1H) ,7.37-7.19 (m,5H),4.76-4.65(m,lH),4.49(dd,J = 9.2,8.6Hz,lH),4.27(dd,J = 8.6,8.0Hz,lH) ,3.31 (dd,J=14.0,5.2Hz,lH) ,2.79(dd,J= 14.0,8.8Hz, 1H) ;13C 匪R: (100.6MHz,CDC13)δ 162.1,150.7,148.0,139.2(q,Jc-F= 34.3) ,137.4,129.2,128.6,126.7,122.4(q,Jc-F = 271.8),121.0(q,Jc-f = 3.6),119.8(q,Jc-F=3.6) ,72.8,68.2,41.5;19F NMR: (11176.5MHz, CDCl3)5-183.3;HRMS(EI)calculated for[Ci6Hi3N20F3]+requires m/z 306.0980,found m/ z 306.0977.
[0070] 實(shí)例14
[0071]
[0072] (S)-(6-(4-benzyl-4,5-dihydrooxazol-2-yl)pyridin-2-yl)methanol(IIIn): yield 45% ; [α]〇20 = + 1.8(c = 1.94, CHC13) ; IR(neat): 3379,2922,1645,1583,1453 , 1366cm-S1!!匪R: (400.1MHz,CDC13)S7.89((1, J = 7.6Hz,lH),7.76(t,J = 7.6Hz,lH) ,7.52 (d,J=7·6Ηζ,1H),7.34-7.26(m,2H),7.26-7.19(m,3H),4.94-4.82(m,3H),4.67-4.55(m, 1H) ,4.41(dd,J = 9.2,8.6Hz,lH),4.20(dd,J = 8.6,8.0Hz,lH),3.24(dd,J=13.8,5.0Hz, 1H),2.73(dd,J=13.8,9.0Hz,lH) ;13C 匪R: (100.6MHz,CDC13)S163.2,160.8,145.3, 137.4,137.2,129.1,128.5,126.5,122.6,122.3,72.4,67.7,64.6,41.4;HRMS(EI) calculated for[Ci6Hi6N202]+requires m/z 268.1212,found m/z 268.1214.
[0073] 實(shí)例15
[0074]
[0075] (S)-4~benzy1-2-(quino1in-2-yl)-4,5-dihydrooxoxazoline(IIIo):yield 81% ; [a]D20 = -16.4(c = l .01 ,CHC13) ;IR(neat) :3060,3027,2923,1640,1596,1501, 1371cm-S1!! NMR: (400.1MHz,CDC13)S8.27(d,J = 8.4Hz,lH) ,8.18(s,2H) ,7.78((1, J = 8.0Hz,1H),7·75-7·68(ι?,1H),7.58-7.51(m,lH),7.36-7.15(m,5H),4.76-4.63(m,lH), 4.50(dd ,J = 9.6,8.6Hz,lH),4.29(dd ,J = 8.6,8.0Hz,lH),3.31(dd ,J=13.6,5.4Hz,lH), 2.80(dd,J=13.6,8.8Hz,lH);13C 匪R: (100.6MHz,CDC13)S163.4,147.6,146.8,137.7, 136.7.130.4.130.0. 129.2.128.8.128.6.127.9.127.5.126.6.120.8.72.7.68.2.41.7; HRMS(EI)calculated for[CigHi6N20]+requires m/z288.1263,found m/z 288.1265.
[0076] 實(shí)例16
[0077]
[0078] (S)-4-benzyl-2-(pyrazin-2-y1)-4,5-dihydrooxoxazoline(IIIp):yield 55% ; [a]D20 = -2.0(c = l. 05, CHC13) ; Lit11: [a]D = -18.5(c= 1.035, CHC13) ;IR(neat): 3027,2924,2855,1646,1525,1472,1358cm-S1!!匪R: (400.1MHz,CDC13)S9.27(d,J = 1,6Hz,lH),8.70-8.65(m,2H),7.34-7.20(m,5H),4.76-4.66(m,lH),4.47(dd,J=9.6, 8.4Hz,lH),4.25(dd ,J = 8.4,7.8Hz,lH),3.29(dd ,J=14.0,5.2Hz,lH),2.80(dd ,J=14.0, 8.6Hz,1H);13C NMR:(100.6MHz,CDC13)S161.2,146.1,145.1,144.0,142.3,137.2,129.1, 128.4.126.5.72.4.68.0. 41.3.
