; 28 °C; 33 | 95 (S) | [95] |
6 | (R,R)-5c | acetophenone | H2O/HCOONa | 2 h; 40 °C; 100 | 94 (R) | [96] |
7 | (R,R)-5d | acetophenone | H2O/HCOONa | 2 h; 40 °C; 100 | 92 (R) | [96] |
Entry | Ligand | Substrate | Solution | S/C [b]; Time; Temp.; Conversion (%) | % ee (config) [c] | Ref. [d] |
---|---|---|---|---|---|---|
1 | (S,S)-6b | acetophenone | i-PrOH/KOH | 20; 48 h; – ; 23 | 84 (S) | [100] |
2 | (S,S)-7a | acetophenone | HCOOH/Et3N/ CH2Cl2 | 100; 18 h; 30 °C; 71 | > 99 (S) | [101] |
3 | (S,S)-7b | acetophenone | HCOOH/Et3N | 100; 28 h; 30 °C; 95 | 96.7 (S) | [101] |
4 | (R,R)-8 | acetophenone | HCOOH/Et3N | 100; 20 h; 50 °C; 95 | 94 (R) | [102] |
5 | (R,R)-8 | acetophenone | H2O/HCOONa | 100; 1 h; 40 °C; 99 | 92 (R) | [103] |
6 | (R,R)-9a | acetophenone | HCOOH/Et3N | 100; 6 h; 40 °C; >99 | 97 (R) | [104] |
7 | (R,R)-9b | acetophenone | H2O/HCOONa; TBAB [e] | 100; 2 h; 40 °C; >99 | 96 (R) | [105] |
8 | (S,S)-10b | 2-cyano-acetophenone | HCOOH/Et3N | 100; 17 h; 30 °C; 98 (isol. yield) | 97 (S) | [107] |
9 | (S,S)-11 | DHIQ [f] | HCOOH/Et3N/CH2Cl2 | 100; 12 h; r.t.; 100 (isol. yield) | 91 (R) | [108] |
10 | (R,R)-12b | acetophenone | H2O/HCOONa | 100; 3 h; 40 °C; 100 | 98 (R) | [109] |
11 | (R,R)-13b | acetophenone | H2O/HCOONa | 100; 3 h; 40 °C; 100 | 98 (R) | [109] |
12 | (R,R)-13a | DHIQ [f] | H2O/HCOONa; CTAC [g] | 100; 24 h; r.t.; 69 | 94 (S) | [110] |
13 | (S,S)-14 | acetophenone | H2O/HCOONa | 100; 2 h; r.t.; >99 | 96 (S) | [111] |
14 | (S,S)-15 | DHIQ [f] | HCOOH/Et3N/CH2Cl2 | 100; 1.5 h; 40 °C; 99 | 94 (R) | [112] |
15 | (R,R)-16 | acetophenone | H2O/HCOONa | 100; 9 h; 40 °C; 100 | 97 (R) | [113] |
Entry | Ligand | Solution | Time; Temp.; Conversion (%) | % ee (config.) [b] | Ref. [c] | |
---|---|---|---|---|---|---|
1 | (S,S)-17 [d] | HCOOH/Et3N | 20 h; 28 °C; >98 | 96.5 (S) | [125] | |
2 | (R,R)-18a | HCOOH/Et3N | 20 h; 28 °C; 99 | 97.6 (R) | [57] | |
3 | (R,R)-19 | HCOOH/Et3N | 20 h; 28 °C; 97 | 97.1 (R) | [57] | |
4 | (R,R)-20 [e] | HCOOH/Et3N | 20 h; 28 °C; 97 | 97.1 (R) | [128] | |
5 | (R,R)-21 [f] | HCOOH/Et3N/CH2Cl2 | 20 h; 28 °C; 97 | 96.1 (R) | [129] | |
6 | (S,S)-17 [e] | i-PrOH/i-PrOK | 48 h; 25 °C; 65 | 95 (S) | [130] | |
7 | (S,S)-22 | H2O/HCOONa; TBAI [g] | 4 h; 40 °C; > 99 | 97 (S) | [131] |
Entry | Ligand | Solution | S/C [a]; Time; Temp.; Conversion (%) | % ee (config.) [b] | Ref. [c] |
---|---|---|---|---|---|
1 | (R,R)-23 [d] | HCOOH/Et3N/[C4C1C1Im]PF6 [e] | 200; 24 h; 35 °C; > 99 | > 99 | [132] |
2 | (S,S)-24 [f] | HCOOH/Et3N/[bmim][PF6] [g] | 100; 24 h; r.t.; 98 | 92 (S) | [72] |
3 | (R,R)-5a [h] | HCOOH/Et3N/[bmim][PF6] [g] | 100; 8 h; 40 °C; 100 | 97 (R) | [99] |
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Václavík, J.; Kačer, P.; Kuzma, M.; Červený, L. Opportunities Offered by Chiral η6-Arene/N-Arylsulfonyl-diamine-RuII Catalysts in the Asymmetric Transfer Hydrogenation of Ketones and Imines. Molecules 2011, 16, 5460-5495. https://doi.org/10.3390/molecules16075460
Václavík J, Kačer P, Kuzma M, Červený L. Opportunities Offered by Chiral η6-Arene/N-Arylsulfonyl-diamine-RuII Catalysts in the Asymmetric Transfer Hydrogenation of Ketones and Imines. Molecules. 2011; 16(7):5460-5495. https://doi.org/10.3390/molecules16075460
Chicago/Turabian StyleVáclavík, Jiří, Petr Kačer, Marek Kuzma, and Libor Červený. 2011. "Opportunities Offered by Chiral η6-Arene/N-Arylsulfonyl-diamine-RuII Catalysts in the Asymmetric Transfer Hydrogenation of Ketones and Imines" Molecules 16, no. 7: 5460-5495. https://doi.org/10.3390/molecules16075460