Characteristic Conformation of Mosher’s Amide Elucidated Using the Cambridge Structural Database
Abstract
:1. Introduction
2. Results and Discussion
2.1. Crystal Structures of MTPA Amides Deposited in the CSD
No. | CCDC Number (b) | Reference | Chirality of MTPA (a) | Amine Moiety | R sp | R ap | O1–C1–C2–C3 (θ1) | C1–C2–C3–F3 | C1'–N–C1–O1 | X1′′–N–C1–O1 (c) | H1′–C1′–N–C1 | O2–C2–C5–C10 (θ2) | C1–C2–O2–C4 |
---|---|---|---|---|---|---|---|---|---|---|---|---|---|
1 (d) | 199868 | [27] | R | Primary amine | Secondary alkyl group | H | −13.1(2) | −172.0(1) | 7.1(2) | −172.9 | −47.4 | 23.3(2) | 54.2(2) |
2 (d) | 199868 | [27] | R | Primary amine | Secondary alkyl group | H | −7.3(2) | −174.6(1) | 6.3(2) | −173.7 | −51.5 | 29.4(2) | 50.4(2) |
3 (d) | 222942 | [28] | R | Primary amine | Secondary alkyl group | H | 30.3(3) (e) | 175.6(2) | −4.2(5) | 169(4) | 47.0 | 11.2(7) | −44.4(4) |
4 (d) | 603055 | [29] | S | Primary amine | Secondary alkyl group | H | 35.0(4) (e) | 165.9(3) | 0.5(5) | −179.5 | 15.2 | −43.7(4) | −72.0(3) |
5 | 651954 | [30] | R | Primary amine | Primary alkyl group | H | −26(2) | −168(1) | −6(2) | 173 | – | 24(2) | 72(1) |
6 | 651954 | [30] | R | Primary amine | Primary alkyl group | H | −25(2) | −166(1) | 8(2) | −172 | – | 22(2) | 60(2) |
7 (d) | 678252 | [31] | R | Primary amine | Secondary alkyl group | H | −22.6(4) | −171.7(3) | 9.5(5) | −170.6 | 29.6 | 19.7(4) | 58.4(3) |
8 (d) | 678252 | [31] | R | Primary amine | Secondary alkyl group | H | −14.4(5) | −173.2(3) | 5.2(6) | −174.8 | 28.3 | 22.5(4) | 54.2(4) |
9 (d,f) | 703912 | [32] | R | Primary amine | Secondary alkyl group | H | −67.7(6) (e) | −174.6(5) | 3.7(9) | 170(5) | −22.5 | −58.9(7) | −162.7(5) |
10 | 734247 | [33] | R | Primary amine | Primary alkyl group | H | −29.1(5) | −168.3(3) | −2.9(6) | 177.0 | – | 24.2(5) | 62.9(4) |
11 | 739753 | [34] | R | Primary amine | Primary alkyl group | H | −36.0(2) (e) | −164.7(2) | 7.1(3) | −172.9 | – | 49.8(2) | 64.5(2) |
12 (d) | 1218697 | [35] | R | Primary amine | Secondary alkyl group | H | −9.8(3) | −176.9(2) | −3.0(4) | 171(2) | 1.3 | 12.0(3) | 55.5(3) |
13 (d) | 1229820 | [36] | R | Primary amine | Secondary alkyl group | H | −31(1) (e) | −169.2(8) | 15(2) | 136 | −7 | 21 | 64 |
14 (d) | 1277744 | [37] | R | Primary amine | Secondary alkyl group | H | −28.4(3) | −170.3(2) | 3.9(4) | −176.0 | −14.4 | 26.9(3) | 65.2(3) |
15 (g) | 140352 | [38] | R | Secondary amine | Secondary alkyl group | Primary Alkyl group | −4.7(5) | −175.4(3) | 5.3(6) | −174.7(4) | 20.4(6) | 27.5(5) | 53.4(4) |
16 (g) | 167289 | [39] | S | Secondary amine | Secondary alkyl group | Primary alkyl group | 5.2(2) | 177.7(1) | −0.5(2) | −177.4(2) | 10(2) | −11.7(2) | −45.0(2) |
