(R)-2-Hydroxy-2-phenyl-acetic acid methyl ester-68a56
Data: 1H NMR (400 MHz, CDCl3) δ 7.43-7.33 (m, 5H, ArH), 5.18 (d, J = 5.2, 1H), 3.76 (s, 3H), 3.45 (d, J = 5.6, 1H, OH); 13C NMR (100 MHz, CDCl3) δ 174.1, 138.2, 128.6, 128.5, C, 126.6, C, 72.9, 53.0; MS C9H10O3 (EI, 166) 166 (M+, 13), 107 (100), 79 (51), 77 (43), 40 (12); TLC Rf 0.30 (EtOAc/Hexane, 1/6); HPLC tR
12.49 min (S, 50%), 13.28 min (R, 50%) (Chiralcel AD-H, i-PrOH/hexane, 6/94, 1.0 ml/min, λ =254 nm). After resolved : 12.49 min (S, minor, 3.40 %), 13.28 min (R, major, 96.60 %). [α]20 -140.92 (c 1.0, MeOH) for 93% ee (lit. [α]20 -144 (c 1.0, MeOH
2) for (R)); The absolute configuration was deduced to be R according to the sign of optical rotation. ; mp: 56-57oC.
OH
O O
(R)-2-Hydroxy-2-phenyl-acetic acid ethyl ester-68b56
Data: 1H NMR (400 MHz, CDCl3) δ 7.43-7.32 (m, 5H, ArH), 5.16 (d, J = 5.6, 1H), 4.31-4.14 (m, 2H), 3.44 (d, J = 5.6, 1H, OH), 1.23 (t, J = 6.8, 3H); 13C NMR (100 MHz, CDCl3)δ 173.6, 138.4, 128.5, 128.3, 126.5, 72.8, 62.1, 14.0; MS C10H12O3
(EI, 180) 180 (M+, 3), 107 (100), 79 (26), 77 (22), 32 (46); TLC Rf 0.31 (EtOAc/Hexane, 1/5); HPLC tR 14.2 min (S, 49.73%), 15.4 min (R, 50.27%) (Chiralcel AD-H, i-PrOH/hexane, 4/96, 1.0 ml/min, λ =254 nm). After resolved : 14.2 min (S, minor, 13.68%), 15.4 min (R, major, 86.32%). [α]32 -125.68 (c 1.0, CHCl3) for 71% ee (lit. [α]25 -130 (c 1.0, CHCl3) for (R)); The absolute configuration was deduced to be R according to the sign of optical rotation. ; mp: 74-76oC.
(R)-2-Hydroxy-2-phenyl-acetic acid isopropyl ester-68c 56
Data: 1HNMR (400 MHz, CDCl3) δ 7.43-7.31 (m, 5H) 5.12-5.02 (m, 2H), 3.45 (bs, 1H, OH), 1.28 (d, J =6.4, 3H), 1.11 (d, J = 6.4, 3H) ; 13C NMR (100 MHz, CDCl3) δ 173.2, 138.6, 128.4, 128.2, 126.4, 72.9, 70.1, 21.6, 21.3; MS C11H14O3 (EI, 194) 194 (M+, 2), 107 (100), 79 (40), 77 (27), 43 (14); TLC Rf 0.38 (EtOAc/Hexane, 1/5);
HPLC tR 9.93 min (S, 50%), 10.99 min (R, 50%) (Chiralcel AD-H, i-PrOH/hexane, 6/94, 1.0 ml/min, λ =254 nm). After resolved : 9.93 min (S, minor, 6.15%), 10.99 min (R, major, 93.85%). [α]21 -89.12 (c 1.0, MeOH) for 88% ee (lit. [α]20-91.6 (c 1.0, MeOH) for (R)); The absolute configuration was deduced to be R according to the sign of optical rotation.
OH
O O
OH
O
O
(R)-2-Hydroxy-2-phenyl-acetic acid benzyl ester-68d57
Data: 1H NMR (400 MHz, CDCl3) δ 7.43-7.30 (m, 7H), 7.21-7.19 (m, 2H), 5.24 (d, J = 12.0, 1H), 5.22 (d, J = 5.2, 1H), 5.14 (d, J = 12.0, 1H), 3.41 (d, J = 5.2,1H, OH); 13C NMR (100 MHz, CDCl3) δ 173.5, 138.2, 135.0, 128.6, 128.5, 128.5, 128.4, 127.9, 126.6, 73.0, 67.6; MS C15H14O3 (EI, 242) 242 (M+, 4), 226 (12), 107 (100), 92(18), 90(24), 80(12), 79(19), 77(11); TLC Rf 0.34 (EtOAc/Hexane, 1/5); HPLC tR 19.1 min (S, 50%), 23.5 min (R, 50%) (Chiralcel AD-H, i-PrOH/hexane, 6/94, 1.0 ml/min, λ
=254 nm). After resolved : 19.1 min (S, minor, 0.78%), 23.5 min (R, major, 99.22%).
[α]26 -53.9 (c 1.0, MeOH) for 98% ee (lit. [α]24 -49.2 (c 1.51, MeOH) for (R)-); The absolute configuration was deduced to be R according to the sign of optical rotation.;
mp: 96-98oC.
(R)-2-Hydroxy-2-phenyl-acetic acid benzhydryl ester-68e58
Data: 1H NMR (400 MHz, CDCl3) δ 7.45-7.31 (m, 10H), 7.21-7.15 (m, 3H), 6.94-6.90 (m, 3H), 5.30 (d, J = 5.6, 1H), 3.54 (d, J = 5.2, 1H); 13C NMR (100 MHz, CDCl3) δ 172.6, 139.2, 139.1, 138.0, 128.53, 128.51, 128.45, 128.2, 127.7, 127.3, 126.8, 126.2, 78.6, 73.1; MS C21H18O3 (EI, 318.) 318 (12), 277 (M+, 100), 165 (66), 148 (70); TLC Rf 0.35 (EtOAc/Hexane, 1/5); HPLC tR
59.3 min (S, 50%), 61.3 min (R, 50%) (Chiralcel AD-H, i-PrOH/hexane, 4/96, 1.0 ml/min, λ =254 nm). After resolved : 59.3 min (S, mimor, 4.64%), 61.3 min (R, major, 95.36%). [α]32 -44.52 (c 1.0, CHCl3) for 91% ee ; The absolute configuration was deduced to be R according to the sign of optical rotation.; mp: 56-57oC.
OH
O O
OH
O O
(R)-2-Hydroxy-2-phenyl-acetic acid benzhydryl ester-68f 59
Data: 1H NMR (400 MHz, CDCl3) δ 7.55 (d, J = 7.2, 2H), 7.45-7.33 (m, 5H), 7.23 (t, J = 7.4, 1H), 7.00 (d, J
= 7.8, 2H), 5.44 (d, J = 4.6, 1H), 3.43 (d, J = 5.5, 1H);
13C NMR (100 MHz, CDCl3) δ 172.3, 150.3, 137.9, 129.5, 128.81, 128. 8, 126.7, 126.3, 121.0, 73.2; MS C14H12O3 (EI, 228.) 228 (7), 135 (100), 107 (42), 92 (67);
TLC Rf 0.38 (EtOAc/Hexane, 1/5); HPLC tR 15.16 min (S, 50.12%), 16.98 min (R, 49.88%) (Chiralcel AD-H, i-PrOH/hexane, 3/97, 1.0 ml/min, λ =254 nm). After resolved : 15.34 min (S, mimor, 10.36%), 16.17 min (R, major, 89.64%). [α]28 -23.8 (c 1.0, CHCl3) for 79% ee ; The absolute configuration was deduced to be R according to the sign of optical rotation.; mp: 87-88oC.
2-Hydroxy-N-isopropyl-2-phenyl-acetamide-69a60
Data: 1H NMR (400 MHz, CDCl3) δ 7.36-7.32 (m, 5H), 6.07 (brs, 1H, -NH), 4.94 (d, J = 2.0, 1H), .03 (heptet, J
= 6.4, 1H), 1.12 (d, J = 6.8, 3H), 1.09 (d, J = 6.4, 3H);
13C NMR (100 MHz, CDCl3) δ 171.2, 139.6, 128.8, 128.5, 126.8, 74.0, 41.6, 22.6, 22.5; MS C11H15 NO2 (ESI,193) 216 (M+Na+, 100);
TLC Rf 0.0.33 (EtOAc/Hexane, 1/2); HPLC tR 22.43min (S, 50%), 26.61 min (R, 50%) (Chiralcel AD-H, i-PrOH/hexane, 94/6, 1.0 ml/min, λ =254 nm). After resolved : 22.51 min (R, mimor, 53.75%), 26.79 min (S, major, 46.25%). [α]28 -23.8 (c 1.0, CHCl3) for 7% ee ; The absolute configuration was deduced to be R according to the sign of optical rotation.; mp: 87-88oC.
(R)-N-Benzyl-2-hydroxy-2-phenyl-acetamide-69b61
Data: 1H NMR (400 MHz, CDCl3) δ 7.42-7.26 (m, 5H),
OH
O O
OH
O H N
7.19-7.17 (m, 2H), 6.48 (brs, 1H, -NH), 5.07 (s, 2H), 4.44 (dd, J = 14.8, 5.6, 2H), 3.61 (brs, 1H, -OH); 13C NMR (100 MHz, CDCl3) δ 172.1, 139.4, 137.7, 128.9, 128.7, 127.6, 126.8, 74.2, 43.4;
MS C15H15 NO2 (ESI, 241) 264 (M+Na+, 12), 505 (2M+Na+, 100); TLC Rf 0.28 (EtOAc/Hexane, 1/2); HPLC tR 18.1 min (S, 50%), 30.2 min (R, 50%) (Chiralcel AD-H, i-PrOH/hexane, 8/92, 1.0 mL/min, λ =254 nm). After resolved : 18.4 min ( R, major, > 99 %), [α]28 -82.4 (c 1.0, CHCl3) for >99 % ee (lit. [α]23-78.7 (c 1.09, CHCl3) for (R)-); mp: 133-135oC.
(R)-N-Benzhydryl-2-hydroxy-2-phenyl-acetamide-69c62
Data: 1H NMR (400 MHz, CDCl3) δ 7.40-7.25 (m,11H), 7.17-7.15 (m, 2H), 6.72 (d, J = 7.4, 1H, -NH ), 6.22 (d, J = 8.3, 2H), 5.10 (d, J = 1.5, 1H); 13C NMR (100 MHz, CDCl3) δ 171.2, 141.0, 140.9, 128.9, 128.7, 128.6, 127.6, 127.4, 127.1, 126.8, 74.2, 56.9; MS C21H19NO2 (ESI, 317) 657 (2M+Na+, 100); TLC Rf 0.28 (EtOAc/Hexane, 1/2); HPLC tR 24.6 min (S, 50%), 86.2 min (R, 50%) (Chiralcel AD-H, i-PrOH/hexane, 8/92, 1.0 ml/min, λ =254 nm). After resolved : 24.3 min (S, major, 3.5 %), 82.4 min (R, minor, 96.5 %). [α]25 -54.6 (c 1.0, CHCl3) for 93% ee ; The absolute configuration was determined according to the sign of optical rotation.;
mp: 152-155oC.
N-tert-Butyl-2-hydroxy-2-phenyl-acetamide-69d 63
Data: 1H NMR (400 MHz, CDCl3) δ 7.38-7.33 (m, 5H), 6.03 (brs, 1H, -NH), 4.84 (s, 1H),1.32 (s, 9H); 13C NMR (100 MHz, CDCl3) δ 171.3, 139.9, 128.8, 128.4, 126.8, 74.2, 51.4, 28.6; MS C12H17NO2 (ESI,207) 231 (M+Na+,21);
TLC Rf 0.41 (EtOAc/Hexane, 1/2); HPLC tR 6.96 min (S, 49.86%), 7.90 min (R, OH
O HN
OH
O HN
OH
O
H N
50.14%) (Chiralcel AD-H, i-PrOH/hexane, 7/93, 1.0 ml/min, λ =254 nm). After resolved : 6.98 min (S, major, 53.84 %), 7.90 min (R, minor, 46.12 %). [α]26 12.6 (c 0.55, MeOH) for 7% ee ; The absolute configuration was determined according to the Literature reported.; mp: 82-83oC.