[0079] 實(shí)例17
[0080]
[0081 ] (S)-4-benzyl-2-(pyrimidin-2-yl)-4,5-dihydrooxoxazoline(Illq): yield 46% ; [a ]d20 = + 12.9( c = l. 79, CHC13) ;IR(neat) :3030,2921,1648,1562,1495,1432, 1362cm-S1!! NMR: (400.1MHz,CDCl3)S8.89(d, J = 4.8Hz,2H),7.42(t,J = 5.0Hz ,1H),7.36-7.19(m,5H),4.81-4.69(m,lH),4.51(dd ,J = 9.2,8.6Hz,lH),4.29(dd ,J = 8.6,8.0Hz,lH), 3.39(dd,J=13.8,5.0Hz,lH),2.80(dd,J=13.8,9.4Hz,lH); 13C NMR: (100.6MHz,CDC13)S 161.6.157.3.155.5.137.2.128.9.128.3.126.3.121.9.72.6.68.0. 41.0;HRMS(EI) calculated for[Ci4Hi3N30]+requires m/z 239.1059,found m/z 239.1057.
[0082] 實(shí)例18
[0083]
[0084] (S)-2-(benzo[d]thiazol-2-yl)-4-benzyl~4,5-dihydrooxoxazoline(Illr): yield 46% ; [a]D20 = +42.9(c = 1.11,CHC13) ; IR(neat): 3028,2924,2855,1645,1505 , 1455,1368cm-S1!! NMR: (400.1MHz,CDCl3)S8.18(d,J = 8.0Hz,lH) ,7.94((1, J = 8.4Hz,lH), 7·59-7.46(m,2H),7.36-7.20(m,5H),4.78-4.66(m,lH),4.52(dd,J=9.2,8.8Hz,lH),4.31 (dd,J = 8.8,7.6Hz,lH),3.30(dd,J=13.6,5.0Hz,lH) ,2.83(dd,J=13.6,8.8Hz,1H);13C NMR:(100.6MHz,CDCl3)Sl59.1,155.6,153.2,137.1,135.9,129.2,128.6,126.9,126.8, 126·7,124·7,121·7,73·0,68·2,41·2;HRMS(EI(calculated for[Ci7Hi4N20S]+requires m/ z 294.0827,found m/z 294.0823.
[0085] 實(shí)例19
[0086]
[0087] (S)-4-benzy1-2_(5_chlor〇-3-methylbenzo[b]thiophen-2-y1)-4,5-dihydrooxoxazoline(Ills) :yield 95%;M.p.95-96°C ; [a]〇20 = +35.8(c = 1.03,CHCl3); 7.67(m,2H),7.37-7.20(m,6H),4.65-4.46(m,lH),4.35(dd,J=9.2,8.4Hz,lH),4.16(dd,J = 8.4,8.0Hz,lH),3.24(dd,J = 13.6,5.2Hz,lH) ,2.75(dd,J=13.6,8.6Hz,lH) ,2.66(s, 3H);13C NMR:(100.6MHz,CDC13)S160.3,141.6,137.8,137.7,135.9,130.6,129.2,128.5, 126.5,126.1,123.4,122.6,71.9,67.9,41.6,13.1;HRMS(El) calculated for [C19H16NOSCI]+requires m/z 341.0641,found m/z 341.0642.