17 (g) | 241708 | [40] | S | Secondary amine | Secondary alkyl group | Primary alkyl group | 6.9(2) | 176.0(1) | −1.7(2) | 169.5(1) | 48.1 | −15.4(2) | −45.1(2) |
18 (g) | 251663 | [41] | R | Secondary amine | Secondary alkyl group | Primary alkyl group | −12.4(2) | −172.3(1) | 1.8(2) | −168.2(1) | 24.3 | 24.5(2) | 56.7(2) |
19 | 288331 | [42] | S | Secondary amine | Secondary alkyl group | Secondary alkyl group | 7.7(3) | 176.5(2) | 8.7(3) | 174.0(2) | −1.3 | −14.0(3) | −50.1(3) |
20 | 296547 | [43] | R | Secondary amine | Primary alkyl group | Primary alkyl group | –13.4(8) | −171.7(5) | −0.9(9) | −170.9(6) | – | 12.6(7) | 47.4(7) |
21 (g) | 604432 | [44] | R | Secondary amine | Secondary alkyl group | Primary alkyl group | −4.1(5) | −176.3(3) | 8.7(5) | −170.3(3) | 17.1 | 15.3(4) | 51.7(4) |
22 (g) | 605818 | [45] | R | Secondary amine | Secondary alkyl group | Primary alkyl group | −15.6(2) | −174.1(1) | 5.8(2) | −164.3(1) | −58.3 | 6.9(2) | 52.1(1) |
23 | 638938 | [46] | R | Secondary amine | Primary alkyl group | Primary alkyl group | −6.2(5) | −173.8(3) | −1.8(5) | −173.7(3) | – | 27.7(4) | 51.2(4) |
24 (g) | 675390 | [47] | R | Secondary amine | Secondary alkyl group | Primary alkyl group | −14.6(2) | −174.7(1) | 10.1(3) | −164.8(2) | −56.5 | 9.2(2) | 50.4(2) |
25 (g) | 706349 | [48] | R | Secondary amine | Secondary alkyl group | Primary alkyl group | −13.7(4) | −172.3(3) | 5.9(5) | −168.6(3) | 19(2) | 19.3(4) | 59.4(4) |
26 (h) | 707825 | [49] | S | Secondary amine | Me | Secondary alkyl group | 8.6(3) | 173.1(2) | 0.1(3) | 173.6(2) | – | −12.7(3) | −50.0(3) |
27 (h) | 707825 | [49] | S | Secondary amine | Me | Secondary alkyl group | 4.0(3) | 176.7(2) | 0.3(3) | −174.7(2) | – | −14.1(3) | −51.0(2) |
28 (h) | 707825 | [49] | S | Secondary amine | Me | Secondary alkyl group | 1.1(3) | 178.0(2) | 1.3(3) | −176.7(2) | – | –18.4(3) | −48.3(3) |
29 (h) | 707825 | [49] | S | Secondary amine | Me | Secondary alkyl group | 3.6(3) | 177.1(2) | 1.2(3) | –179.7(2) | – | −9.4(3) | −46.0(3) |
30 | 766837 | [50] | S | Secondary amine | Primary alkyl group | Primary alkyl group | 9.4(2) | 175.1(1) | 2.0(2) | 177.8(1) | – | −14.7(2) | −44.7(1) |
31 (g) | 830079 | [51] | R | Secondary amine | Tertiary alkyl group | Primary alkyl group | −18(1) | −173.1(6) | −1(1) | −178.3(7) | – | 20(1) | 55.8(9) |
32 | 1104875 | [52] | R | Secondary amine | Primary alkyl group | Primary alkyl group | −2.2(2) | −176.5(2) | −5.2(3) | −176.7(2) | – | 27.1(2) | 45.2(2) |
33 | 1105464 | [53] | R | Secondary amine | Primary alkyl group | Primary alkyl group | −8.2(8) | 178.4(5) | −0.7(9) | −172.4(6) | – | 12.0(8) | 46.6(8) |