(R)-N-Phenyl-2-hydroxy-benzeneacetamide-69e64
Data: 1H NMR (400 MHz, CDCl3) δ 8.18 (s, 1H, -NH), 7.52-7.29 (m, 9H), 7.12 (t, J = 7.2, 1H), 5.15 (s, 1H), 3.36 (brs, 1H, -OH); 13C NMR (100 MHz, CDCl3) δ 166.9, 139.0, 137.0, 129.0, 128.98, 128.90, 126.9, 124.7, 119.8, 74.7; MS C14H13NO2 (ESI, 227) 251 (M+Na+, 32), 477 (2M+Na+, 100);
TLC Rf 0.30 (EtOAc/Hexane, 1/2); HPLC tR 17.6 min (R, 49.87%), 46.9 min (S, 50.03%) (Chiralcel AD-H, i-PrOH/hexane, 8/92, 1.0 mL/min, λ =254 nm). After resolved : 25.3 min (S, major, 85.5%), 36.7 min (R, minor, 14.1%), 72 % ee. [α]27 -22.3 (c 2.36, Acetone) for 72% ee (lit. [α]21 26.2 (c 2.36, Acetone) for (S)-); The absolute configuration was deduced to be R according to the sign of optical rotation.;
104-106oC.
(R)-2-Hydroxy-2-(p-tolyl)-acetic acid benzyl ester-70
Data: 1H NMR (400 MHz, CDCl3) δ 7.33-7.29 (m, 5H), 7.23-7.20 (m, 2H), 7.17-7.16 (m, 2H), 5.25 (d, J = 12.4, 1H), 5.19 (d, J = 5.6, 1H), 5.12 (d, J = 12.4, 1H), 3.37 (d, J
= 5.6, 1H, -OH), 2.35 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 173.6, 138.3, 135.3, 135.1, 129.3, 128.5, 128.4, 128.0, 126.5, 72.8, 67.6, 21.2; TLC Rf 0.39 (EtOAc/Hexane, 1/4); MS C16H16O3 (EI, 256) 256 (M+, 14), 121 (100), 93 (27), 91 (49);HR-MS Calcd. For M+, C16H16O3 : 256.1099, found : 256.1110; Anal.
OH
O O OH
O HN
Calcd. for C16H16O3 :C, 74.98; H, 6.29. Found: C, 75.09; H, 6.19.; HPLC tR 18.6 min (S, 50%), 23.9 min (R, 50%) (Chiralcel AD-H, i-PrOH/hexane, 6/94, 1.0 ml/min, λ =254 nm). After resolved : 18.6 min (S, minor, 12.40%), 23.9 min (R, major, 87.60%). [α]28 -39.4 (c 1.0, CHCl3) for 75% ee; The absolute configuration was deduced to be R according to the sign of optical rotation.; mp: 79-81oC.
(R)-2-Hydroxy-2-(4-methoxy-phenyl)-acetic acid benzyl ester -71
Data: 1H NMR (400 MHz, CDCl3) δ 7.34-7.31 (m, 5H), 7.23-7.21 (m, 2H), 6.89-6.87 (m, 2H) , 5.24 (d, J = 12.4, 1H), 5.17 (d, J = 6.0, 1H), 5.13 (d, J = 12.4, 1H), 3.81(s, 3H), 3.42 (d, J = 6.0, 1H); 13C NMR (100 MHz, CDCl3) δ 173.6, 159.7, 135.0, 130.4, 128.5, 128.4, 127.9, 127.85, 114.0, 72.5, 67.5, 55.2; TLC Rf 0.39 (EtOAc/Hexane, 1/3); HR-MS Calcd. For M+, C16H16O4 : 272.1049, found : 272.1042; Anal.
Calcd. for C16H16O4 :C, 70.57; H, 5.92. Found: C, 70.56; H, 5.68.; HPLC tR
29.2 min (S, 50%), 36.5 min (R, 50%) (Chiralcel AD-H, i-PrOH/hexane, 6/94, 1.0 ml/min, λ =254 nm). After resolved : 29.2 min (S, minor, 15.50%), 36.5 min (R, major, 84.50%). [α]29 -37.52 (c 1.0, CHCl3) for 69% ee; The absolute configuration was deduced to be R according to the sign of optical rotation.; mp: 94-96oC.
.
(R)-2-(4-Chloro-phenyl)-2-hydroxy-acetic acid benzyl ester-72
Data: 1H NMR (400 MHz, CDCl3) δ 7.37-7.31 (m, 7H), 7.23-7.21 (m, 2H), 5.23 (d, J = 12, 1H), 5.21 (d, J = 6.0, 1H), 5.09 (d, J = 12.0, 1H), 3.66 (bs, 1H, OH); 13C NMR (100 MHz, CDCl3) δ 173.0, 136.6, 134.7, 134.3, 128.7, 128.54, 128.51, 128.0, 127.9, 72.2, 67.8; TLC Rf 0.33 (EtOAc/Hexane, 1/4); MS C15H13ClO3 (EI, 276) 276 (M+, 5), 152 (33), 141 (100), 91 (49), 77 (40);HR-MS Calcd. For M+, C15H13ClO3 :
OH
O O O
OH
O O Cl
276.0553, found : 276.0554, Anal. Calcd. for C15H13ClO3 :C, 65.11; H, 4.74. Found: C, 64.98; H, 4.39.; HPLC tR 19.0 min (S, 50%), 24.0 min (R, 50%) (Chiralcel AD-H, i-PrOH/hexane, 6/94, 1.0 ml/min, λ =254 nm). After resolved : 19.0 min (S, minor, 7.05%), 24.0 min (R, major, 92.95%). [α]30 -28.0 (c 1.0, CHCl3) for 86% ee; The absolute configuration was deduced to be R according to the sign of optical rotation.; mp: 109-111oC.
(R)-2-(4-Bromo-phenyl)-2-hydroxy-acetic acid benzyl ester-73
Data: 1H NMR (400 MHz, CDCl3) δ 7.49-7.47 (m, 2H), 7.43-7.29 (m, 5H), 7.22-7.21 (m, 2H), 5.23 (d, J = 12.0, 1H), 5.17 (d, J = 5.6, 1H), 5.14 (d, J = 12.0, 1H), 3.43 (d, J = 5.6, 1H, -OH); 13C NMR (100 MHz, CDCl3) δ 172.9, 137.1, 134.7, 131.6, 128.5, 128.48, 128.0, 122.4, 72.3, 67.8; TLC Rf 0.38 (EtOAc/Hexane, 1/4); HR-MS Calcd. For M+, C15H13BrO3 : 320.0048, found : 320.0045; Anal. Calcd. for C15H13BrO3 :C, 56.10; H, 4.08. Found: C, 56.09; H, 3.94.; HPLC tR 19.3 min (S, 49.49%), 24.3 min (R, 50.51%) (Chiralcel AD-H, i-PrOH/hexane, 6/94, 1.0 ml/min, λ =254 nm). After resolved : 18.8 min (S, minor, 6.09%), 23.3 min (R, major, 93.91%).
[α]30 -25.76 (c 1.0, CHCl3) for 88% ee; The absolute configuration was deduced to be R according to the sign of optical rotation.; mp: 107-109oC.
(R)-2-Hydroxy-2-(o-tolyl)-acetic acid benzyl ester-74
Data: 1H NMR (400 MHz, CDCl3) δ 7.31-7.28 (m, 4H), 7.23-7.17 (m, 5H), 5.42 (d, J = 5.2, 1H), 5.25 (d, J = 12.4, 1H), 5.15 (d, J = 5, 12.4, 1H), 3.35 (d, J = 5.2, 1H, -OH), 2.40 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 173.9, 136.5, 136.3, 135.0, 130.7, 128.44, 128.38, 128.3, 127.8, 126.7, 126.2, 70.4, 67.4, 19.2; TLC Rf 0.38
OH
O O OH
O O Br
(EtOAc/Hexane, 1/6); MS C16H16O3 (EI, 256) 256 (M+, 1), 120 (100), 90 (38);
HR-MS Calcd. For M+, C16H16O3 : 256.1099, found : 256.1096; Anal.
Calcd. for C16H16O3 :C, 74.98; H, 6.29. Found: C, 74.53; H, 5.95.; HPLC tR 16.5 min (S, 50%), 20.8 min (R, 50%) (Chiralcel AD-H, i-PrOH/hexane, 6/94, 1.0 ml/min, λ =254 nm). After resolved : 16.5 min (S, minor, 7.86%), 20.8 min (R, major, 92.14%). [α]29 -70.92 (c 1.0, CHCl3) for 84% ee; The absolute configuration was deduced to be R according to the sign of optical rotation.
(R)-2-(2-Chloro-phenyl)-2-hydroxy-acetic acid benzyl ester-75
Data: 1H NMR (400 MHz, CDCl3) δ 7.28-7.25 (m, 2H), 7.20-7.10 (m, 7H), 5.53 (d, J = 5.2, 1H), 5.14 (d, J = 12.8, 1H), 5.07 (d, J = 12.8, 1H), 3.54 (d, J = 5.2, 1H, OH);
13C NMR (100 MHz, CDCl3) δ 173.0, 135.9, 134.9, 133.5, 129.9, 129.7, 128.7, 128.4, 128.3, 127.7, 127.1, 70.4, 67.7; TLC Rf 0.39 (EtOAc/Hexane, 1/4); MS C15H13ClO3
(ESI, 275) 299 (M+Na++H+, 6), 572 (2M+Na+, 51); Anal. Calcd. for C15H13ClO3 :C, 65.11; H, 4.74. Found: C, 65.17; H, 4.47.; HPLC tR 19.3 min (S, 50%), 28.9 min (R, 50%) (Chiralcel AD-H, i-PrOH/hexane, 6/94, 1.0 ml/min, λ
=254 nm). After resolved : 19.3 min (S, minor, 2.87%), 23.9 min (R, major, 97.13%).
[α]23 -79.09 (c 1.0, CHCl3) for 94% ee; The absolute configuration was deduced to be R according to the sign of optical rotation.
(R)-2-Hydroxy-2-(2-nitro-phenyl)-acetic acid benzyl ester-76
Data: 1H NMR (400 MHz, CDCl3) δ 8.00 (d, J = 8.0, 1H), 7.66-7.60 (m, 2H), 7.50 (td, J = 8.0, 1.6, 1H,), 7.32-7.30 (m, 3H), 7.22-7.20 (m, 2H), 5.89 (d, J = 4.8, 1H), 5.22 (d, J = 12.0, 1H), 5.16 (d, J = 12.0, 1H), 3.59 (d, J = 5.2, 1H, OH); 13C
OH
O O Cl
OH
O O NO2
NMR (100 MHz, CDCl3) δ 171.6, 147.9, 134.6, 133.4, 132.9, 129.8, 129.3, 128.5, 128.1, 125.1, 70.2, 68.1; TLC Rf 0.36 (EtOAc/Hexane, 1/3); HR-MS Calcd. For M+, C15H15NO5 : 287.0794, found : 287.0791; Anal. Calcd. for C15H13NO3
(287.27) :C, 62.72; H, 4.56. Found: C, 62.64; H, 4.65.; HPLC tR 24.8 min (S, 50.26%), 27.4 min (R, 49.74%) (Chiralcel AD-H, i-PrOH/hexane, 4/96, 1.0 ml/min, λ
=254 nm). After resolved : 24.8 min (S, minor, 9.55%), 27.5 min ( R, major, 90.45 %).
