Heteroatom Substitution at Amide Nitrogen—Resonance Reduction and HERON Reactions of Anomeric Amides
Abstract
:1. Introduction
2. Properties of Anomeric Amides
2.1. Structural Properties
2.2. Resonance Energies and Amidicities
2.3. The Anomeric Effect
2.4. Spectroscopic Properties of Anomeric Amides
3. Reactivity of Anomeric Amides
3.1. Reactivity at the Amide Nitrogen
3.1.1. SN2 Reactions
3.1.2. Elimination Reactions
3.2. The HERON Reaction
3.2.1. HERON Reactions of N-Amino-N-Alkoxymides
3.2.2. Theoretical and Experimental Validation of the HERON Reaction
3.2.3. HERON Reaction of 1-Acyl-1-Alkoxydiazenes
3.2.4. HERON Reactions of Anionic Systems
3.2.5. HERON Reactions of N-Alkoxy-N-Aminocarbamates
3.2.6. HERON Reactions of N-Acyloxy-N-Alkoxyamides
3.2.7. HERON Reactions of N,N-Dialkoxyamides
3.2.8. N-Alkoxy-N-Alkylthiylamides
3.3. Driving Force for the HERON Reaction
4. Conclusions
Conflicts of Interest
References
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Structure | N–C(O)/Å | (N)C=O/Å | θ/° | χN/° | τ/° | Anomeric Twist 1/° |
---|---|---|---|---|---|---|
5a [33] | 1.409 | 1.206 | 331.2 | 58.3 | 6.7 | C10-O3-N1-O2: 95.9 C8-O2-N1-O3: −114.1 |
5b [33] | 1.421 | 1.211 | 334.5 | 55.6 | 13.9 | C8-O2-N1-O3: −101.6 C15-O3-N1-O2: −63.8 |
6a [29] | 1.439 | 1.205 | 323.5 | 65.3 | 15.5 | C18-O3-N1-O1:96.2 C7-O1-N1-O3: −141.6 |
6b [29] | 1.441 | 1.207 | 324.1 | 65.6 | 13.9 | C14-O3-N1-O1:96.7 C7-O1-N1-O3: −137.6 |
7 [65] | 1.411 | 1.203 | 330.3 | 59.7 | −14.0 | C8-O1-N1-O5:−91.8 C9-O5-N1-O1: 116.2 |
8(N1) [32] | 1.412 | 1.213 | 343.2 | 47.3 | −8.5 | LP (N2)-N2 -N1-O2: 47.3 |
8(N2) | 1.410 | 1.207 | 341.1 | 48.9 | −11.4 | LP (N1)-N1-N2-O3: 178.6 |
9 [65] | 1.408 | 1.204 | 337.5 | 52.5 | −13.3 | C8-O2-N1-Cl1: −84.2 |
Structure | N–C(O)/Å | (N)C=O/Å | θ/° | χN/° | τ/° | Anomeric Twist 2/° |
---|---|---|---|---|---|---|
10a [66] | 1.443 1 | 1.226 | 329.1 | 59.9 | 8.2 | C-O-N-Cl: –90.9 |
10b [66] | 1.472 1 | 1.210 | 325.8 | 61.9 | −13.4 | C-O-N-Cl: –100.1 |
11a [67] | 1.426 1 | 1.222 | 333.6 | −57.1 | −6.8 | C-O-N-Oacyl: –104.0 |
11b [68] | 1.441 1 | 1.233 | 323.7 | 64.6 | 11.8 | C-O-N-Oacyl: –98.2 |
12 [68] | 1.438 1 | 1.220 | 331.8 | 57.4 | 0.8 | C-O2-N1-O1:–89.3 C-O1-N1-O2: 55.2 |
13 [67] | 1.424 | 1.198 | 334.2 | −56.3 | 2.9 | C-O-N-Oacyl: –95.5 |
14 [69] (N1)/(N2) 3 | 1.408 | 1.194 | 340.0 | 59.8 | −9.4 | LP (N1)-N1-N2-O: 189.2 |
