一种磺酰自由基引发的1,6-二烯类化合物碘化/磺酰化反应方法转让专利
申请号 : CN202110509203.3
文献号 : CN113214129B
文献日 : 2022-06-24
发明人 : 刘益林 , 林红卫 , 魏文廷 , 秦金香 , 唐伯孝 , 连琰 , 刘文柱
申请人 : 怀化学院
摘要 :
权利要求 :
1.一种1,6‑二烯类化合物与磺酰肼的碘化/磺酰化反应方法,其特征在于,包括如下步骤:向Schlenk反应瓶中加入式1所示的1,6‑二烯类化合物、式2所示的磺酰肼、碘源[I]、氧化剂和溶剂,将反应瓶置于一定温度、空气气氛条件下搅拌反应,经TLC或GC监测反应进程,至原料反应完全,经后处理得到碘化/磺酰化产物I;
式1、式2、式I表示的化合物中,
1
R选自取代或未取代的苯基、对甲苯磺酰基;
2
R选自C1‑C6烷基、苯基‑C1‑C6烷基;
3
R选自C1‑C6烷基、苯基‑C1‑C6烷基;
4
R选自C1‑C6烷基、取代或未取代的苯基、未取代的萘基、噻吩基;
其中,所述“取代或未取代的”中的取代基选自卤素、C1‑C6烷基、C1‑C6烷氧基、‑NO2、C1‑C6卤代烷基;
所述的碘源[I]选自CuI;
所述的氧化剂选自叔丁基过氧化氢;
所述的溶剂为乙腈。
2.根据权利要求1所述的方法,其特征在于,所述“取代或未取代的”中的取代基选自氟、氯、溴、碘、甲基、乙基、丙基、叔丁基、甲氧基、乙氧基、叔丁氧基、‑NO2、三氟甲基。
1
3.根据权利要求2所述的方法,其特征在于,R选自苯基、对甲氧基苯基、对甲基苯基、对氟苯基、对溴苯基、间甲基苯基、对三氟甲基苯基、对甲苯磺酰基;
2
R选自甲基、乙基、苄基;
3
R选自甲基、乙基、苄基;
4
R选自甲基、乙基、正丁基、苯基、萘基、对甲氧基苯基、间氯苯基、间甲基苯基、邻氯苯基、邻甲基苯基、邻甲氧基苯基、对硝基苯基、对溴苯基、对氯苯基、对氟苯基、对甲基苯基、
2‑噻吩基。
4.根据权利要求1‑3任意一项所述的方法,其特征在于,碘源[I]与式1所示的1,6‑二烯类化合物的投料摩尔比为(1~3):1。
5.根据权利要求4所述的方法,其特征在于,碘源[I]与式1所示的1,6‑二烯类化合物的投料摩尔比为(1.2~2):1。
6.根据权利要求5所述的方法,其特征在于,碘源[I]与式1所示的1,6‑二烯类化合物的投料摩尔比为1.2:1。
7.根据权利要求1‑3任意一项所述的方法,其特征在于,氧化剂与式1所示的1,6‑二烯类化合物的投料摩尔比为(1~3):1。
8.根据权利要求7所述的方法,其特征在于,氧化剂与式1所示的1,6‑二烯类化合物的投料摩尔比为2:1。
9.根据权利要求1‑3任意一项所述的方法,其特征在于,所述一定温度为60~120℃。
10.根据权利要求9所述的方法,其特征在于,所述一定温度为80~100℃。
11.根据权利要求10所述的方法,其特征在于,所述一定温度为90℃。
12.根据权利要求1‑3任意一项所述的方法,其特征在于,所述搅拌反应的反应时间为8~48h。
13.根据权利要求12所述的方法,其特征在于,所述搅拌反应的反应时间为12~24h。
14.根据权利要求13所述的方法,其特征在于,所述搅拌反应的反应时间为20h。
15.根据权利要求1‑3任意一项所述的方法,其特征在于,所述的后处理操作如下:将反应完成后的反应液用乙酸乙酯萃取,有机相用无水硫酸钠干燥,过滤并减压浓缩除去溶剂,将残余物经柱层析分离,洗脱溶剂为:乙酸乙酯/正己烷,得到碘化/磺酰化产物I。
说明书 :
一种磺酰自由基引发的1,6‑二烯类化合物碘化/磺酰化反应
方法
技术领域
背景技术
发明内容
具体实施方式
1
酯/正已烷)得到目标产物I‑1(9%yield,d.r.>20:1);H NMR(500MHz,CDCl3)δ:7.86‑7.81(m,2H),7.60‑7.54(m,2H),7.42‑7.34(m,4H),7.18(t,J=9.5Hz,1H),4.04‑3.90(m,2H),
3.65‑3.61(m,2H),3.59‑3.51(m,1H),3.40‑3.37(m,1H),2.46(s,3H),1.66(s,3H),1.59(s,
13
3H);C NMR(125MHz,CDCl3)δ:174.4,145.0,138.6,138.2,130.0,129.0,127.6,125.3,
120.3,59.2,57.8,51.5,41.7,21.7,20.8,20.2,16.1;HRMS m/z(ESI)calcd for +