[α]31 -260.56 (c 1.0, CHCl3) for 81% ee; The absolute configuration was deduced to be R according to the sign of optical rotation.; mp: 89-91oC
(R)-2-Hydroxy-2-(naphthalen-1-yl)-acetic acid benzyl ester-77
Data: 1H NMR (400 MHz, CDCl3) δ 8.17-8.14 (m, 1H), 7.89-7.84 (m, 2H), 7.53-7.42 (m, 4H), 7.25-7.21 (m, 3H), 7.10-7.08 (m, 2H), 5.88 (d, J = 5.2, 1H), 5.25 (d, J
= 12.4, 1H), 5.13 (d, J = 12.4, 1H), 3.47 (d, J = 4.8, 1H); 13C NMR (100 MHz, CDCl3) δ 173.4, 134.8, 133.87, 133.86, 130.9, 129.3, 128.6, 128.3, 128.1, 127.7, 126.4, 125.7, 125.6, 125.1, 123.7, 71.3, 67.4; TLC Rf 0.34 (EtOAc/Hexane, 1/4); MS C19H16O3 (EI, 292) 292 (M+, 13), 157 (100), 129 (48), 128 (50), 91 (18); HR-MS Calcd. For M+, C19H16O3 : 292.1094, found : 292.1099; HPLC tR 28.2 min (S, 50.38%), 32.0 min (R, 49.62%) (Chiralcel AD-H, i-PrOH/hexane, 6/94, 1.0 ml/min, λ =254 nm).
After resolved : 28.5 min (S, minor, 9.76%), 32.4 min (R, major, 90.24%). [α]28 -93.44 (c 1.0, CHCl3) for 80% ee; The absolute configuration was deduced to be R according to the sign of optical rotation.
(R)-1-Hydroxy-2-(naphthalen-1-yl)-acetic acid benzyl ester-78 OH
O O
Data: 1H NMR (400 MHz, CDCl3) δ 7.91 (s, 1H), 7.86-7.82 (m, 2H), 7.54-7.50 (m, 3H), 7.31-7.29 (m, 3H), 7.22-7.20 (m, 2H), 5.41 (s, 1H), 5.27 (d, J = 12.3, 1H), 5.15 (d, J = 12.3, 1H); 13C NMR (100 MHz, CDCl3) δ 173.4, 135.5, 134.9, 133.3, 133.1, 128.5, 128.4, 128.39, 128.1, 128.0, 127.6, 126.28, 126.27, 125.9, 124.2, 73.1, 67.7; TLC Rf 0.32 (EtOAc/Hexane, 1/4); MS C19H16O3 (ESI, 292) 315 (M+Na+, 6), 607 (2M+Na+, 100); Anal. Calcd. for C19H16O3: C, 78.06; H, 5.52. Found: C, 78.06; H, 5.43.HPLC tR 28.2 min (S, 50.38%), 32.0 min (R, 49.62%) (Chiralcel AD-H, i-PrOH/hexane, 6/94, 1.0 ml/min, λ =254 nm). After resolved : 28.5 min (S, minor, 9.76%), 32.4 min (R, major, 90.24%).
[α]28 -93.44 (c 1.0, CHCl3) for 80% ee; The absolute configuration was deduced to be R according to the sign of optical rotation.; mp: 121-123oC.
(R)-2-(Furan-2-yl)-2-hydroxy-acetic acid benzyl ester-7965
Data: 1H NMR (400 MHz, CDCl3) δ 7.39 (d, J = 1.2, 1H), 7.37-7.32 (m, 3H), 7.31-7.26 (m, 2H), 6.53 (d, J = 1.6, 2H), 5.27 (d, J = 12.4 H), 5.25 (s, 1H ), 5.24 (d, J = 12.4, 1H); 13C NMR (100 MHz, CDCl3) δ 171.3, 150.6, 143.0, 134.8, 128.6, 128.50, 128.1, 110.5, 108.7, 67.9, 66.9; MS C13H12O4 (ESI, 232) 255 (M+Na+, 30), 487 (2M+Na+, 100); TLC Rf 0.20 (EtOAc/Hexane, 1/19); HPLC tR 20.0 min (S, 50%), 26.0 min (R, 50%) (Chiralcel AD-H, i-PrOH/hexane, 6/94, 1.0 ml/min, λ =254 nm). After resolved : 20.0 min (S, minor, 22.26%), 26.0 min (R, major, 77.74%). [α]32 -28.5 (c 1.0, CHCl3) for 55% ee; The absolute configuration was deduced to be R according to the sign of optical rotation.
OH
O O
OH
O O O
(R)-2-Hydroxy-2-(thiophen-2-yl)-acetic acid benzyl ester-80
Data: 1H NMR (400 MHz, CDCl3) δ 7.38-7.34 (m, 3H ), 7.31-7.28 (m, 3H), 7.09 (dd, J = 6.6, 1.0, 1H ), 6.98 (dd, J = 5.4, 4, 1H), 5.47 (s, 1H), 5.38 (d, J = 12.4, 1H), 5.21 (d, J =12.4, 1H), 3.47 (s, 1H, OH); 13C NMR (100 MHz, CDCl3) δ 172.3, 141.2, 134.7, 128.6, 128.55, 128.17, 126.8), 125.7, 125.4, 69.1, 68.0; TLC Rf 0.22 (EtOAc/Hexane, 1/19); MS C13H12O3S (ESI, 248) 519 (2M+Na+, 100); HR-MS Calcd. For M+, C13H12O3S: 248.0507, found: 248.0503; HPLC tR 19.6 min (S, 49.30%), 23.7 min (R, 50.70%) (Chiralcel AD-H, i-PrOH/hexane, 4/96, 1.0 ml/min, λ
=254 nm). After resolved : 19.8 min (S, minor, 2.59%), 23.92 min (R, major, 97.4%).
[α]31 -16.72 (c 1.0, CHCl3) for 95 % ee; The absolute configuration was deduced to be R according to the sign of optical rotation.
(R)-2-Hydroxy-4-phenyl-but-3-enoic acid methyl ester-8166
Data: 1H NMR (400 MHz, CDCl3) δ 7.41-7.39 (d, J = 7.2, 2H), 7.35-7.31 (t, J = 7.2, 2H), 7.28-7.24 (t, J = 7.2, 1H), 6.81 (d, J = 16.0, 1H), 6.26 (dd, J = 16.0, 5.6, 1H), 4.86 (d, J = 5.2, 1H), 3.83 (s, 3H, OCH3), 3.16 (bs, 1H, OH); 13C NMR (100 MHz, CDCl3) δ173.7, 136.0, 132.3, 128.5, 128.0, 126.6, 125.2, 71.3, 52.9; MS C11H12O3 (EI, 192) 192 (M+, 2), 147 (28), 133 (15), 131 (100), 102 (41), 77 (34), 51 (21); TLC Rf
0.30 (EtOAc/Hexane, 1/3); HPLC tR 23.4 min (S, 48.11%), 25.5 min (R, 51.89%) (Chiralcel AD-H, i-PrOH/hexane, 4/96, 1.0 ml/min, λ =254 nm). After resolved : 23.8 min (S, minor, 1.91%), 25.7 min (R, major, 98.09%). [α]29 -100.42 (c 1.0, CHCl3) for 96% ee (lit. [α]20 -115 (c 1.0, CHCl3) for (R)-); The absolute configuration was deduced to be R according to the sign of optical rotation.
OH O O
OHO O S
(R)-2-Hydroxy-4-phenyl-but-3-ynoic acid ethyl ester -8267
Data: 1H NMR (400 MHz, CDCl3)δ 7.46 (dd, J = 7.6, 1.6, 2H), 7.34-7.31 (m, 3H), 5.06 (s, 1H), 4.36 (q, J = 7.2, 2H), 1.36 (t, J = 7.2, 3H); 13C NMR (100 MHz, CDCl3) δ 170.3, 131.8, 128.8, 128.2, 121.8, 85.3, 84.2, 62.8, 61.9, 14.0; MS C12H12O3
(ESI, 204) 227 (M+Na+, 28), 431 (2M+Na+, 67), 635 (3M+Na+, 100); TLC Rf 0.36 (EtOAc/Hexane, 1/5); HPLC tR 22.05 min (S, 49.97%), 24.47 min (R, 50.03%) (Chiralcel AD-H, i-PrOH/hexane, 3/97, 1.0 ml/min, λ =254 nm). After resolved : 21.62 min (S, major, 20.67%), 23.78 min (R, minor, 79.33%). [α]25 -48.64 (c 1.0, CHCl3) for 59% ee; The absolute configuration was deduced to be R according to the sign of optical rotation.
(R)-2-Hydroxy-propionic acid benzyl ester-8368
Data: 1H NMR (400 MHz, CDCl3) δ 7.40-7.34 (m, 5H), 5.21 (s, 2H), 4.32 (q, J = 6.8, 1H), 2.84 (bs, 1H, OH), 1.44 (d, J = 6.8, 3H); 13C NMR (100 MHz, CDCl3) δ 175.5, 135.2, 128.6, 128.5, 128.2, 67.3, 66.8, 20.3; MS C10H12O3 (ESI, 180) 204 (M+Na++H+, 100), 383 (2M+Na+, 84); TLC Rf 0.30 (EtOAc/Hexane, 1/7); HPLC tR
13.4 min (S, 41.95%), 15.9 min (R, 58.05%) (Chiralcel AS, i-PrOH/hexane, 2/98, 1.0 ml/min, λ =254 nm). After resolved : 14.7 min (S, minor, 31.32%), 17.7 min (R, major, 68.68%). [α]28 +19.8 (c 2.0, CHCl3) for 23% ee (lit. [α]24 13.4 (c 2.0, CHCl3) for (R)-);
The absolute configuration was deduced to be R according to the sign of optical rotation.
OH
O O
OH
O
O
(R)-2-Hydroxyl-4-methyl-pentanoic acid benzyl ester -8469
Data: 1H NMR (400 MHz, CDCl3) δ 7.38-7.35 (m, 5H ), 5.21 (s, 2H), 4.25 (dt, J = 8.0, J = 5.6, 1H), 2.69-2.66 (m, 1H, OH), 1.89 (heptet, J = 6.8, 1H), 1.60-1.56 (m, 2H), 0.94 (s, J = 6.8, 3H), 0.93 (d, J = 6.8, 3H); 13C NMR (100 MHz, CDCl3) δ 175.7, 135.2, 128.6, 128.5, 128.3, 69.2, 67.3, 43.4, 24.4, 23.2, 21.5; MS C13H18O3 (EI, 222) 222 (M+, 3), 91 (100), 87 (31), 69 (36); TLC Rf 0.30 (EtOAc/Hexane, 1/15); HPLC tR
8.4 min (S, 50.18%), 10.7 min (R, 49.82%) (Chiralcel AS, i-PrOH/hexane, 2/98, 1.0 ml/min, λ =254 nm). After resolved : 8.4 min (S, minor, 14.44%), 10.8 min (R, major, 85.56%). [α]32 +11.36 (c 1.02, CHCl3) for 71% ee (lit.40 [α]23 -15.5 (c 1.02, CHCl3) for (S)-); The absolute configuration was deduced to be R according to the sign of optical rotation.