Structure | N–C(O)/Å | (N)C=O/Å | (N–X,N–Y)/Å | θ/° | χN/° | τ/° | Anomeric Twist Angles 1/° |
---|---|---|---|---|---|---|---|
15a ONCl [34] | 1.432 | 1.207 | Cl:1.787 O2:1.389 | 337.6 | 52.3 | −5.3 | C2-O2-N1-Cl: 88.8 |
15b ONOAc [61] | 1.429 | 1.209 | O2:1.423 O3:1.395 | 332.1 | 58.0 | 2.3 | C4-O3-N1-O2: 101.1 |
4b ONO [33] | 1.417 | 1.212 | O2:1.387 O3:1.412 | 342.9 | 48.1 | 8.5 | C2-O2-N1-O3: 66.6 C3-O3-N1-O2: 83.8 |
15c NNO [62] | 1.404 | 1.217 | O1:1.430 N2:1.387 | 346.5 | 41.8 | 5.4 | LP (N2)-N2-N1-O1: 190 |
15d ONS [61] | 1.408 | 1.215 | S1:1.717 O2:1.420 | 352.4 | 31.7 | −4.6 | C4-S1-N1-O2: −79 C3-O2-N1-S1: −86.6 |
15e NNCl [34] | 1.414 | 1.209 | Cl:1.820 N2:1.351 | 360.0 | 0 | 0 | LP(N2)N2-N1-Cl: 180 |
16a NNO [61] | 1.406 | 1.212 | O1:1.404 N2:1.383 | 342 | 46.3 | 0 | LP (N2)-N2-N1-O1: 169.4 |
16b NNO | 1.428 | 1.217 | O1:1.397 N2:1.428 | 340.0 | 49.6 | −1.7 | LP (N2)-N2-N1-O1: 167.5 |
Amide (R = Me) | ΔECOSNAR1 /kJ mol−1 | ΔETA /kJ mol−1 | ΔEind /kJ mol−1 | RETA1, 2 /kJ mol−1 |
---|---|---|---|---|
15a (ONCl) [34] | −29.6(38) | 69.9 | 23.4 | −29.5(39) |
15a3 | −27.2 (36) | |||
15a4 | −34.4(45) | |||
15b (ONOAc) [61] | −39.7(52) | 65.3 | 29.7 | −40.5(53) |
15b4 | −39.5 (52) | |||
4b (ONO) [35] | −36.0(47) | 58.2 | 18.0 | −36.0(47) |
4b4 | −39.5(53) | - | ||
15c (ONN) [62] | −52.3(69) | 35.1 | 10.0 | −51.0(67) |
15c4 | −55.7(73) | |||
15d (ONS) [61] | −48.6(64) | 26.8 | 5.0 | −48.6(64) |
15d4 | −47.3(62) | |||
15e (NNCl) [34] | −28.7(38) | 64.5 | 17.6 | −29.0(37) |
15e3 | −28.6(38) | |||
15e4 | −48.7(64) | |||
16a (ONN) [61] | −47.7(63) | 31.8 | 14.6 | −50.6(67) |
1 | −75.9(100) | |||
14 [34] | −75.9(100) |
System | X | Y | R | Amide ν/cm−1 (δ13C) | Hydroxamic Ester ν/cm−1 (δ13C) |
---|---|---|---|---|---|
2a [79] | Cl | OBu | Me | 1740 1(175.3) | 1678 (167.9) |
2a [35] | Cl | OBu | Ph | 1719 (174.2) | 1654 (165.7) |
2b [79] | OAc | OBu | Me | 1746 (176.2) | 1678 (167.9) |
2b [80] | OAc | OBu | Ph | 1732 (173.9) | 1654 (165.7) |
2c [81] | OBu | OBu | Me | 1707 (174.1) | 16781 (167.9) |
2c [55] | OMe | OMe | Ph | 1711 (174.3) | 1683 (166.4) |
2d [76] | 4-MeBnONAc | 4-MeBnO | Me | 1734/1700 (171.3) | 1693 (168.0) |
2d [76] | BzNOEt | OEt | Ph | 1708 (170.0) | 1685 (166.5) |
Series | System | EA/kJ mol−1 | ΔS‡/J K−1 mol−1 | 106.k298/s−1 |
---|---|---|---|---|
Series 19: σ+ reaction constant ρ = −0.35 1 | 19a | 99.2 (4.3) | −21.2 (13) | 5.56 |