C21H25INO3S([M+H])498.0594,found498.0598。
乙酸乙酯/正已烷)得到目标产物I‑2(85%yield,d.r.>20:1);H NMR(500MHz,CDCl3)δ:
7.89‑7.84(m,2H),7.54(d,J=8.5Hz,2H),7.38‑7.33(m,2H),7.18‑7.14(m,1H),7.01(d,J=8.5Hz,2H),3.92(d,J=10.5Hz,2H),3.88(s,3H),3.70‑3.60(m,2H),3.58(d,J=10.0Hz,
13
1H),3.39(t,J=7.5Hz,1H),1.64(s,3H),1.58(s,3H);C NMR(125MHz,CDCl3)δ:174.4,
163.9,138.6,132.8,129.8,129.0,125.2,120.3,114.6,59.5,57.8,55.8,51.5,41.7,+
20.9,20.1,16.1;HRMS m/z(ESI)calcd for C21H25INO4S([M+H] )514.0543,found
514.0547。
1
酯/正已烷)得到目标产物I‑3(80%yield,d.r.>20:1);H NMR(500MHz,CDCl3)δ:7.96‑7.90(m,2H),7.68‑7.65(m,1H),7.60‑7.56(m,2H),7.56‑7.54(m,2H),7.39‑7.35(m,2H),7.19‑
7.16(m,1H),3.94‑3.90(m,2H),3.66‑3.63(m,2H),3.58(d,J=10.0Hz,1H),3.41(d,J=
13
15.5Hz,1H),1.66(s,3H),1.59(s,3H);C NMR(125MHz,CDCl3)δ:174.3,141.0,138.6,
134.0,129.5,129.0,127.6,125.3,120.3,59.2,57.8,51.6,41.7,20.8,20.2,16.0;HRMS +
m/z(ESI)calcd for C20H23INO3S([M+H])484.0438,found 484.0434。
1
酯/正已烷)得到目标产物I‑4(78%yield,d.r.>20:1);H NMR(500MHz,CDCl3)δ:7.98‑7.95(m,2H),7.55‑7.53(m,2H),7.39‑7.36(m,2H),7.27‑7.24(m,2H),7.20‑7.17(m,1H),3.92‑
3.89(m,2H),3.65‑3.62(m,2H),3.58(d,J=10.5Hz,1H),3.41(d,J=15.0Hz,1H),1.66(s,
13
3H),1.58(s,3H);C NMR(125MHz,CDCl3)δ:174.2,165.9(d,JC‑F=255.5Hz),138.5,137.1,
130.5(d,JC‑F=9.5Hz),129.1,125.3,120.3,116.8(d,JC‑F=22.5Hz),59.4,57.8,51.6,
19
41.7,20.8,20.2,15.8;FNMR(471MHz,CDCl3)δ:‑102.8;HRMS m/z(ESI)calcd for +
C20H22FINO3S([M+H])502.0344,found 502.0340。
1
酯/正已烷)得到目标产物I‑5(77%yield,d.r.>20:1);H NMR(500MHz,CDCl3)δ:7.92‑7.87(m,2H),7.59‑7.51(m,4H),7.38(t,J=8.0Hz,2H),7.19(t,J=7.5Hz,1H),3.97‑3.87(m,
2H),3.65‑3.62(m,2H),3.57(d,J=10.5Hz,1H),3.40(d,J=15.0Hz,1H),1.65(s,3H),1.58
13
(s,3H);C NMR(125MHz,CDCl3)δ:174.1,140.8,139.4,138.5,129.8,129.1(2),125.4,
120.3,59.3,57.8,51.6,41.7,20.9,20.2,15.7;HRMS m/z(ESI)calcd for C20H22ClINO3S+
([M+H])518.0048,found518.0054。
1
酯/正已烷)得到目标产物I‑6(76%yield,d.r.>20:1);H NMR(500MHz,CDCl3)δ:7.84‑7.78(m,2H),7.73‑7.69(m,2H),7.53(t,J=4.0Hz,2H),7.40‑7.36(m,2H),7.19(t,J=7.5Hz,
