亲电二氟甲基试剂S⁃(二氟甲基)硫𬭩盐对1,1⁃偕二氰基烯烃的二氟甲基化: 二氟甲基取代全碳中心的有效构建

doi:10.7503/cjcu20200383

摘要/Abstract

摘要：

以亲电的S-(二氟甲基)硫??盐作为二氟甲基源, 在有机碱作用下, 对1,1-偕二氰基烯烃的二氟甲基化反应进行了研究. 在最优反应条件下, 一系列1,1-偕二氰基烯烃发生二氟甲基化反应, 以43%~99%的分离收率获得结构多样的含有二氟甲基取代全碳中心的目标化合物. 实验结果表明, 该方法底物普适性良好, 不同的给电子和吸电子取代基、环状及链状底物、杂环、苯环、萘环和菲环等均适用于该反应, 可顺利发生转化得到相应的二氟甲基化目标产物.

关键词: S-(二氟甲基)硫&#x2cb69, 盐, 二氟甲基化, 全碳中心, 1,1-偕二氰基烯烃

Abstract:

An efficient approach for difluoromethylation of dicyanoalkylidenes by electrophilic S-（difluoromethyl）sulfonium salt under organic base was described. A wide range of structurally and functionally diverse dicyanoalkylidenes was readily transferred into corresponding desirable difluoromethylated compounds bearing difluoromethylated all-carbon-substituted centers in good to excellent yields under standard reaction conditions.

Key words: S-（Difluoromethyl）sulfonium salt, Difluoromethylation, All-carbon-substituted centers, 1, 1-Dicyanoalkylidene

中图分类号:

O621.3

TrendMD:

秦文兵, 林伟锋, 李鑫, 熊威, 刘国凯. 亲电二氟甲基试剂S⁃(二氟甲基)硫𬭩盐对1,1⁃偕二氰基烯烃的二氟甲基化: 二氟甲基取代全碳中心的有效构建. 高等学校化学学报, 2020, 41(10): 2230.

QIN Wenbing, LIN Weifeng, LI Xin, XIONG Wei, LIU Guokai. Difluoromethylation of Dicyanoalkylidenes by Electrophilic S-（Difluoromethyl）sulfonium Salt： Efficient Construction of Difluoromethylated All-carbon-substituted Centers^†. Chem. J. Chinese Universities, 2020, 41(10): 2230.

图/表 6

参考文献 30

1	Smart B. E.， Chem. Rev.，1996， 96， 1555—1556
2	Furuya T.， Kuttruff C.， Ritter T.， Curr. Opin. Drug Discovery Dev.，2008， 11， 803—819
3	Ojima I.， Fluorine in Medicinal Chemistry and Chemical Biology， Blackwell， Oxford， 2009，199—212
4	Wang J.， Sánchez⁃Roselló M.， Aceña J. L.， del Pozo C.， Sorochinsky A. E.， Fustero S.， Soloshonok V. A.， Liu H.， Chem. Rev.， 2014， 114， 2432—2506
5	Bassetto M.， Ferla S.， Pertusati F.， Future Med. Chem.，2015， 7， 527—546
6	Goure W. F.， Leschinsky K. L.， Wratten S. J.， Chupp J. P.， J. Agric. Food Chem.，1991， 39， 981—986
7	Pérez R. A.， Sánchez⁃Brunete C.， Miguel E.， Tadeo J. L.， J. Agric. Food Chem.，1998， 46， 1864—1869
8	Kirsch P.， Bremer B.， Angew. Chem. Int. Ed.，2000， 39， 4216—4239
9	Tasaka T.， Takenaka S.， Kabu K.， Morita Y.， Okamoto H.， Ferroelectronics， 2002， 276， 83—92
10	Boltalina O. V.， Nakajima T.， New Fluorinated Carbons： Fundamentals and Applications， Elsevier， Amsterdam， 2016， 305—323
11	Prakash G. K. S.， Mandal M.， Schweizer S.， Petasis N. A.， Olah G. A.， J. Org. Chem.， 2002， 67， 3718—3723
12	Narjes F.， Koehler K. F.， Koch U.， Gerlach B.， Colarusso S.， Steink_hler C.， Brunetti M.， Altamura S.， de Francesco R.， Matassa V. G.， Bioorg. Med. Chem. Lett.， 2002， 12（4）， 701—704
13	Hu J.， Zhang W.， Wang F.， Chem. Commun.， 2009， 7465—7578
14	Li Y.， Hu J.， Angew. Chem. Int. Ed.， 2005， 44， 5882—5886
15	Erickson J. A.， McLoughlin J. I.， J. Org. Chem.， 1995， 60， 1626—1631
16	Zafrani Y.， Yeffet D.， Sod⁃Moriah G.， Berliner A.， Amir D.， Marciano D.， Gershonov E.， Saphier S.， J. Med. Chem.，2017， 60， 797—804
17	Prakash G. K. S.， Weber C.， Chacko S.， Olah G. A.， Org. Lett.，2007， 9（10）， 1863—1866
18	Prakash G. K. S.， Zhang Z.， Wang F.， Ni C.， Olah G. A.， J. Fluorine Chem.， 2011， 132（10）， 792—798
19	Zhang W.， Wang F.， Hu J.， Org. Lett.， 2009， 11（10）， 2109—2112
20	Zhu J.， Liu Y.， Shen Q.， Angew. Chem. Int. Ed.， 2016， 55， 9050—9054
21	Lu S. L.， Li X.， Qin W. B.， Liu J. J.， Huang Y. Y.， Wong H. N. C.， Liu G. K， Org. Lett.， 2018， 20， 6925—6929
22	Liu G. K.， Li X.， Qin W. B.， Peng X. S.， Wong H. N. C.， Zhang L.， Zhang X.， Chem. Commun.， 2019， 55， 7446—7449
23	Liu G. K.， Qin W. B.， Li X.， Lin L. T.， Wong H. N. C.， J. Org. Chem.， 2019， 84（24）， 15948—15957
24	Liu G. K.， Li X.， Qin W. B.， Lin W. F.， Lin L. T.， Chen J. Y.， Liu J. J.， Chin. Chem. Lett.， 2019， 30， 1515—1518
25	Xue D.， Chen Y. C.， Cui X.， Wang Q. W.， Zhu J.， Deng J. G.， J. Org. Chem.，2005， 70， 3584—3591
26	Liu G. K.， Wang X.， Lu X.， Xu X. H.， Tokunaga E.， Shibata N.， Chemistry Open， 2012， 1， 227—231
27	Barnes D. M.， Haight A. R.， Hameury T.， McLaughlin M. A.， Mei J.， Tedrow J. S.， Riva Toma J. D.， Tetrahedron， 2006， 62， 11311—11319
28	Chen H.， Zhao S.， Cheng S.， Dai X.， Xu X.， Yuan W.， Zhang X.， J. Heterocyclic Chem.，2019， 56， 1672—1683
29	Aksu K.， Özgeriş B.， Tümer F.， Org. Commun.，2019， 12， 38—42
30	Matsnev A.， Noritake S.， Nomura Y.， Tokunaga E.， Nakamura S.， Shibata N.， Angew. Chem. Int. Ed.， 2010， 49， 572—576