34 | 1105464 | [53] | R | Secondary amine | Primary alkyl group | Primary alkyl group | –9.0(8) | –175.6(5) | –6.1(9) | –168.0(6) | – | 13.7(8) | 45.8(7) |
35 (g) | 1267150 | [54] | S | Secondary amine | Secondary alkyl group | Primary alkyl group | 7.1(6) | 176.2(4) | −3.0(7) | −179.1(4) | 19.5 | −15.3(6) | −42.6(5) |
36 (g) | 1267151 | [54] | R | Secondary amine | Secondary alkyl group | Primary alkyl group | −14.0(7) | −170.3(4) | 8.4(7) | −163.3(5) | 24.4 | 29.7(7) | 59.7(6) |
37 (g) | 1280861 | [55] | R | Secondary amine | Secondary alkyl group | Primary alkyl group | −15.6(6) | −170.9(4) | 11.4(7) | −174.1(4) | −15.1 | 28.5(7) | 50.1(6) |
38 (g) | 1280861 | [55] | R | Secondary amine | Secondary alkyl group | Primary alkyl group | −5.5(6) | −177.6(4) | 7.8(7) | −177.4(4) | −17.0 | 25.0(6) | 41.3(6) |
39 | 1294281 | [56] | R | Secondary amine | Primary alkyl group | Primary alkyl group | −6(1) | −175.0(7) | 1(1) | −172.0(7) | – | 26(1) | 44.0(9) |
40 | 1294281 | [56] | R | Secondary amine | Primary alkyl group | Primary alkyl group | −15(1) | −172.9(7) | 1(1) | −163.7(8) | – | 14(1) | 47(1) |
41 (i) | 113953 | [57] | R | Aniline derivative | ortho-Substituted phenyl group | H | −17(1) | −174.9(6) | −11(1) | 178.6 | – | 8(1) | 54.6(8) |
42 (i) | 113953 | [57] | R | Aniline derivative | ortho-Substituted phenyl group | H | −28(1) | −168.0(7) | −1(1) | −170.3 | – | 47.7(9) | 65.9(8) |
43 (f,i) | 113953 | [57] | R | Aniline derivative | ortho-Substituted phenyl group | H | −58.4(9) (e) | −175.1(6) | −1(1) | 176.4 | – | −56.4(9) | −153.6(6) |
44 (i) | 113953 | [57] | R | Aniline derivative | ortho-Substituted phenyl group | H | −15(1) | −170.8(6) | 6(1) | 175.4 | – | 36.1(9) | 57.7(8) |
45 (i) | 1310848 | [58] | R | Aniline derivative | ortho-Substituted phenyl group | H | −2(2) | −172(1) | −5(3) | – | – | 35(2) | 51(2) |
46 (f,i) | 1310848 | [58] | R | Aniline derivative | ortho-Substituted phenyl group | H | −60(2) (e) | 179(2) | 3(3) | – | – | −34(2) | −172(2) |
47 (i) | 1310848 | [58] | R | Aniline derivative | ortho-Substituted phenyl group | H | −41(2) (e) | −169(2) | 0(3) | – | – | 13(2) | 71(2) |
48 (f,i) | 1310848 | [58] | R | Aniline derivative | ortho-Substituted phenyl group | H | −51(2) (e) | −165(2) | −1(3) | – | – | 85(2) | −154(2) |
49 | 655554 | [59] | R | Benzotriazole | ortho-Substituted phenyl group | N | −9.3(1) | −175.21(7) | −2.8(1) | 178.81(8) | – | 25.7(1) | 46.6(1) |
50 (f) | 1142231 | [60] | S | Diethyl 1-aminoalkylphos-phonate derivative | 1-(Diethoxy-phophoryl)alkyl group | H | 57(3) (e) | 169(2) | 9(4) | – | −14 | 77(2) | 148(2) |