1H),3.92‑3.87(m,2H),3.67‑3.61(m,2H),3.57(d,J=10.0Hz,1H),3.40(d,J=15.0Hz,
13
1H),1.65(s,3H),1.58(s,3H);C NMR(125MHz,CDCl3)δ:174.1,139.9,138.5,132.8,
129.4,129.2,129.1,125.4,120.3,59.2,57.8,51.6,41.7,20.9,20.2,15.7;HRMS m/z+
(ESI)calcd for C20H22BrINO3S([M+H])561.9543,found 561.9547。
乙酸乙酯/正已烷)得到目标产物I‑7(81%yield);68%yield,d.r.>20:1);H NMR(500MHz,CDCl3)δ:8.37‑8.35(m,2H),8.08‑8.05(m,2H),7.47‑7.44(m,2H),7.41‑7.38(m,
1H),7.31(d,J=7.5Hz,2H),4.78(d,J=52.0Hz,2H),4.31‑4.22(m,2H),4.03‑3.99(m,1H),
13
2.98‑2.95(m,1H),1.78(s,3H),1.12(d,J=7.0Hz,3H);C NMR(125MHz,CDCl3)δ:172.9,
150.8,145.6,141.6,140.3,129.7,129.3,128.4,124.4,59.5,56.7,55.8,41.3,32.0,+
20.3,18.7;HRMS m/z(ESI)calcd for C20H22IN2O5S([M+H])529.0289,found 529.0293。
乙酸乙酯/正已烷)得到目标产物I‑8(84%yield,d.r.>20:1);H NMR(500MHz,CDCl3)δ:
7.97‑7.95(m,1H),7.61‑7.56(m,3H),7.37(t,J=8.0Hz,2H),7.18(t,J=7.5Hz,1H),7.11(t,J=8.0Hz,1H),7.04(d,J=8.5Hz,1H),4.01(s,3H),3.95(d,J=10.0Hz,1H),3.90(t,J
13
=10.0Hz,1H),3.85(d,J=14.5Hz,2H),3.74‑3.64(m,2H),1.65(s,3H),1.59(s,3H);C NMR(125MHz,CDCl3)δ:174.6,157.2,138.6,135.8,130.1,129.0,128.7,125.2,120.9,
120.3,112.4,57.9,57.0,56.6,51.4,41.6,21.1,20.3,16.2;HRMS m/z(ESI)calcd for +
C21H25INO4S([M+H])514.0543,found 514.0547。
乙酸乙酯/正已烷)得到目标产物I‑9(81%yield,d.r.=1.5:1);H NMR(500MHz,CDCl3)δ:
8.02(d,J=7.5Hz,0.4H),7.81(d,J=8.5Hz,0.6H),7.56‑7.53(m,3H),7.39‑7.34(m,4H),
7.18(t,J=7.0Hz,1H),3.95‑3.89(m,2H),3.66‑3.57(m,3H),3.45‑3.37(m,1H),2.75(s,
13
1.8H),2.45(s,1.2H),1.66(s,1.8H),1.65(s,1.2H),1.59(s,1.8H),1.59(s,1.2H);C NMR(125MHz,CDCl3)δ:174.4(2),145.0,139.2,138.6(2),137.8,134.0,133.0,130.0,129.5,
128.9,127.6,126.9,125.3,120.3,59.3,58.0,57.8,51.6,51.5,41.7(2),21.7,20.8,+
20.5,20.3,16.1,16.0;HRMS m/z(ESI)calcd for C21H25INO3S([M+H])498.0594,found
498.0590。
1
酯/正已烷)得到目标产物I‑10(76%yield,d.r.>20:1);H NMR(500MHz,CDCl3)δ:8.16‑
8.14(m,1H),7.60‑7.54(m,4H),7.50‑7.47(m,1H),7.39‑7.36(m,2H),7.18(t,J=7.0Hz,