Compd.	Appearance	m.p./℃(ref.)	MS^a(calcd.), m/z
2a	White solid	115.1—117.5(115.3—117.8)^[25]	194(194)
2b	Yellow solid	—	225.0(225.1)
2c	Light yellow solid	—	225.0(225.1)
2d	White solid	—	225.0(225.1)
2e	Brown solid	—	255.0(255.1)
2f	White solid	—	272.9(273.0), 275.0(275.0)^b
2g	White solid	—	208(208)
2h	Off?white solid	171.9—173.8(172.9—174.0)^[28]	208(208)
2i	Colorless oil	—	146(146)
2j	Yellow solid	121.0—123.0(120.9—123.2)^[25]	274(274), 276(276)^b
2k	Yellow solid	122.6—125.1(122.2—125.6)^[25]	212(212)
2m	White solid	157.1—159.5(157.2—159.3)^[25]	180(180)
2n	White solid	70.2—71.9(70.2—71.9)^[25]	194(194)
2o	White solid	—	194(194)
4a	White solid	—	168(168)
4b	Light yellow solid	93.2—94.(93.5—94.5)^[27]	246(246), 248(248)^b
4c	White solid	113.2—115.1(113—115)^[26]	260(260), 262(262)^b
4d	White solid	—	196(196)
4e	White solid	—	210(210)
4f	White solid	84.5—86.8(85.4—88.9)^[25]	244(244)
4g	Yellow solid	130.2—131.9(130—132)^[29]	268(268)
4h	Light yellow solid	114.0—116.3(114.1—116.1)^[25]	218(218)
4i	White solid	86.8—88.3(87—88)^[27]	174(174)
4j	Colorless oil	—	182(182)

Compd.	Appearance	m.p./℃(ref.)	MS^a(calcd.), m/z
2a	White solid	115.1—117.5(115.3—117.8)^[25]	194(194)
2b	Yellow solid	—	225.0(225.1)
2c	Light yellow solid	—	225.0(225.1)
2d	White solid	—	225.0(225.1)
2e	Brown solid	—	255.0(255.1)
2f	White solid	—	272.9(273.0), 275.0(275.0)^b
2g	White solid	—	208(208)
2h	Off?white solid	171.9—173.8(172.9—174.0)^[28]	208(208)
2i	Colorless oil	—	146(146)
2j	Yellow solid	121.0—123.0(120.9—123.2)^[25]	274(274), 276(276)^b
2k	Yellow solid	122.6—125.1(122.2—125.6)^[25]	212(212)
2m	White solid	157.1—159.5(157.2—159.3)^[25]	180(180)
2n	White solid	70.2—71.9(70.2—71.9)^[25]	194(194)
2o	White solid	—	194(194)
4a	White solid	—	168(168)
4b	Light yellow solid	93.2—94.(93.5—94.5)^[27]	246(246), 248(248)^b
4c	White solid	113.2—115.1(113—115)^[26]	260(260), 262(262)^b
4d	White solid	—	196(196)
4e	White solid	—	210(210)
4f	White solid	84.5—86.8(85.4—88.9)^[25]	244(244)
4g	Yellow solid	130.2—131.9(130—132)^[29]	268(268)
4h	Light yellow solid	114.0—116.3(114.1—116.1)^[25]	218(218)
4i	White solid	86.8—88.3(87—88)^[27]	174(174)
4j	Colorless oil	—	182(182)