(R)-2-Hydroxy-3-phenyl-propionic acid benzyl ester-8569
Data: 1H NMR (400 MHz, CDCl3) δ 7.43-7.35 (m, 5H ), 7.31-7.28 (m, 3H), 7.20- 7.19 (m, 2H), 5.23 (d, J = 12.0, 1H), 5.19 (d, J = 12.0, 1H), 4.52 (td, J = 4.8, 4.8, 1H), 3.16 (dd, J = 12.0, 4.8, 1H, -OH) , 3.04-2.96 (m, 2H); 13C NMR (100 MHz, CDCl3) δ 173.9, 136.1, 134.9, 129.4, 128.5, , 128.48, 128.3, 126.7, 71.2, 67.2, 40.4;
MS C16H16O3 ( EI, 256) 256 (M+, 2), 238 (25), 192 (38), 121 (84), 103 (26), 91 (100), 77 (15); TLC Rf 0.38 (EtOAc/Hexane, 1/5); HPLC tR 16.6 min (S, 50.43%), 19.9 min (R, 49.57%) (Chiralcel AS, i-PrOH/hexane, 2/98, 1.0 ml/min, λ =254 nm). After resolved : 16.1 min (S, minor, 2.24%), 18.7 min (R, major, 97.76%). [α]31 +70.28 (c 1.0, CHCl3) for 95% ee (lit.41 [α]25 -54.2 (c 4.0, CHCl3) for (S)-); The absolute configuration was deduced to be R according to the sign of optical rotation.
OH
O O
OH
O
O
(2R, 3S)-(-)-N-Benzoylamino-2-hydroxy-3-phenyl-propionic methyl ester-8670
Data: 1H NMR (400 MHz, CDCl3) δ 7.76 (d, J = 7.4, 2H), 7.53-7.30 (m, 5H), 7.01 (d, J = 9.0, 1H), 5.74 (dd, J = 9.0, 1.7, 1H), 4.63 (d, J = 1.9, 1H), 3.84 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 173.4, 166.9, 138.7, 134.1, 131.8, 128.7, 128.6, 127.9, 127.1, 127.0, 73.2, 55.8, 53.3; MS C17H17NO4 (ESI, 299) 203 (M+Na++H+, 75), 381 (2M+Na+, 100); TLC Rf 0.22 (EtOAc/Hexane, 1/2); HPLC tR
27.43 min (2R, 3S, 49.39%), 31.45 min (2S, 3R, 50.61%) (Chiralcel AD, i-PrOH/hexane, 10/90, 1.0 ml/min, λ =254 nm). After resolved :27.62 min (2R, 3S), major, >99%. [α]30 -56.2 (c 1.0, MeOH) for 99% ee (lit. [α]25-48.7 (c 1.0, MeOH) for (2R, 3S)); The absolute configuration was deduced to the sign of optical rotation.; mp:
184-186oC.
(R)-2-Cyclohexyl-2-hydroxyl-acetic acid benzyl ester -8771
Data: 1H NMR (400 MHz, CDCl3) δ 7.38- 7.34 (m, 5H ), 5.22 (s, 2H), 4.06 (dd, J = 6.4, 3.6, 1H), 2.74 (d, J = 6.0, 1H, OH), 1.77-1.63 (m, 5H), 1.38-1.16 (m, 6H); 13C NMR (100 MHz, CDCl3) δ 174.7, 135.2, 128.6, 128.5, 128.3, 74.8, 67.2, 42.0, 29.0, 26.2, 26.18, 26.0, 25.9; MS C15H20O3 (EI, 248) 248 (M+, 3), 113 (49), 95 (100) , 92 (13), 91 (61); TLC Rf 0.35 (EtOAc/Hexane, 1/15); HPLC tR 7.1 min (S, 50.05%), 9.1 min (R, 49.95%) (Chiralcel AS, i-PrOH/hexane, 5/95 1.0 ml/min, λ =254 nm). After resolved : 7.2 min (S, minor, 19.91%), 9.1 min (R, major, 80.09%). [α]32 +5.48 (c 1.0, CHCl3) for 60% ee; The absolute configuration was deduced to be R according to the sign of optical rotation.
O O
OH NH Ph
O
OH
O O
(R)-N-Benzyl-2-hydroxy-2-p-tolyl-acetamide-88:
Data: 1H NMR (400 MHz, CDCl3)δ 7.33-7.27 (m, 5H), 7.19-7.15 (m, 4H), 6.39 (brs, 1H, -NH), 5.05 (s, 1H),
4.48 (dd, J = 14.9, 6.0, 1H), 4.43 (dd, J = 14.9, 6.0, 1H), 3.90 (brs, -OH), 2.35 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 172.4, 138.4, 137.7, 136.5, 129.4, 128.6, 127.53, 127.48, 126.7, 74.0, 43.4, 21.1; MS C16H17NO2 (ESI, 255) 278 (M+Na+, 5), 533 (2M+Na+, 100); TLC Rf 0.31 (EtOAc/Hexane, 1/2); HPLC tR
19.55 min (R, 49.94%), 36.97 min (S, 50.06%) (Chiralcel AD-H, i-PrOH/hexane, 8/92, 1.0 ml/min, λ =254 nm). After resolved : 19.56 min (R, major, 99.82%), 36.19 min (S, minor, 0.18%). [α]24 -22.3 (c 1.0, CHCl3) for >99% ee; The absolute configuration was deduced to be R according to the sign of optical rotation.; Anal. Calcd. For C16H17NO2: C, 75.27; H, 6.71. Found: C, 75.56; H, 6.56.; mp: 103-104oC.
(R)-N-Benzyl-2-hydroxy-2-(4'-methoxyphenyl)acetamide-8973
Data: 1H NMR (400 MHz, CDCl3) δ 7.32-7.27 (m, 5H), 7.18 (d, J = 7.6, 2H), 6.68 (d, J=7.8, 2H), 6.65 (brs, 1H, -NH), 5.00 (s, 1H), 4.43 (dd, J = 14.8, 6.0, 1H), 4.37 (dd, J = 14.8, 6.0, 1H), 3.78 (s, 3H); 13C NMR (100 MHz, CDCl3)δ172.5, 159.8, 137.7, 131.6, 128.7, 128.2, 127.6, 127.5, 114.2, 73.8, 55.3, 43.4; MS C16H17NO3 (ESI, 271) 294 (M+Na+, 6), 565 (2M+Na+, 100); TLC Rf 0.32 (EtOAc/Hexane, 1/2); HPLC tR
29.19 min (S, 50%), 54.40 min (R, 50%) (Chiralcel AD-H, i-PrOH/hexane, 8/92, 1.0 ml/min, λ =254 nm). After resolved : 27.2 min (R, major, 88.66%), 50.67 min (S, minor, 11.34%). [α]25 -47 (c 1.0, CH2Cl2) for 77% ee (lit. [α]25 66 (c 1.0, CHCl3) for (S)-); The absolute configuration was deduced to be R according to the sign of optical rotation.; mp: 105-107oC.
OH
O HN
OH
O HN
O
(R)-N-Benzyl-2-hydroxy-2-(4'-chlorophenyl)acetamide-9073
Data: 1H NMR (400 MHz, CDCl3) δ 7.34-7.25 (m, 7H), 7.18 (d, J = 7.2, 2H), 6.53 (brs, 1H, -NH), 5.05 (s,1H), 4.45 (dd, J = 15.6, 6.0, 1H), 4.40 (dd, J = 15.6, 6.0, 1H);
13C NMR (100 MHz, CDCl3) δ 172.0, 138.0, 137.5, 134.3, 128.73, 128.69, 128.0, 127.6, 127.5, 73.4, 43.3; MS C15H14ClNO2 (ESI, 275) 298 (M+Na+, 6), 573 (2M+Na+, 100); TLC Rf 0.37 (EtOAc/Hexane, 1/2); HPLC tR 16.34 min (R, 49.73%), 36.60 min (S, 50.27%) (Chiralcel AD-H, i-PrOH/hexane, 8/92, 1.0 ml/min, λ =254 nm). After resolved : 16.52 min (R, major, 98.24%), 36.65 min (S, minor,1.76%). [α]25 -57.20 (c 1.0, CHCl3) for >97% ee (lit. [α]26 64 (c 1.0, CHCl3) for (S)-); The absolute configuration was deduced to be R according to the sign of optical rotation; mp:
117-118oC.
(R)-N-Benzyl-2-hydroxy-2-(2'-bromophenyl)acetamide-91:
Data: 1H NMR (400 MHz, CDCl3) δ 7.48 (d, J = 8.4, 2H), 7.35-7.48 (m, 5H), 7.18 (d, J = 8.2, 2H), 6.70 (brs, 1H, -NH), 5.01 (d, J = 3.2, 1H), 4.43 (dd, J = 14.8, 6.0, 1H), 4.38 (dd, J = 14.8, 6.0, 1H), 3.84 (d, J = 3.6, 1H); 13C NMR (100 MHz, CDCl3)δ171.5, 138.3, 137.5, 131.9, 128.8, 128.4, 127.7, 127.6, 122.7, 73.5, 43.5; MS C15H14BrNO2 (ESI, 320) 320 (M +, 10), 344 (M+Na++H+, 12), 663 (2M+Na+, 100);
TLC Rf 0.39 (EtOAc/Hexane, 1/2); HPLC tR 16.24 min (S, 50.69%), 35.24 min (R, 49.31%) (Chiralcel AD-H, i-PrOH/hexane, 8/92, 1.0 ml/min, λ =254 nm). After resolved :16.34 min (R, >99%). [α]28 -72.6 (c 1.0, CHCl3) for >99% ee; The absolute configuration was deduced to be R according to the sign of optical rotation; Anal.
Calcd. For C15H14BrNO2: C, 56.27; H, 4.41. Found: C,56.64; H, 4.21.; mp:142-143oC
OH
O HN
Cl
OH
O HN
Br
(R)-N-Benzyl-2-hydroxy-2-o-tolyl-acetamide-92:
Data: 1H NMR (400 MHz, CDCl3) δ 7.34-7.15 (m, 9H), 6.61 (brs, 1H, -NH), 5.20 (s, 1H), 4.44 (dd, J = 14.8, 6.0, 1H), 4.38 (dd, J=14.8, 6.0, 1H), 2.37 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 172.6, 137.7, 137.4, 136.8, 130.9, 128.6, 128.5, 127.53, 127.5, 127.4, 126.2, 71.9, 43.2, 19.2); MS C16H17NO2 (ESI, 255) 279 (M+Na++H+, 10), 533 (2M+Na+, 100); TLC Rf 0.32 (EtOAc/Hexane, 1/2); HPLC tR 17.76 min (R, 50.78%), 26.86 min (S, 49.22%) (Chiralcel AD-H, i-PrOH/hexane, 8/92, 1.0 ml/min, λ =254 nm). After resolved : 17.02 min (R, major, 96.79%), 25.99 min (S, minor, 3.21%).
[α]24 -20.8 (c 1.0, CHCl3) for 94% ee; The absolute configuration was deduced to be R according to the sign of optical rotation. Anal. Calcd. For C16H17NO2: C, 75.27; H, 6.71. Found: C, 75.27; H, 7.05.; mp: 90-92oC;
(S)-N-Benzyl-2-hydroxy-2-(2'-methoxyphenyl)acetamide-93:
Data: 1H NMR (400 MHz, CDCl3) δ 7.48 (d, J = 7.6, 1H), 7.32-7.27 (m, 3H), 7.15 (d, J = 7.2, 2H), 7.03 (t, J = 7.6, 1H), 6.91 (d, J = 8.0, 1H), 5.44 (s, 1H), 4.50 (dd, J = 14.8, 5.6, 1H), 4.44 (dd, J = 14.8, 5.6, 1H), 4.22 (brs, 1H, -OH), 3.78 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 172.7, 155.8, 137.9, 129.2, 128.6, 128.2, 127.5, 127.4, 127.3, 121.5, 110.8, 69.3, 55.6, 43.6; MS C16H17NO3 (ESI, 271) 294 (M+Na+, 7), 565 (2M+Na+, 100); TLC Rf 0.33 (EtOAc/Hexane, 1/2); HPLC tR 30.65 min (R, 50.21%), 39.88 min (R, 49.79%) (Chiralcel AD-H, i-PrOH/hexane, 10/90, 1.0 ml/min, λ =254 nm). After resolved : 30.17 min (R, minor, 33.11%), 39.79 min (S, minor, 66.89%). [α]29 26 (c 1.0, CHCl3) for 33% ee; The absolute configuration was deduced to be S according to the sign of optical rotation.; Anal.