1H),3.97‑3.87(m,3H),3.73(d,J=15.0Hz,1H),3.64(t,J=11.0Hz,2H),1.68(s,3H),1.58
13
(s,3H);C NMR(125MHz,CDCl3)δ:174.1,138.5,138.2,135.0,132.8,132.1,131.2,129.0,
127.6,125.2,120.2,57.8,56.9,51.5,41.8,20.9,20.2,15.8;HRMS m/z(ESI)calcd for +
C20H22ClINO3S([M+H])518.0048,found 581.0054。
乙酸乙酯/正已烷)得到目标产物I‑11(71%yield,d.r.>20:1);80%yield,d.r.>20:1);H NMR(500MHz,CDCl3)δ:7.74‑7.70(m,2H),7.56‑7.53(m,2H),7.47‑7.45(m,2H),7.37(t,J=
8.0Hz,2H),7.17(t,J=7.0Hz,1H),3.97‑3.90(m,2H),3.62(t,J=7.5Hz,2H),3.58(d,J=
13
10.0Hz,1H),3.39(t,J=7.5Hz,1H),2.45(s,3H),1.67(s,3H),1.59(s,3H);C NMR(125MHz,CDCl3)δ:174.4,140.9,139.8,138.6,134.7,129.3,129.0,127.9,125.3,124.6,
120.3,59.1,57.8,51.6,41.8,21.4,20.8,20.2,16.2;HRMS m/z(ESI)calcd for +
C21H25INO3S([M+H])498.0594,found498.0590。
1
酯/正已烷)得到目标产物I‑12(62%yield,d.r.>20:1);75%yield,d.r.>20:1);HNMR(500MHz,CDCl3)δ:7.93(t,J=2.0Hz,1H),7.83(d,J=8.0Hz,1H),7.63(d,J=9.0Hz,1H),
7.55‑7.50(m,3H),7.37(t,J=8.0Hz,2H),7.18(t,J=7.5Hz,1H),3.90(t,J=10.0Hz,2H),
3.65(t,J=7.5Hz,2H),3.56(d,J=10.0Hz,1H),3.41(d,J=15.0Hz,1H),1.66(s,3H),1.58
13
(s,3H);C NMR(125MHz,CDCl3)δ:174.1,142.6,138.5,135.8,134.2,130.8,129.1,127.7,
125.7,125.3,120.3,59.2,57.8,51.6,41.8,20.8,20.2,15.8;HRMS m/z(ESI)calcd for +
C20H22ClINO3S([M+H])518.0048,found 518.0052。
1
酯/正已烷)得到目标产物I‑13(71%yield,d.r.>20:1);H NMR(500MHz,CDCl3)δ:8.50(d,J=1.0Hz,1H),8.00‑7.97(m,2H),7.92‑7.87(m,2H),7.66‑7.62(m,2H),7.54(d,J=8.0Hz,
2H),7.37‑7.33(m,2H),7.15(t,J=7.0Hz,1H),3.98‑3.91(m,2H),3.73(d,J=15.0Hz,1H),
13
3.62(t,J=10.0Hz,2H),3.48(d,J=15.0Hz,1H),1.68(s,3H),1.61(s,3H);C NMR(125MHz,CDCl3)δ:174.3,138.6,137.8,135.4,132.2,129.9,129.5(2),129.4,129.0,
128.1,127.9,125.3,122.2,120.3,59.2,57.8,51.6,41.8,20.9,20.2,16.2;HRMS m/z+
(ESI)calcd for C24H25INO3S([M+H])534.0594,found 534.0590。
1
酯/正已烷)得到目标产物I‑14(62%yield,d.r.>20:1);68%yield,d.r.>20:1);HNMR(500MHz,CDCl3)δ:7.74‑7.72(m,2H),7.56‑7.54(m,2H),7.40‑7.37(m,2H),7.19‑7.15(m,
2H),3.92‑3.88(m,2H),3.82(d,J=15.0Hz,1H),3.65‑3.63(m,1H),3.58(t,J=12.0Hz,