51 | 1142231 | [60] | S | Diethyl 1-aminoalkylphos-phonate derivative | 1-(Diethoxy-phophoryl)alkyl group | H | 24(3) | 172(2) | 4(3) | – | −12 | −35(2) | −65(2) |
52 | 1236701 | [61] | R | Diethyl 1-aminoalkylphos-phonate derivative | 1-(Diethoxy-phophoryl)alkyl group | H | −23.1(5) | −171.5(3) | −3.1(6) | 176.6 | 19.2 | 7.3(5) | 59.3(4) |
53 | 1236702 | [61] | R | Diethyl 1-aminoalkylphos-phonate derivative | 1-(Diethoxy-phophoryl)alkyl group | H | −19.4(6) | −174.3(4) | −3.2(7) | 177.2 | 18.8 | 5.8(6) | 55.8(5) |
54 | 1236703 | [61] | R | Diethyl 1-aminoalkylphos-phonate derivative | 1-(Diethoxy-phophoryl)alkyl group | H | −24(2) | −166(1) | 4(2) | −173 | 11 | 31(2) | 59(2) |
55 | 1236703 | [61] | R | Diethyl 1-aminoalkylphos-phonate derivative | 1-(Diethoxy-phophoryl)alkyl group | H | −24(2) | −166(1) | 9(2) | −171 | −14 | 35(2) | 57(1) |
56 | 1216345 | [62] | R | Oxazolidine-2-selone derivative | Selenoxo group | Secondary alkyl group | −15.9(4) | −172.9(2) | 24.5(4) | −147.8(3) | – | 18.5(4) | 56.6(3) |
57 | 630372 | [63] | R | Thiocarbamide derivative | N-Substituted thiocarbamoyl group | Secondary alkyl group | −16.7(3) | −174.1(2) | 11.2(4) | −152.6(2) | – | 24.8(3) | 57.7(3) |
58 | 143886 | [64] | R | p-Toluene-sulfonamide derivative | p-Toluene-sulfonyl group | Primary alkyl group | −5.4(6) | −177.4(3) | 7.4(5) (j) | −177.6(4) | – | 18.2(6) | 37.8(5) |
2.2. Dihedral Angles of Amide Carbonyl Group and Trifluoromethyl Group: O1–C1–C2–C3
2.3. Staggered Conformation of Trifluoromethyl Group: C1–C2–C3–F3
2.4. Resonance Effects of Amide Bond: C1′–N–C1–O1
2.5. Resonance Effects of Amide Bond: X1′′–N–C1–O1
2.6. Conformation of the Amine Moiety: H1′–C1′–N–C1
2.7. Dihedral Angle between the Methoxy Group and Phenyl Group: O2–C2–C5–C10
2.8. Conformation of the Methoxy Group: C1–C2–O2–C4
3. Experimental Section
3.1. Database Study of MTPA Amide
3.2. Caution
4. Conclusions
Acknowledgments
Author Contributions
Conflicts of Interest
References and Notes
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Ichikawa, A.; Ono, H.; Mikata, Y. Characteristic Conformation of Mosher’s Amide Elucidated Using the Cambridge Structural Database. Molecules 2015, 20, 12880-12900. https://doi.org/10.3390/molecules200712880
Ichikawa A, Ono H, Mikata Y. Characteristic Conformation of Mosher’s Amide Elucidated Using the Cambridge Structural Database. Molecules. 2015; 20(7):12880-12900. https://doi.org/10.3390/molecules200712880
Chicago/Turabian StyleIchikawa, Akio, Hiroshi Ono, and Yuji Mikata. 2015. "Characteristic Conformation of Mosher’s Amide Elucidated Using the Cambridge Structural Database" Molecules 20, no. 7: 12880-12900. https://doi.org/10.3390/molecules200712880