Calcd. For C16H17NO3: C, 70.83; H, 6.32. Found: C, 70.52; H, 6.19.; mp: 113-115oC.
OH
O HN O
OH
O HN
(R)-N-Benzyl-2-hydroxy-2-(2'-chlorophenyl)acetamide-94:
Data: 1H NMR (400 MHz, CDCl3) δ 7.47 (dd, J = 7.6, 1.6, 1H), 7.38 (dd, J=7.6, 1.6, 1H), 7.39-7.25 (m, 5H), 7.17 (m, 2H), 6.55 (brs, 1H, -NH), 5.55 (d, J = 4.4, 1H), 4.52 (dd, J = 14.8, 6.0, 1H), 4.42 (dd, J = 14.8, 6.0, 1H), 4.10 (d, J = 4.4, 1H, -OH);
13C NMR (100 MHz, CDCl3) δ 171.5, 137.4, 137.2, 132.6, 129.7, 128.7, 128.6, 127.6, 127.4, 70.2, 43.8; MS C15H14ClNO2 (ESI, 275) 299 (M+Na++H+, 96), 573 (2M+Na+, 100); TLC Rf 0.38 (EtOAc/Hexane, 1/2); HPLC tR 17.99 min (R, 51.2%), 22.31 min (S, 50%) (Chiralcel AD-H, i-PrOH/hexane, 10/90, 1.0 ml/min, λ =254 nm). After resolved : 18.04 min (R, major, 95.6%), 22.24 min (S, minor, 4.4%). [α]27 -72.84 (c 1.0, CHCl3) for 91% ee; The absolute configuration was deduced to be R according to the sign of optical rotation.; Anal. Calcd. For C15H14ClNO2: C, 65.34; H, 5.12. Found:
C, 65.14; H, 5.19.; mp: 111-113oC.
(R)-N-Benzyl-2-hydroxy-2-naphthalen-1-yl-acetamide-95:
Data: 1H NMR (400 MHz, CDCl3) δ 8.14 (dd, J = 6.3, 1H), 7.91-7.86 (m, 2H), 7.55-7.54 (m, 3H), 7.45 (t, J=7.6, 1H), 7.29-7.26 (m, 2H), 7.11 (t, J = 3.6, 2H), 6.04
(brs,1H, -NH), 5.61 (s, 1H), 4.47 (dd, J = 15.2, 6.4, 1H), 4.39 (dd, J = 15.2, 6.4, 1H), 4.0 (brs, 1H, -OH); 13C NMR (100 MHz, CDCl3) δ 172.6, 137.5, 134.2, 131.0, 129.8, 128.9, 127.5, 127.47, 127.1, 126.8, 126.1, 125.2, 123.9, 73.2, 43.6; MS C19H17NO2 (ESI, 291) 315 (M+Na++H+, 13), 605 (2M+Na+, 100);
TLC Rf 0.36 (EtOAc/Hexane, 1/2); HPLC tR 24.26 min (R, 50.26%), 36.14 min (S, 49.74%) (Chiralcel AD-H, i-PrOH/hexane, 10/90, 1.0 ml/min, λ =254 nm). After resolved : 24.94 min (R, major, 99.67%), [α]29 -38.8 (c 1.0, CHCl3) for >99% ee; The absolute configuration was deduced to be R according to the sign of optical rotation.;
OH
O HN Cl
OH
O HN
Anal. Calcd. For C19H17NO2: C, 78.33; H, 5.88. Found: C, 78.47; H, 5.52.; mp:
196-197oC.
(R)-N-Benzyl-2-hydroxy-2-naphthalen-2-yl-acetamide-96:
Data: 1H NMR (400 MHz, DMSO-D6) δ 8.63 ( t, J = 6.0, 1H), 7.92-7.86 (m, 4H), 7.60 ( s, 1H), 7.51-7.49 (m, 2H), 7.26-7.20 (m, 5H), 6.37 (d, J = 4.4, 1H), 5.14 (d, J = 4.2, 1H), 4.29 (d, J = 6.2, 2H); 13C NMR (100 MHz, DMSO-D6) δ 172.3, 139.6, 138.9, 132.7, 132.5, 128.2, 127.8, 127.6, 127.5, 127.2, 126.8, 126.2, 126.0, 125.3, 124.9, 73.8, 41.9; MS C19H17NO2 (ESI, 291) 291 (M+, 100); TLC Rf 0.27 (EtOAc/Hexane, 1/2); HPLC tR 31.92 min (R, 50.62%), 66.75 min (S, 49.38%) (Chiralcel AD-H, i-PrOH/hexane, 8/92, 1.0 ml/min, λ =254 nm). After resolved : 34.56 min (R, major,
>99%), [α]29 -62.0 (c 1.0, CHCl3) for >99% ee; The absolute configuration was deduced to be R according to the sign of optical rotation.; Anal. Calcd. For C19H17NO2: C, 78.33; H, 5.88. Found: C, 78.69; H, 6.06.; mp: 217-219oC.
(R)-N-Benzyl-2-furan-2-yl-2-hydroxy-acetamide-97:
Data: 1H NMR (400 MHz, CDCl3) δ 7.35-7.21 (m, 5H), 6.94 (brs, 1H, -NH), 6.33 (d, J = 3.2, 1H), 6.31 (dd, J = 3.2, 1.6, 1H), 5.10 (brs, 1H), 4.46 (dd, J = 14.9, 6.0, 1H), 4.41 (dd, J = 14.9, 6.0, 1H); 13C NMR (100 MHz, CDCl3) δ 170.0, 151.6, 142.9, 137.4, 128.7, 127.54, 127.52, 110.5, 108.6, 67.7, 43.4; MS C13H13NO3 (ESI, 231) 255 (M+Na++Na+, 33), 485 (2M+Na+, 56); TLC Rf 0.28 (EtOAc/Hexane, 1/2); HPLC tR
25.3 min (R, 49.54%), 36.7 min (S, 50.46%) (Chiralcel AD-H, i-PrOH/hexane, 8/92, 1.0 ml/min, λ =254 nm). After resolved : 22.74 min (R, major, 92.39%), 30.40 min (S, minor, 7.61%). [α]25 -21.5 (c 1.0, CHCl3) for 86% ee; The absolute configuration was
OH
O HN
OH
O HN O
deduced to be R according to the sign of optical rotation; Anal. Calcd. For C19H17NO2: C, 67.52; H, 5.67. Found: C, 67.21; H, 5.37.; mp: 94-95oC.
(R)-N-Benzyl-2-hydroxy-2-thiophen-2-yl-acetamide-9873
Data: 1H NMR (400 MHz, CDCl3) δ 7.33-7.27 (m, 4H), 7.22-7.20 (m, 2H), 7.08 (d, J = 3.2, 1H), 6.83 (brs, 1H, -NH), 5.30 (brs, 1H), 4.50 (dd, J = 15.2, 6.0, 1H), 4.39 (dd, J = 15.2, 6.0, 1H); 13C NMR (100 MHz, CDCl3) δ 171.2, 142.3, 137.5, 128.7, 127.6, 126.9, 126.1, 70.1, 43.5; MS C13H13NO3 (ESI, 247) 270 (M+Na+, 12), 485 (2M+Na+, 100); TLC Rf 0.29 (EtOAc/Hexane, 1/2); HPLC tR
20.10 min (R, 50%), 30.62 min (S, 50%) (Chiralcel AD-H, i-PrOH/hexane, 8/92, 1.0 ml/min, λ =254 nm). After resolved : 20.13 min (R, major, 99.59%), 30.68 min (S, minor, 0.41%). [α]26 -15.08 (c 1.0, CHCl3) for >99% ee (lit. [α]2527.4 (c 1.0, CHCl3) for (S)-); The absolute configuration was deduced to be R according to the sign of optical rotation.; mp: 93-95oC.
(R)-2-Hydroxy-4-phenyl-but-3-enoic acid methylamide-99:
Data: 1H NMR (400 MHz, CDCl3) δ 7.37-7.16 (m, 10H), 6.85 (dt, J = 5.2, 1H, -NH), 6.73 (dd, J = 16.0, 0.92, 1H), 6.33 (dd, J = 16.0, 6.4, 1H), 4.76 (dd, J = 6.4, 1.2, 1H), 4.46 (dd, J = 14.8, 3.2, 1H), 4.41 (dd, J = 14.8, 3.2, 1H); 13C NMR (100 MHz, CDCl3) δ 172.3, 137.5, 135.9, 132.5, 128.6, 128.5, 127.9, 127.54, 127.48, 126.7, 126.6, 72.7, 43.3; MS C17H17NO2 (ESI, 267) 289 (M+Na+, 100), 553 (2M+Na+, 73);
TLC Rf 0.28 (EtOAc/Hexane, 1/2); HPLC tR 19.09 min (S, 49.88%), 28.57 min (R, 50.12%) (Chiralcel AD-H, i-PrOH/hexane, 8/92, 1.0 ml/min, λ =254 nm). After resolved : 19.15 min (R, major, >99%). [α]27 -24.3 (c 1.0, CHCl3) for >99% ee; The absolute configuration was deduced to be R according to the sign of optical rotation;
OH
O HN S
OH
O HN
Anal. Calcd. For C17H17NO2: C, 76.38; H, 6.41. Found: C, 76.53; H, 6.29.; mp:
127-128oC.
(R)-N-benzyl-2-hydroxy-propionamide-10074
Data: 1H NMR (400 MHz, CDCl3) δ 7.32-7.21 (m, 5H), 4.37 (d, J = 6.0, 2H), 4.19 (q, J = 6.8, 1H), 4.02 (brs, 1H,
-OH), 1.38 (d, J = 6.8, 3H); 13C NMR (100 MHz, CDCl3) δ 175.2, 137.7, 128.6, 128.3, 127.44, 127.41, 68.1, 42.9, 21.0; MS (EI, 70 eV) 277 (M+, 100), 165 (66), 148 (70); TLC Rf 0.4 (EtOAc/Hexane, 1/8); MS C10H13NO2
(ESI, 179) 203 (M+Na++H+, 75), 381 (2M+Na+, 100); TLC Rf 0.26 (EtOAc/Hexane, 1/1); HPLC tR 19.21 min (R, 50.17%), 23.32 min (S,49.83%) (Chiralcel AD-H, i-PrOH/hexane, 4/96, 1.0 ml/min, λ =254 nm). After resolved: 19.11 min (R, major, 63.89%), 23.08 min (S, minor, 36.11 %). [α]25 +14.2.1 (c 1.0, CHCl3) for37% ee (lit.
[α]26-20.6 (c 1.0, CHCl3) for (S)-); The absolute configuration was deduced to be R according to the sign of optical rotation.; mp: 47-48oC.
(R)-2-Hydroxy-4-methyl-pentanoic acid benzylamide -10175
Data: 1H NMR (400 MHz, CDCl3) δ 7.36-7.26 (m, 5H), 6.93 (brs, 1H, -NH), 4.45 (dd, J = 5.9, 2.3, 2H), 4.18 (ddd, J = 6.4, 5.2, 5.1, 1H), 2.98 (d, J = 5.1, 1H, -OH), 1.86 (m, 1H), 1.72-1.65; 1.60-1.52 (Complex m, 2H, each 1H), 0.97 (d, J = 3.9, 3H), 0.95 (d, J
= 3.9, 3H); 13C NMR (100 MHz, CDCl3) δ174.7, 137.9, 128.7, 127.6, 127.5, 70.7, 43.8, 24.5, 23.4, 21.3; MS C13H19NO2 (ESI, 221) 244 (M+Na+, 20), 465 (2M+Na+, 100); TLC Rf 0.32 (EtOAc/Hexane, 1/2); HPLC tR 8.60 min (R, 49.56%), 12.92 min (S, 50.44%) (Chiralcel AD-H, i-PrOH/hexane, 8/92, 1.0 mL/min, λ =254 nm). After resolved : 8.88 min (S, major, 2.47%), 12.96 min (R, minor, 97.53%), 95 % ee. [α]29 -27.91 (c1, CHCl3) for 95% ee; The absolute configuration was deduced to be R
OH
O HN OH
O HN
according to the sign of optical rotation.; mp: 94-95oC.