13
2H),1.66(s,3H),1.56(s,3H);C NMR(125MHz,CDCl3)δ:174.2,142.3,138.5,134.1,
133.9,129.1,128.0,125.3,120.3,60.9,57.8,51.6,41.8,20.7,20.1,15.9;HRMS m/z+
(ESI)calcd for C18H21INO3S2([M+H])490.0002,found 490.0008。
1
酯/正已烷)得到目标产物I‑15(63%yield,d.r.=1:1);H NMR(500MHz,CDCl3)δ:7.59‑
7.57(m,2H),7.41‑7.36(m,2H),7.21‑7,16(m,1H),3.89(d,J=10.5Hz,0.5H),3.80‑3.78(m,0.5Hz),3.69(d,J=10.0Hz,0.5H),3.64‑3.62(m,0.5H),3.56‑3.52(m,1H),3.39(d,J=
10.0Hz,0.5H),3.33(d,J=15.0Hz,0.5H),3.13‑3.05(m,2H),1.62(t,J=8.0Hz,2H),1.51
13
(s,3H),1.45‑1.42(m,3H),1.38(s,1.5H),1.29(s,1.5H);C NMR(125MHz,CDCl3)δ:175.6,
174.5,139.2,138.5,129.1,129.0,125.4,125.0,120.4,119.9,59.3,57.8,54.3,54.1,
51.9,50.9,50.5(2),41.6,38.9,25.1,21.2,20.8,20.1,17.9,15.7,6.9,6.8;HRMS m/z+
(ESI)calcd for C16H23INO3S([M+H])436.0438,found 436.0442。
1
酯/正已烷)得到目标产物I‑16(62%yield,d.r.=1:1);H NMR(500MHz,CDCl3)δ:7.59‑
7.57(m,2H),7.41‑7.36(m,2H),7.21‑7.16(m,1H),3.89(d,J=10.5Hz,0.5H),3.79(d,J=
10.0Hz,0.5H),3.68(d,J=9.5Hz,0.5H),3.62(d,J=10.5Hz,0.5H),3.58‑3.52(m,1.5H),
3.39(d,J=10.0Hz,1H),3.33(d,J=14.5Hz,0.5H),3.19(d,J=14.5Hz,0.5H),3.09‑3.05(m,1.5H),3.04‑3.01(m,1H),1.88‑1.83(m,2H),1.50(s,3H),1.48‑1.41(m,2H),1.38(s,
13
1.5H),1.29(s,1.5H),0.99‑0.95(m,3H);C NMR(125MHz,CDCl3)δ:175.7,174.5,139.2,
138.5,129.1,129.0,125.3,125.0,120.3,119.9,59.2,57.8,55.9(2),54.9,54.8,52.0,
51.0,41.6,38.9,25.1,24.3,24.2,21.7(2),21.2,20.8,20.1,17.9,15.7,13.6,13.5;HRMS +
m/z(ESI)calcd for C18H27INO3S([M+H])464.0751,found 464.0754。
乙酸乙酯/正已烷)得到目标产物I‑17(87%yield,d.r.>20:1);H NMR(500MHz,CDCl3)δ:
7.87‑7.84(m,2H),7.45‑7.42(m,2H),7.02‑7.00(m,2H),6.90‑6.88(m,2H),3.92(d,J=
9.5Hz,1H),3.87(s,3H),3.85(d,J=10.5Hz,1H),3.78(s,3H),3.62‑3.59(m,2H),3.58(d,J
13
=2.5Hz,1H),3.38(d,J=15.0Hz,1H),1.63(s,3H),1.56(s,3H);C NMR(125MHz,CDCl3)δ:
174.0,163.9,157.1,132.7,131.7,129.8,122.1,114.6,114.2,59.5,58.2,55.8,55.5,+
51.3,41.8,20.8,20.1,16.3;HRMS m/z(ESI)calcd for C22H27INO5S([M+H] )544.0649,found 544.0655。