19b | 100.7 (8.2) | −19.6 (25) | 3.72 | |
19c | 100.4 (5.1) | −23.8 (15) | 2.52 | |
19d | 107.7 (1.7) | 0.9 (5) | 2.50 | |
19e | 104.0 (1.7) | −15.4 (5) | 1.57 | |
Series 20: σ reaction constant ρ = +1.02 1 | 108.k298/s−1 | |||
20a | 111.4 (0.9) | −21.1 (2) | 4.02 | |
20b | 125.9 (1.0) | 24.5 (3) | 2.76 | |
20c | 114.1 (3.9) | −8.7 (11) | 6.21 | |
20d | 125.1 (8.5) | 27.4 (24) | 5.44 | |
20e | 98.8 (0.3) | −46.4 (1) | 31.9 |
R | R′ | Isolated Crude Yield/% |
---|---|---|
Ph | (CH3)3C | 87 |
(CH3)3C | (CH3)3C | 30 |
1-adamantyl | (CH3)3C | 82 |
(CH3)3C | cyclohexyl | 97 |
Ph | (CH3)2CH | 92 |
Ph | PhCH2 | 93 |
CH3 | PhCH2 | 92 |
p-NO2C6H4 | Et | 94 |
Ph | Et | 94 |
Migratory Mode | EA | XNY 1 | RETA 2 | Erearr |
---|---|---|---|---|
MeO from anti 15c | 95.0 | ONN | −51.5 | 43.5 |
MeO from 4b | 156.5 | ONO | −35.9 | 120.5 |
MeO from syn 16a | 92.4 | ONN | −50.7 | 41.8 |
AcO from syn 15b | 181.0 | AcONO | −40.5 | 140.5 |
MeO from syn 15b | 207.9 | ONOAc | −40.5 | 167.4 |
AcO from anti 15b | 181.5 | AcONO | −40.5 | 141.0 |
MeO from anti 15b | 182.8 | ONOAc | −40.5 | 142.3 |
MeO from anti 15d | 174.1 | ONS | −48.6 | 125.4 |
MeO from 15f 3 | 48.0 | ONO– | −32.4 | 15.6 |
MeO from 15g | 8.8 | ONNitrene | −14.8 | −6.0 |
Ring opening 81 | 113.0 | ONO | −19.2 | 93.8 |
Ring contraction 82 | 145.2 | ONO | −36.7 | 108.4 |
Ring opening of 82 | 136.4 | ONO | −36.7 | 99.7 |
Scheme 17 i X=NMe | 59.0 | ONN | 0.0 | 59.0 |
Scheme 17 i X=O | 146.9 | ONO | 0.0 | 146.9 |
Scheme 17 i X=S | 152.7 | ONS | 0.0 | 152.7 |
Scheme 17 ii X=CH2 | 242.7 | ONCH2 | 0.0 | 242.7 |
Scheme 18 i | 133.5 | AcONO | 0.0 | 133.5 |
Scheme 18 ii | 161.5 | ONOAc | 0.0 | 161.5 |
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Glover, S.A.; Rosser, A.A. Heteroatom Substitution at Amide Nitrogen—Resonance Reduction and HERON Reactions of Anomeric Amides. Molecules 2018, 23, 2834. https://doi.org/10.3390/molecules23112834
Glover SA, Rosser AA. Heteroatom Substitution at Amide Nitrogen—Resonance Reduction and HERON Reactions of Anomeric Amides. Molecules. 2018; 23(11):2834. https://doi.org/10.3390/molecules23112834
Chicago/Turabian StyleGlover, Stephen A., and Adam A. Rosser. 2018. "Heteroatom Substitution at Amide Nitrogen—Resonance Reduction and HERON Reactions of Anomeric Amides" Molecules 23, no. 11: 2834. https://doi.org/10.3390/molecules23112834