[0088] 實(shí)例20
[0089]
[0090] 、b;-4-〇enzy 丄一z_、o -〇rom〇-[2 , 2 ' - bipyridin]-6-yl )-4,5-dihydrooxoxazoline(IIIt) :yield30% ;M.p. 133-135°C ;[α]〇20 = -12.0(ο = 1.04,CHCl3); IR(neat):3062,2921,1641,1574,1550,1420,1369cm-S1!!匪R:(400.lMHz,CDCl3)S8.52 (dd,J = 7.6,5.2Hz,2H),8.09(d,J = 7.6Hz,lH),7.90(dd,J = 8.0,7.6Hz,lH) ,7.66(t,J = 7.6Hz,lH),7.49(d ,J = 7.6Hz,lH),7.37-7.19(m,5H),4.74-4.62(m,lH),4.47(dd ,J = 9.2, 8.6Hz,lH),4.27(dd ,J = 8.6,8.0Hz,lH),3.32(dd ,J=13.6,4.8Hz,lH),2.78(dd ,J=13.6, 9.0Hz,1H);13C NMR:(100.6MHz,CDC13)S163.1,156.4,154.5,146.3,141.4,139.2,137.7, 137.6,129.2,128.6,128.3,126.6,124.5,123.3,120.3,72.5,68.1,41.6;HRMS(EI) calculated for[C20Hi6BrN30]+requires m/z 393.0477,found m/z393.0470.
[0091] 實(shí)例21
[0092]
[0093] (S)-4-benzyl-2-(4-methoxyphenyl)-4,5-dihydrooxoxazoline(IIIu): yield 92% ; [a]D20 = + 17.9(c = 0.99,CHCl3);Lit12: [a]10 = + 12.8(c = 0.641,CHCl3);IR(neat): 2903,2840,1645,1609,1512,1359,1310cm-S 1!!匪R: (400.1MHz,CDCl3)S7.92-7.86(m, 2H),7.34-7.18(m,5H),6.94-6.87(m,2H),4.60-4.49(m,lH),4.30(dd,J=9.2,8.4Hz,lH), 4. ll(dd,J = 8.4,7.6Hz,lH) ,3.83(s,3H) ,3.24(dd,J=13.6,5.2Hz,lH) ,2.71(dd,J = 13.6,9.0Hz,1H);13C NMR:(100.6MHz,CDCl3)Sl63.7,162.0,138.1,129.9,129.2,128.5, 126.4,120.2,113.6,71.7,67.8,55.3,41.9;HRMS(EI)calculated for[Ci7Hi7N02]+ requires m/z 267.1259,found m/z 267.1252.
[0094] 實(shí)例22
[0095]
[0096] 丄丄丄uurophenyl )_4,5-dihydrooxox&zoline( IIIv): yield 93% ;[a]D20 = + 1.0(c = 1.08,CHCl3);[a]D20 = -40.3(c = 1.00,PhCH3);Lit12:[a]D20 = + 10.1 (c = 0.801 ,CHCl3) ;>99%ee,determined by HPLC,HPLC conditions:Chiralcel 0D-H,n-hexane/i-Pr0H = 90/10,1. OmL/min ,n = 254nm, tr 5.3(minor) ,6.5(major) ; IR(neat): 2924,1651,1605,1510,1358cm-1;4 NMR:(400·1MHz,CDC13)δ7·98-7·91(m,2H),7·34-7·28 (m,2H),7.27-7.20(m,3H),7.20-7.05(m,2H),4.62-4.52(m,lH),4.35(dd,J=9.6,8.4Hz, lH),4.14(dd ,J = 8.4,7.2Hz,lH),3.23(dd ,J=13.6,5.2Hz,lH),2.73(dd ,J=13.6,8.8Hz, lH);HRMS(EI)calculated for[Ci6Hi4N0F]+requires m/z 255.1059,found m/z 255.1057.
[0097] 實(shí)例23
[0098]
[0099] (S)-2-(4-benzyl-4,5-dihydrooxazol-2-yl)benzonitrile(IIIw):yield 95%; M.p.74-76〇C ;[a]D20 = -15.5(c = 1.01,CHCl3) ; , IR(neat): 3027,2853,2228,1653,1494, 1453,1359cm-S1!! NMR: (400.1MHz,CDCl3)S7.99(dd,J = 7.6,1.2Hz,lH),7.74(dd,J = 7.6, 1.2Hz,lH),7.61(td,J =