乙酸乙酯/正已烷)得到目标产物I‑18(84%yield,d.r.>20:1);H NMR(500MHz,CDCl3)δ:
7.85(d,J=8.5Hz,2H),7.42(d,J=8.0Hz,2H),7.16(d,J=8.0Hz,2H),7.01(d,J=8.5Hz,
2H),3.92(d,J=10.0Hz,1H),3.87(s,3H),3.84(d,J=20.5Hz,1H),3.69‑3.52(m,3H),3.38
13
(d,J=15.0Hz,1H),2.32(s,3H),1.63(s,3H),1.57(s,3H);C NMR(125MHz,CDCl3)δ:
174.2,163.9,136.1,135.0,132.8,129.8,129.5,120.4,114.6,59.5,57.9,55.8,51.4,+
41.8,20.9,20.8,20.1,16.3;HRMS m/z(ESI)calcd for C22H27INO4S([M+H] )528.0700,found 528.0704。
乙酸乙酯/正已烷)得到目标产物I‑19(79%yield,d.r.>20:1);H NMR(500MHz,CDCl3)δ:
7.87‑7.84(m,2H),7.52‑7.49(m,2H),7.07‑7.01(m,4H),3.91(d,J=7.5Hz,1H),3.88(s,
3H),3.86(d,J=10.5Hz,1H),3.62‑3.59(m,3H),3.39(d,J=15.0Hz,1H),1.63(s,3H),1.57
13
(s,3H);C NMR(125MHz,CDCl3)δ:174.3,163.9,159.9(d,JC‑F=243.6Hz),134.7(d,JC‑F=
2.9Hz),132.6,129.8,122.1(d,JC‑F=7.9Hz),115.7(d,JC‑F=22.4Hz),114.6,59.5,58.1,
19
55.8,51.4,41.8,21.0,20.1,15.9;F NMR(471MHz,CDCl3)δ:‑116.5;HRMS m/z(ESI)calcd +
for C21H24FINO4S([M+H])532.0449,found 532.0453。
乙酸乙酯/正已烷)得到目标产物I‑20(75%yield,d.r.>20:1);H NMR(500MHz,CDCl3)δ:
7.86‑7.83(m,2H),7.49‑7.44(m,4H),7.02‑7.00(m,2H),3.89(d,J=3.0Hz,1H),3.88(s,
3H),3.85(d,J=10.5Hz,1H),3.61‑3.57(m,3H),3.39(d,J=15.0Hz,1H),1.62(s,3H),1.56
13
(s,3H);C NMR(125MHz,CDCl3)δ:174.5,163.9,137.7,132.6,132.0,129.8,121.6,118.1,
114.6,59.4,57.7,55.8,51.5,41.6,21.0,20.2,15.8;HRMS m/z(ESI)calcd for +
C21H24BrINO4S([M+H])591.9649,found 591.9653。
乙酸乙酯/正已烷)得到目标产物I‑21(82%yield,d.r.>20:1);H NMR(500MHz,CDCl3)δ:
7.87‑7.83(m,2H),7.37(s,1H),7.33(d,J=8.0Hz,1H),7.24(t,J=8.0Hz,1H),7.01‑6.97(m,3H),3.92(d,J=10.0Hz,1H),3.88(d,J=2.5Hz,1H),3.86(s,3H),3.63‑3.56(m,3H),
13
3.39(d,J=15.0Hz,1H),2.35(s,3H),1.63(s,3H),1.56(s,3H);C NMR(125MHz,CDCl3)δ:
174.4,163.9,138.9,138.6,132.8,129.8,128.8,126.1,121.0,117.4,114.6,59.5,57.9,+
55.8,51.5,41.7,21.6,20.9,20.1,16.2;HRMS m/z(ESI)calcd for C22H27INO4S([M+H])
528.0700,found528.0704。
1
酯/正已烷)得到目标产物I‑22(71%yield,d.r.>20:1);H NMR(500MHz,CDCl3)δ:7.93(t,J=2.0Hz,1H),7.84‑7,82(m,1H),7.65‑7.63(m,1H),7.54(d,J=8.0Hz,1H),7.52‑7.49(m,