(R)-N-benzyl-2-hydroxy-3-phenyl-propionamide -10276
Data: 1H NMR (400 MHz, CDCl3) δ 7.34-7.20 (m, 10H), 6.76 (brs, 1H, -NH), 4.49 (dd, J = 14.8, 6.4, 1H), 4.43 (dd, J = 14.8, 6.4, 1H), 4.37 (dd, J = 8.4, 4.0, 1H), 3.28 (dd, J = 8.4, 8.0, 1H); 13C NMR (100 MHz, CDCl3) δ 172.6, 137.8, 136.8, 129.6, 128.6, 127.7, 127.5, 126.9, 72.8, 43.0, 40.8; MS C16H17NO2 (ESI, 255) 279 (M+Na++H+, 13), 533 (2M+Na+, 100); TLC Rf 0.30 (EtOAc/Hexane, 1/2); HPLC tR
8.06 min (S, 49.56%), 12.92 min (R, 50.44%) (Chiralcel AD-H, i-PrOH/hexane, 8/92, 1.0 ml/min, λ =254 nm). After resolved : 8.88 min (S, major, 97.53%), 12.96 min (R, minor, 2.47%). [α]30 49.7 (c 1.15, CHCl3) for >99% ee (lit. [α]23-57.7 (c 1.15, CHCl3) for (S)-); The absolute configuration was deduced to be R according to the literature.;
mp: 82-83oC.
(R)-N-Benzyl-2-cyclohexyl-2-hydroxy-acetamide-10377
Data: 1H NMR (400 MHz, CDCl3) δ 7.35-7.26 (m, 5H), 6.90 (brs, 1H, -NH), 4.48 (dd, J = 14.8, 6.0, 1H), 4.43 (dd, J = 14.8, 6.0, 1H), 3.99 (d, J = 2.4, 1H), 2.30 (brs, 1H, -OH), 1.85-1.65 (m, 5H), 1.65 (m, 1H), 1.31-1.11 (m, 5H); 13C NMR (100 MHz, CDCl3)δ173.1, 138.0, 128.7, 127.5, 76.2, 43.1, 41.7, 29.6, 26.3, 26.1, 25.9, 25.8; MS C15H21NO2 (ESI, 247) 270 (M+Na+, 18), 517 (2M+Na+, 100); TLC Rf 0.38 (EtOAc/Hexane, 1/2); HPLC tR 12.39 min (R, 50.11%), 17.37 min (S, 49.89%) (Chiralcel AD-H, i-PrOH/hexane, 8/92, 1.0 mL/min, λ =254 nm). After resolved : 12.34 min (S, major, 4.89%), 17.27 min (R, minor, 95.11%), 90 % ee. [α]30 -16.8 (c, CHCl3) for 90% ee; The absolute configuration was deduced to be R according to the
OH
O HN
OH
O HN
sign of optical rotation.; mp: 94-95oC.
Oxo-phenyl-acetic acid methyl ester- 68a’78
Data: 1H NMR (400 MHz, CDCl3) δ 8.03-8.01 (m, 2H) , 7.68 (t, J = 7.4, 1H), 7.52 (t, J = 7.8, 2H), 3.99 (s, 3H, OCH3); 1 3C NMR (100 MHz, CDCl3) δ 186.0, 164.0, 134.9, 132.3, 130.0, 128.8, 52.7; MS C9H8O3 (EI, 164) 164 (M+, 6), 105 (100), 77 (45), 51(13); TLC Rf 0.33 (EtOAc/Hexane, 1/15)
Oxo-phenyl-acetic acid ethyl ester -68b’ 78
Data: 1H NMR (400 MHz, CDCl3)δ 8.02 (d, J = 7.6, 2H), 7.67 (d, J = 7.6, 1H), 7.52 (d, J = 7.6, 2H), 4.46 (q, J = 7.2, 2H), 1.43 (t, J = 7.2, 3H, CH3);
13C NMR (100 MHz, CDCl3) δ 186.4, 163.8, 134.8, 132.4, 130.0, 128.8, 62.3, 14.1;
MS C10H10O3 (EI, 178) 178 (M+, 9), 105 (100), 77 (14); 178.18; TLC Rf 0.39 (EtOAc/Hexane, 1/23)
Oxo-phenyl-acetic acid isopropyl ester -68c’ 79
Data: 1H NMR (400 MHz, CDCl3) δ 8.00-7.98 (m, 2H ), 7 . 6 8 - 7 . 6 4 ( m , 1 H ) , 7 . 5 1 ( t , J = 7 . 8 , 2 H ) , 5.33 (heptet, J = 6.0, 1H), 1.41 (d, J = 6.0, 6H); 13C NMR (100 MHz, CDCl3) δ 186.5, 163.5, 134.6, 132.3, 129.7, 128.7, 70.4, 21.4; MS C11H12O3 : (EI, 1921) 92 (M+, 6), 105 (100), 77 (36), 51(17), 43(30), 41(13); TLC Rf
0.32 (EtOAc/Hexane, 1/13) O
O O
O
O O
O
O
O
Oxo-phenyl-acetic acid benzyl ester-68d’80
Data: 1H NMR (400 MHz, CDCl3) δ 7.98-7.96 (m, 2H), 7.69-7.63 (m, 1H), 7.51-7.37 (m, 7H), 5.42 (s, 2H);
13C NMR (100 MHz, CDCl3) δ 185.9, 163.5, 134.7, 134.4, 132.2, 129.7, 128.7, 128.6, 128.5, 128.3, 67.5; MS C15H12O3 (ESI, 240) 264 (M+Na++H+, 87), 504 (2M+Na++H+, 72); TLC Rf 0.32 (EtOAc/Hexane, 1/25)
Oxo-phenyl-acetic acid benzhydryl ester-68e’81
Data: 1H NMR (400 MHz, CDCl3) δ 7.93-7.91 (m, 2H ), 7.64 (t, J = 7.2, 1H), 7.49-7.33 (m, 12H), 7.17 (s, 1H);
13C NMR (100 MHz, CDCl3) δ 186.0, 163.0, 138.9, 134.9, 132.4, 130.0, 128.9, 128.7, 128.4, 127.2, 78.8; MS C21H16O3 (ESI, 316) 339 (M+Na+, 35), 656 (2M+Na+, 100); TLC Rf 0.30 (EtOAc/Hexane, 1/30)
Oxo-phenyl-acetic acid phenyl ester-68f’82
Data: 1H NMR (400 MHz, CDCl3) δ 8.13 (d, J = 7.2, 2H ), 7.70 (t, J = 7.2, 1H), 7.56 (t, J = 8.0, 2H), 7.46 (t, J = 7.6, 2H),7.34-7.28 (m, 3H); 13C NMR (100 MHz, CDCl3) δ 185.2, 161.8, 149.9, 135.2, 132.3, 130.1, 129.7, 129.0, 126.7, 121.2; MS C14H10O3 (EI, 226) 226 (M+, 12), 133 (68), 105 (100), 93 (42); TLC Rf 0.28 (EtOAc/Hexane, 1/30).
Oxo-p-tolyl-acetic acid benzyl ester-‘70
Data: 1H NMR (400 MHz, CDCl3) δ 7.88-7.86 (m, 2H ), 7.46-7.38 (m, 5H), 7.29-7.27 (m, 2H), 5.41 (s, 2H), 2.42 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 185.6, O
O O
O
O O
O
O O O
O O
163.8, 146.2, 134.6, 130.1, 129.9, 129.6, 128.68, 128.65, 128.5, 67.6, 21.8; TLC Rf
0.36 (EtOAc/Hexane, 1/15); MS C16H14O3 (ESI, 254) 278 (M+Na++H+, 87), 531 (2M+Na++H+, 100); HR-MS Calcd. For M+, C16H14O3 : 254.0943, found : 254.0950; Anal. Calcd. for C16H14O3 : C, 75.57; H, 5.55. Found: C, 75.70;
H, 5.48.
Oxo-(4-methoxy-phenyl)-acetic acid benzyl ester 71’
Data: 1H NMR (400 MHz, CDCl3) δ 7.95 (d, J = 8.4, 2H), 7.44-7.37 (m, 5H), 6.94 (d, J = 8.8, 2H), 5.40 (s, 2 H ) , 3 . 8 7 ( s , 3 H , O C H3) ; 1 3C N M R ( 1 0 0 MHz,CDCl3) δ 184.5, 165.0, 163.9, 134.7, 132.5, 128.7 , 128.5, 125.4, 114.2, 67.5, 55.6; TLC Rf 0.38 (EtOAc/Hexane, 1/10); HR-MS Calcd. For M+, C16H14O4 : 270.0892, found : 270.0898; Anal. Calcd. for C16H14O4: C, 71.10;
H, 5.22. Found: C, 71.21; H, 5.02.
(4-Chloro-phenyl)-oxo-acetic acid methyl ester -72’
Data: 1H NMR (400 MHz, CDCl3) δ 7.95-7.92 (m, 2H ) , 7.46-7.37 (m, 7H), 5.41 (s, 2H); 13C NMR (100 MHz, CDCl3) δ 184.4, 163.0, 141.6, 134.4, 131.3, 130.8, 129.2, 128.8, 128.7, 128.6, 67.9; TLC Rf 0.39 (EtOAc/Hexane, 1/17); HR-MS Calcd. For M+, C15H11ClO3: 274.0397, found : 274.0400; Anal. Calcd. for C15H11ClO3: C, 65.58; H, 4.04. Found: C, 65.30; H, 4.07.
(4-Bromo-phenyl)- oxo-acetic acid benzyl ester-73’
Data: 1H NMR (400 MHz, CDCl3) δ 7.86-7.84 (m, 2H), O
O O O
O
O O Cl
7.63-7.61 (m, 2H), 7.46-7.38 (m, 5H), 5.41 (s, 2H); 13C NMR (100 MHz, CDCl3) δ 184.6, 162.9, 134.3, 132.2, 131.3, 131.2, 130.5, 128.8, 128.7, 128.5, 128.2, 67.8; TLC Rf 0.35 (EtOAc/Hexane, 1/30); HR-MS Calcd. For M+, C15H13BrO3 : 317.9892, found : 317.9885;Anal. Calcd. for C15H13BrO3: C, 56.45; H, 3.47. Found: C, 56.55; H, 3.63. mp: 50-51oC.
Oxo-o-tolyl-acetic acid benzyl ester-74’
Data: 1H NMR (400 MHz, CDCl3) δ 7.64 (d, J = 8.0, 1H), 7.48-7.38 (m, 6H), 7.29 (d, J = 7.6, 2H), 5.41 (s, 2H), 2.60 (s, 3H, CH3); 13C NMR (100 MHz, CDCl3) δ 188.3 , 164.4, 141.4, 134.5, 133.7, 132.3, 131.1, 128.7, 128.66, 128.6, 125.9, 67.6, 21.4; MS C16H14O3 (EI, 254) 254 (M+, 100), 165 (66), 148 (70); TLC Rf 0.35 (EtOAc/Hexane, 1/15); Anal. Calcd. for C16H14O3: C, 75.57; H, 5.55. Found:
C, 75.74; H, 5.68.
(2-Chloro-phenyl)-oxo-acetic acid methyl ester-75’
Data: 1H NMR (400 MHz, CDCl3) δ 7.76 (dd, J = 7.6, 1.6, 1H), 7.50 (td, J = 7.6, 1.6, 1H), 7.45-7.39 (m, 7H), 5.38 (s, 2H); 13C NMR (100 MHz, CDCl3) δ 186.1, 162.9, 134.4, 134.1, 133.9, 133.0, 131.6, 130.5, 128.8, 128.7, 128.6, 127.2, 68.3);
HR-MS Calcd. For M+, C15H11ClO3 : 274.0397, found : 274.0398; TLC Rf
0.32 (EtOAc/Hexane, 1/15); Anal. Calcd. for C15H11ClO3: C, 65.58; H, 4.04.
Found: C, 66.05; H, 3.93.
Oxo-(2-nitro-phenyl)-acetic acid benzyl ester-76’
O
O O Br
O
O O Cl
O
O O
Data: 1H NMR (400 MHz, CDCl3) δ 8.17 (dd, J = 7.6, 0.8, 1H), 7.79 (td, J = 7.6, 0.8, 1H), 7.71 (td, J = 7.6, 1.6, 1H), 7.61 (dd, J = 7.6, 1.6, 1H), 7.38-7.35 (m, 5H), 5.28 (s, 2H); 13C NMR (100 MHz, CDCl3) δ 183.5, 159.5, 147.3, 134.8, 134.1, 132.8, 132.4, 130.1, 128.7, 128.6, 123.9, 68.5; HR-MS Calcd. For M+, C15H11NO5 : 285.0637, found : 285.0635; TLC Rf 0.36 (EtOAc/Hexane, 1/5); mp: 56-57oC.
Oxo-naphthalen-1-yl-acetic acid benzyl ester-77’
Data: 1H NMR (400 MHz, CDCl3) δ 9.07 (d, J = 8.4, 1H), 8.08 (d, J = 8.0, 1H), 7.91 (m, 2H), 7.67 (t, J = 8.0, 1H), 7.58 (t, J = 8.0, 1H), 7.50-7.40 (m, 6H), 5.48 (s, 2H); 13C NMR (100 MHz, CDCl3) δ 188.4, 164.3, 135.8, 134.5, 134.0, 133.8, 130.8, 129.2, 128.7, 128.6, 128.5, 127.9, 126.9, 125.4, 124.2, 67.7; TLC Rf 0.36 (EtOAc/Hexane, 1/20); MS C19H14O3 (EI, 290) 290 (M+, 3), 155 (100), 127 (50), 91 (14); HR-MS Calcd. For M+, C19H14O3 : 290.0937, found : 290.0943; Anal.
Calcd. for C19H14O3: C, 78.61; H, 4.86. Found: C, 78.32; H, 4.88.
Oxo-naphthalen-2-yl-acetic acid benzyl ester-78’83
Data: 1H NMR (400 MHz, CDCl3) δ 8.45 (s, 1H), 8.03 (dd, J = 8.6, 1.7, 1H), 7.90-7.85 (m, 3H), 7.62 (td, J = 6.9, 1.2, 1H), 7.57-7.50 (m, 3H), 7.45- 7.40 (m, 3H), 5.49 (s, 2H); 13C NMR (100 MHz, CDCl3) δ 185.9, 163.7, 136.3, 134.6, 133.5, 132.1, 129.9, 129.7, 129.5, 128.9, 128.8, 128.7, 128.6, 127.8, 127.1, 123.7 ; TLC Rf 0.35 (EtOAc/Hexane, 1/20); MS C19H14O3 (ESI, 290) 313 (M+Na+, 18), 603 (2M+Na+, 100); Anal. Calcd. for C19H14O3: C, 78.61; H, 4.86. Found: C, 78.50; H, 4.71.; mp: 78-79oC.
O
O O O
O O O
O O NO2
Furan-2-yl-oxo-acetic acid benzyl ester-79’83
Data: 1H NMR (400 MHz, CDCl3) δ 7.72 (d, J = 1.6, 1H), 7.65 (d, J = 4.0, 1H), 7.42 (dd, J = 8.2, 1.8, 2H, 7.39-7.33 (m,3H), 6.58 (dd, J = 3.6, 1.6, 1H) , 5.36 (s, 2H); 13C NMR (100 MHz, CDCl3) δ 170.6, 160.7, 149.5, 149.5, 134.3, 128.7, 128.6, 128.5, 124.7, 112.9, 68.0; MS C13H10O4 (ESI, 230) 253 (M+Na+, 45), 483 (2M+Na+, 100); TLC Rf 0.32 (EtOAc/Hexane, 1/19).
Thiophen-2-yl-oxo-acetic acid benzyl ester-80’
Data: 1H NMR (400 MHz, CDCl3) δ 8.08 (d, J = 3.6, 1H), 7.80 (d, J = 4.8, 1H), 7.47-7.38 (m, 5H), 7.17 (t, J = 4.4, 1H), 5.39 (s, 2H); 1 3C NMR (100 MHz, CDCl3) δ 176.0, 161.4, 139.0, 137.5, 137.2, 134.4, 128.8, 128.7, 68.1; TLC Rf 0.30 (EtOAc/Hexane, 1/19); MS C13H10O3S(ESI, 246) 269 (M+Na+, 2), 483 (2M+Na+, 100); HR-MS Calcd. For M+, C13H10O3S: 246.0351, found : 246.0353;.
2-Oxo-4-phenyl-but-3-enoic acid methyl ester-81’83
Data: 1H NMR (400 MHz, CDCl3) δ 7.88 (d, J = 16.0, 1H), 7.65-7.63 (m, 2H), 7.46-7.42 (m, 3H), 7.38 (d, J = 16.0, 1H), 3.94 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 182.4, 162.5, 148.7, 134.0, 131.7, 129.1, 129.07, 120.4, 53.0; MS C11H10O3
(ESI, 190) 214 (M+Na++H+, 100), 404 (2M+Na++H+, 14); TLC Rf 0.34 (EtOAc/Hexane, 1/7)
2-Oxo-4-phenyl-but-3-ynoic acid ethyl ester-82’84 O
O O O
O
O S O
O O O
Data: Data: 1H NMR (400 MHz, CDCl3) δ 7.66 (d, J = 7.0, 2H), 7.52 (t, J = 7.5, 1H), 7.42 (t, J = 7.4, 2H), 4.41 (q, J = 7.2, 2H), 1.42 (t, J = 7.2, 3H); 13C NMR (100 MHz, CDCl3)δ169.5, 159.2, 133.7, 131.7, 131.8, 128.7, 119.0, 97.9, 87.1, 63.2, 13.9;
MS C12H10O3 (ESI, 202) 225 (M+Na+, 94); TLC Rf 0.32 (EtOAc/Hexane, 1/8)
2-Oxo-propionic acid benzyl ester-83’85
Data: 1H NMR (400 MHz, CDCl3) δ 7.40-7.37 (m, 5H), 5.28 (s, 2H), 2.47 (s, 3H); 13C NMR (100 MHz, C D C l3) δ 1 9 1 . 5 , 1 6 0 . 6 , 1 3 4 . 4 , 1 2 8 . 8 , 128.7, 128.6, 68.0, 26.7; MS C10H10O3 (EI, 178) 178 (M+, 17), 154 (88), 126 (57) , 90 (100), 77 (38) , 63 (23), 43 (39); TLC Rf 0.32 (EtOAc/Hexane, 1/20)
2-Oxo-4-methyl-pentanoic acid benzyl ester-84’86
Data: 1H NMR (400 MHz, CDCl3) δ 7.39-7.35 (m, 5H ), 5.27 (s, 2H), 2.71 (d, J = 6.8, 2H), 2.18 (heptet, J = 6.8, 1H ), 0.95 (d, J = 6.8, 6H); 13C NMR (100 MHz, CDCl3) δ 193.9 , 161.1, 134.5, 128.7, 128.6, 128.5, 67.7, 47.9, 24.1, 22.3; MS C13H16O3 (EI, 220) 220 (M+, 2), 181 (25), 91 (100) , 85 (28), 57 (14); TLC Rf 0.36 (EtOAc/Hexane, 1/15)
2-Oxo -cyclohexyl-acetic acid benzyl ester -85’
Data: 1H NMR (400 MHz, CDCl3) δ 7.41-7.34 (m, 5H ), 5.28 (s, 2H), 3.04-3.01 (m, 1H, OH), 1.90-1.66 (m, 5H), 1.36-1.21 (m, 5H); 13C NMR (100 MHz, CDCl3) δ 197.1 , 161.7, 134.6, 128.63, 128.62, 128.4, 67.6, 46.3, 27.4, 25.6, 25.2; MS C15H18O3
O
O O O
O O O
O O
O
O O
(ESI, 246) 270 (M+Na+, 37), 516 (2M+Na+, 100); TLC Rf 0.38 (EtOAc/Hexane, 1/30);
Anal. Calcd. for C15H18O3 :C, 73.15; H, 7.37. Found: C, 73.43; H, 7.22.
N-Isopropyl-2-oxo-2-phenyl-acetamide-69a’87
Data: 1H NMR (400 MHz, CDCl3) δ 8.33 (d, J = 7.5, 2H), 7.61 (t, J = 6.0, 1H), 7.47 (d, J = 7.6, 2H), 6.91 (brs, 1H, -NH), 4.17 (heptet, J = 6.4, 1H), 1.27 (d, J = 6.4, 6H); 13C NMR (100 MHz, CDCl3) δ 188.0, 160.9, 134.2, 133.4, 131.2, 128.4, 41.7, 22.4; MS C11H13NO2 (ESI, 191) 214 (M+Na+, 42); TLC Rf 0.44 (EtOAc/Hexane, 1/8); mp 87-88oC.
N-Benzyl-2-oxo-2-phenyl-acetamide-69b’88
Data: 1H NMR (400 MHz, CDCl3)δ 8.36 (d, J = 8.0, 2H), 7.62 (m, 1H), 7.47 (t, J = 8.0, 2H), 7.39-7.30 (m, 6H), 4.58 (d, J = 6.0, 2H); 13C NMR (100 MHz, CDCl3) δ 187.5, 161.5, 137.1, 134.4, 133.3, 131.2, 128.9, 128.5, 127.9, 127.8, 43.5; MS C15H13NO2 (ESI, 239) 262 (M+Na+, 52), 501 (2M+Na+, 100); TLC Rf 0.42 (EtOAc/Hexane, 1/8); mp 97-98oC.
N-Benzhydryl- 2-oxo-2-phenyl-acetamide-69c’89:
Data: 1H NMR (400 MHz, CDCl3) δ 8.37 (d, J = 7.6, 2H), 7.77 (d, J = 8.0, 1H, -NH), 7.63 (t, J = 7.6, 2H), 7.47 (t, J = 8.0, 2H), 7.38-7.29 (m, 10H), 6.31 (d, J=8.4, 1H); 13C NMR (100 MHz, CDCl3) δ 187.3, 160.7, 140.6, 134.5, 133.2, 131.3, 128.8, 128.5, 127.8, 127.4, 57.1; MS C21H17NO2 (ESI, 315) 315 (2M+Na+, 5); TLC Rf 0.46 (EtOAc/Hexane, 1/8); mp112-114oC.
O
O HN
O
O HN O
O HN
N-tert-Butyl-2-oxo-2-phenyl-acetamide-69d’90
Data: 1H NMR (400 MHz, CDCl3) δ 8.29(d, J = 7.2, 2H), 7.60 (t, J = 7.6, 1H), 7.47 (d, J = 7.6, 2H), 6.93 (brs, 1H, -NH), 1.45 (s, 9H); 13C NMR (100 MHz, CDCl3)δ188.5, 161.1, 134.1, 133.4, 131.2, 128.4, 51.6, 28.4; MS C12H15NO2 (ESI, 205) 228 (M+Na+, 34); TLC Rf 0.47 (EtOAc/Hexane, 1/8); mp 78-79oC.