2H),7.08‑7.05(m,2H),3.87(d,J=10.5Hz,2H),3.64‑3.57(m,3H),3.41(d,J=15.0Hz,
13
1H),1.66(s,3H),1.58(s,3H);C NMR(125MHz,CDCl3)δ:174.0,160.0(d,JC‑F=243.9Hz),
142.5,135.8,134.5(d,JC‑F=2.9Hz),134.2,130.8,127.7,125.7,122.2(d,JC‑F=8.0Hz),
19
115.8(d,JC‑F=22.4Hz),59.2,58.1,51.5,41.8,20.9,20.2,15.5;F NMR(471MHz,CDCl3)+
δ:‑116.3;HRMS m/z(ESI)calcd for C20H21ClFINO3S([M+H])535.9954,found 535.9950。
1
酯/正已烷)得到目标产物I‑23(62%yield,d.r.>20:1);H NMR(500MHz,CDCl3)δ:7.94(t,J=2.0Hz,1H),7.85‑7.83(m,1H),7.71(d,J=8.5Hz,2H),7.66‑7.63(m,3H),7.54(t,J=
8.0Hz,1H),3.94(d,J=10.5Hz,1H),3.86(d,J=10.0Hz,1H),3.67(d,J=10.5Hz,1H),3.63(d,J=15.0Hz,1H),3.58(d,J=10.0Hz,1H),3.42(d,J=15.0Hz,1H),1.67(s,3H),1.60(s,
13
3H);C NMR(125MHz,CDCl3)δ:174.6,142.4,141.4,135.8,134.3,130.9,127.7,126.3(q,
19
JC‑F=2.7Hz),125.7,125.0,122.9,119.7,59.1,57.5,51.7,41.6,21.0,20.3,15.2;F NMR+
(471MHz,CDCl3)δ:‑62.2;HRMS m/z(ESI)calcd for C21H21ClF3INO3S([M+H])585.9922,found 585,9926。
乙酸乙酯/正已烷)得到目标产物I‑24(62%yield,d.r.>20:1);H NMR(500MHz,CDCl3)δ:
7.95(d,J=8.5Hz,2H),7.81‑7.79(m,2H),7.35(d,J=8.5Hz,2H),7.04‑7.02(m,2H),4.47(d,J=11.0Hz,1H),3.89(s,3H),3.73(d,J=11.0Hz,1H),3.21‑3.17(m,2H),3.11(d,J=
13
14.0Hz,1H),3.01(d,J=11.0Hz,1H),2.45(s,3H),1.38(s,3H),1.13(s,3H);C NMR(125MHz,CDCl3)δ:172.7,164.1,145.6,134.6,133.8,132.4,129.8,128.3,114.8,59.1,
55.8,53.9,51.3,42.5,21.8,21.0,18.8,6.5;HRMS m/z(ESI)calcd for C22H27INO6S2([M++
H])592.0319,found592.0323。
乙酸乙酯/正已烷)得到目标产物I‑25(79%yield,d.r.>20:1);H NMR(500MHz,CDCl3)δ:
7.88(d,J=8.0Hz,2H),7.51‑7.45(m,2H),7.38(t,J=8.0Hz,2H),7.29(s,2H),7.23(t,J=
10.0Hz,4H),7.03(d,J=7.5Hz,2H),4.28(t,J=13.0Hz,1H),3.89(s,3H),3.82‑3.77(m,
13
1H),3.68(t,J=22.0Hz,1H),3.59‑3.52(m,3H),3.27‑3.16(m,2H),1.59(s,3H);C NMR(125MHz,CDCl3)δ:172.7,164.0,135.9,132.7,130.9,130.6,129.7,129.1,128.2,127.3,
125.1,120.0,114.6,57.4,56.8,56.3,55.8,43.2,37.7,19.2,17.2;HRMS m/z(ESI)calcd +
for C27H29INO4S([M+H])590.0856,found 590.0852。