2-Oxo-2-N-diphenyl-acetamide-69e’91
Data: 1H NMR (400 MHz, CDCl3) δ 8.93 (brs, 1H, -NH), 8.42 (dd, J = 8.5, 1.28, 2H), 7.72-7.65 (m, 3H), 7.52 ( t, J
= 8.1, 2H), 7.41 ( t, J = 8.2, 2H), 7.20 ( t, J = 7.4, 1H);
13C NMR (100 MHz, CDCl3) δ 187.4, 158.8, 136.6, 134.6, 133.1, 131.5, 129.2, 128.6, 125.3, 119.9; MS C14H11NO2 (ESI, 225) 225 (M +, 66); TLC Rf 0.43 (EtOAc/Hexane, 1/8); mp 62-64 oC.
N-Benzyl-2-oxo-2-p-tolyl-acetamide-88’：
Data: 1HNMR (400 MHz, CDCl3) δ 8.28 (d, J = 8.2, 2H), 7.45 (brs, 1H, -NH), 7.38-7.27 (m, 7H), 4.56 (d, J = 6.0, 2H), 2.43 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 187.0, 161.8, 145.7, 137.2, 131.4, 130.8, 129.2, 128.8, 127.83, 127.75, 43.4, 21.8; MS C16H15NO2 (ESI, 253) 278 (M+Na++2H+, 100), 530 (2M+Na++H+, 63), 1037 (4M+Na++H, 16); TLC Rf 0.43 (EtOAc/Hexane, 1/8); Anal. Calcd. For C16H15NO2: C, 75.87; H, 5.97. Found: C, 75.62; H, 5.76.; mp 92-95 oC.
N-Benzyl-2-(4-methoxy-phenyl)-2-oxo-acetamide-89’73 O
O HN
O
O HN O
O HN
Data: 1H NMR (400 MHz, CDCl3) δ 8.43 (d, J = 8.8, 2H), 7.48 (brs, 1H, -NH), 7.38-7.28 (m, 5H), 6.95 (d, J=8.9, 2H), 4.56 (d, J = 6.0, 2H), 3.89 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 185.4, 164.7, 162.1, 137.2, 134.0, 128.8, 127.8, 127.7, 126.4, 113.8, 55.5, 43.4; MS C16H15NO3 (ESI, 269) 292 (M+Na +, 60), 561 (2M+Na +, 60);
mp 106-107 oC.
N-Benzyl-2-(4-chloro-phenyl)-2-oxo-acetamide-90’ 73
Data: 1H NMR (400 MHz, CDCl3) δ 8.35 (d, J = 6.7, 2H), 7.45 (d, J = 6.7, 2H), 7.38-7.31 (m, 5H), 4.56 (d, J =
6.1, 2H); 13C NMR (100 MHz, CDCl3) δ 186.1, 161.1, 141.2, 136.9, 132.7, 131.6, 128.85, 128.83, 127.9, 43.5; TLC Rf 0.41 (EtOAc/Hexane, 1/8); MS C15H12ClNO2 (ESI, 253) 296 (M+Na+, 35), 569 (2M+Na+, 100); mp 106-107
oC.
N-Benzyl-2-(4-bromo-phenyl)-2-oxo-acetamide-91’:
Data: 1H NMR (400 MHz, CDCl3 )δ 8.28 (d, J = 8.4, 2H), 7.36 (d, J = 8.4, 2H), 7.41 (brs, 1H, -NH), 7.39-7.30 (m, 5H), 4.56 (d, J = 6.0, 2H); 13C NMR (100 MHz, CDCl3) δ 186.3, 161.1, 136.9, 132.8, 132.1, 131.9, 130.2, 128.9, 127.9, 43.5; MS C15H12BrNO2 (ESI, 318) 341 (M+Na+, 22), 659 (2M+Na+, 100), 1259 (4M+Na+, 32);
TLC Rf 0.42 (EtOAc/Hexane, 1/8); Anal. Calcd. For C15H12BrNO2: C, 56.62; H, 3.80.
Found: C, 56.97; H, 4.02.; mp 117-119 oC.
N-Benzyl-2-oxo-2-o-tolyl-acetamide-92’：
O
O HN
O
O
O HN
Br
O
O HN
Cl
Data: 1H NMR (400 MHz, CDCl3) δ 7.97 (d, J = 7.7, 1H), 7.47-7.27 (m, 10H), 4.57 (d, J=6.0, 2H), 2.50 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 191.1, 161.8, 140.2, 137.1 132.8, 132.7, 132.0, 131.7, 128.8, 127.9, 127.8, 125.4, 43.6, 20.9; MS C16H15NO2
(ESI, 253) 277 (M+Na++Na+, 100), 529 (2M+Na+, 92), 1036 (4M+Na+, 27); TLC Rf
0.44 (EtOAc/Hexane, 1/8); Anal. Calcd. For C16H15NO2: C, 75.87; H, 5.97. Found: C, 76.19; H, 6.07.; mp 71-72 oC.
N-Benzyl-2-(2-methoxy-phenyl)-2-oxo-acetamide-93’:
Data: 1H NMR (400 MHz, CDCl3) δ 7.68 (dd, J = 7.6, 1.6, 1H), 7.52 (t, J = 1.6, 1H), 7.37-7.30 (m, 5H), 7.06 (t, J = 7.2, 1H), 6.97 (d, J = 8.4, 1H), 4.57 (d, J = 6.4, 2H), 3.80 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 191.4, 163.0, 159.6, 137.5, 134.6, 131.1, 128.7, 127.8, 127.7, 124.5, 120.7, 112.0, 56.0, 43.3; MS C16H15NO3 (ESI, 269) 292 (M+Na +, 4), 561 (2M+Na +, 100); Anal. Calcd. For C16H15NO3: C, 70.83; H, 6.32.
Found: C, 70.97; H, 6.02.; mp 102-103 oC.
N-Benzyl-2-(2-chloro-phenyl)-2-oxo-acetamide -94’:
Data: 1H NMR (400 MHz, CDCl3) δ 7.70 (d, J = 1.4, 1H), 7.49-7.43 (m, 2H), 7.40-7.29 (m, 7H), 4.56 (d, J = 6.0, 2H); 13C NMR (100 MHz, CDCl3) δ 190.0, 160.6, 136.9, 133.9, 133.1, 133.0, 131.2, 130.4, 128.8, 127.9, 127.8, 126.5, 43.7; TLC Rf
0.40 (EtOAc/Hexane, 1/8); C15H12ClNO2 (ESI, 253) 296 (M+Na+, 12), 569 (2M+Na+, 74); Anal. Calcd. For C15H12ClNO2: C, 65.82; H, 4.42. Found: C, 65.56; H, 4.17. ; mp 91-92 oC.
O
O HN Cl
O
O HN O
O
O HN
N-Benzyl-2-naphthalen-1-yl-2-oxo-acetamide-95’92
Data: 1H NMR (400 MHz, CDCl3)δ 8.60 (d, J = 8.4, 1H), 8.35 (d, J = 7.2, 1H), 8.08 (d, J = 8.4, 1H), 7.90 (d, J=8.4, 1H), 7.64-7.54 (m, 2H), 7.41-7.32 (m,5H), 4.62 (d, J = 6.0, 2H); 13C NMR (100 MHz, CDCl3)δ190.2, 162.0, 137.1, 134.6, 133.8, 133.2, 131.1, 129.5, 128.8, 128.7, 128.4, 127.9, 127.8, 126.5, 125.3, 124.2, 43.7; MS C19H15NO2 (ESI, 289) 312 (M+Na+, 8), 601 (2M+Na+, 94); TLC Rf 0.37 (EtOAc/Hexane, 1/8);
mp:123-125oC.
N-Benzyl-2-naphthalen-2-yl-2-oxo-acetamide-96’:
Data: 1H NMR (400 MHz, CDCl3)δ 9.25 (brs, 1H), 8.21 (dd, J = 8.7, 1.6, 1H), 8.01 (d, J=8.1, 1H), 7.89 (t, J = 9.0, 2H), 7.64 (td, J = 7.0, 1.0, 1H), 7.56 (td, J = 7.0, 1.0, 1H), 7.50 (brs, 1H), 7.28-7.32 (m, 5H), 4.62 (d, J = 6.0, 2H); 13C NMR (100 MHz, CDCl3) δ 187.1 ,161.8, 137.2, 136.2, 135.1, 132.4, 130.6, 130.4, 129.4, 128.9, 128.4, 128.0, 127.9, 127.8, 126.9, 125.3, 43.6; MS C19H15NO2 (ESI, 289) 313 (M+Na++ H+, 21), 601 (2M+Na+, 79); TLC Rf 0.35 (EtOAc/Hexane, 1/8); Anal.
Calcd. For C19H15NO2: C, 78.87; H, 5.23. Found: C, 78.59; H, 5.43. ; mp:134-136oC.
2-Furan-2-yl-2-oxo-N-benzyl-acetamide -97’93
Data: 1H NMR (400 MHz, CDCl3) δ 8.22 (d, J = 3.6, 1H), 7.76 (d, J = 1.6, 1H), 7.37-7.28 (m, 5H), 6.33 (dd, J = 3.6, 1.6, 1H), 4.54 (d, J = 6.0, 2H); 13C NMR (100 MHz, CDCl3) δ 173.4, 160.0, 149.4, 136.9, 128.8, 127.9, 127.0, 113.2, 43.4; MS C13H11NO3 (ESI, 229) 252 (M+Na++H+, 42), 481(2M+Na+, 31); TLC Rf 0.38
O
O HN
O
O HN O
O
O HN
(EtOAc/Hexane, 1/8); mp:78-80oC.
N-Benzyl-2-oxo-2-thiophen-2-yl-acetamide-98’ 73
Data: 1H NMR (400 MHz, CDCl3) δ 8.41 (dd, J = 3.92, 0.96, 1H), 7.82 (dd, J = 4.96, 1.12, 1H), 7.71 (brs, 1H, -NH), 7.41-7.28 (m, 5H), 7.18 (dd, J = 4.72, 4.12, 1H), 4.56 (d, J = 6.16, 2H); 13C NMR (100 MHz, CDCl3) δ 178.2, 160.6, 138.6, 138.1, 136.9, 136.7, 128.7, 128.2, 127.8, 127.7, 43.4; MS C13H11NO2S (ESI, 245) 268 (M+Na+, 86), 513 (2M+Na+, 100); TLC Rf 0.39 (EtOAc/Hexane, 1/8); mp:93-95oC.
N-Benzyl-4-phenyl-but-3-enoic acid-2-oxo-acetamide-99’:
Data: 1H NMR (400 MHz, CDCl3) δ 7.96 (d, J = 16.0, 1H), 7.81 (d, J = 16.0, 1H), 7.67 (dd, J = 8.0, 2.0, 2H), 7.49-7.40 (m, 4H), 7.38-7.29 (m, 5H), 4.55 (d, J = 6.4, 2H); 13C NMR (100 MHz, CDCl3) δ 185.3, 161.2, 148.1, 137.1, 134.4, 131.5, 129.2, 129.0, 128.8, 127.9, 127.8, 118.6, 110.4, 43.5; MS C17H15NO2 (ESI, 265) 289 (M+Na++H+, 100), 553 (2M+Na+, 73); TLC Rf 0.41 (EtOAc/Hexane, 1/8); Anal.
Calcd. For C17H15NO2: C, 79.96; H, 5.07. Found: C, 79.69; H, 5.70. ; mp:127-128oC.
N-Benzyl-2-oxo-propionamide-100’94
Data: 1H NMR (400 MHz, CDCl3) δ 7.33-7.27 (m, 5H), 4.45 (d, J = 6.4, 2H), 2.48 (s, 3H) ; 13C NMR (100 MHz, CDCl3) δ 196.9, 159.9, 136.9, 128.7, 127.74, 127.69, 43.3, 24.4; MS C10H11NO2 (ESI, 177) 377 (2M+Na+, 14), 731 (4M, 90); TLC Rf 0.36 (EtOAc/Hexane, 1/6).
O
O HN O
O HN S
O
O HN
4-Methyl-2-oxo-pentanoic acid benzylamide-101’95
procedure for oxovanadium complex preparation
O