Compd.	Appearance	m.p./℃	HRMS(calcd.)^a, m/z
3a	White solid	95.0—97.1	277.1148(277.1147)
3b	White solid	59.5—62.0	275.0987(275.0990)
3c	White solid	47.0—49.1	275.0987(275.0990)
3d	White solid	79.0—81.2	307.1248(307.1253)
3e	White solid	124.2—126.3	305.1098(305.1096)
3f	White solid	110.2—112.4	355.0246(355.0252)
3g	White solid	84.0—85.6	291.1308(291.1303)
3h	White solid	66.1—67.8	291.1306(291.1303)
3i	Colorless oil	—	229.1147(229.1147)
3j	White solid	135.0—137.2	357.0044(357.0045)
3k	Light yellow solid	97.1—99.8	295.0714(295.0711)
3l	Light yellow solid	144.7—146.8	313.0614(313.0617)
3m	White solid	85.7—88.0	263.0987(263.0990)
3n	White solid	100.7—102.4	277.1144(277.1147)
3o	White solid	76.5—78.6	277.1145(277.1147)
5a	White solid	37.3—39.0	251.0987(251.0990)
5b	White solid	53.0—55.1	329.0096(329.0096)
5c	White solid	91.7—94.0	343.0246(343.0252)
5d	Colorless oil	—	279.1315(279.1303)
5e	Colorless oil	—	293.1458(293.1460)
5f	White solid	81.3—82.4	327.1300(327.1303)
5g	White solid	115.3—117.2	351.1301(351.1303)
5h	White solid	86.8—88.0	301.1144(301.1147)
5i	Colorless oil	—	257.0551(257.0555)
5j	White solid	37.0—39.3	265.1148(265.1147)

Compd.	Appearance	m.p./℃	HRMS(calcd.)^a, m/z
3a	White solid	95.0—97.1	277.1148(277.1147)
3b	White solid	59.5—62.0	275.0987(275.0990)
3c	White solid	47.0—49.1	275.0987(275.0990)
3d	White solid	79.0—81.2	307.1248(307.1253)
3e	White solid	124.2—126.3	305.1098(305.1096)
3f	White solid	110.2—112.4	355.0246(355.0252)
3g	White solid	84.0—85.6	291.1308(291.1303)
3h	White solid	66.1—67.8	291.1306(291.1303)
3i	Colorless oil	—	229.1147(229.1147)
3j	White solid	135.0—137.2	357.0044(357.0045)
3k	Light yellow solid	97.1—99.8	295.0714(295.0711)
3l	Light yellow solid	144.7—146.8	313.0614(313.0617)
3m	White solid	85.7—88.0	263.0987(263.0990)
3n	White solid	100.7—102.4	277.1144(277.1147)
3o	White solid	76.5—78.6	277.1145(277.1147)
5a	White solid	37.3—39.0	251.0987(251.0990)
5b	White solid	53.0—55.1	329.0096(329.0096)
5c	White solid	91.7—94.0	343.0246(343.0252)
5d	Colorless oil	—	279.1315(279.1303)
5e	Colorless oil	—	293.1458(293.1460)
5f	White solid	81.3—82.4	327.1300(327.1303)
5g	White solid	115.3—117.2	351.1301(351.1303)
5h	White solid	86.8—88.0	301.1144(301.1147)
5i	Colorless oil	—	257.0551(257.0555)
5j	White solid	37.0—39.3	265.1148(265.1147)

Compd.	¹H NMR(500 MH_Z, CDCl₃), δ	¹³C NMR(126 MH_Z, CDCl₃), δ	¹⁹F NMR(471 MH_Z, CDCl₃), δ
3a	7.57—7.52(m, 1H), 7.32—7.26(m, 3H), 6.86(t, J=4.9 Hz, 1H), 6.39(t, J=54.3 Hz, 1H), 2.84—2.77(m, 2H), 2.51—2.44(m, 2H)	137.2, 136.5, 129.1, 129.0, 128.5, 127.0, 123.2, 122.5, 110.1(t, J=3.0 Hz), 109.9(t, J=259.3 Hz),46.8(t, J=24.7 Hz), 27.3, 23.5	-119.1(d, J=54.4 Hz)
3b	7.26(t, J=8.1 Hz, 1H), 7.18(d, J=7.9 Hz, 1H), 6.92(d, J=8.2 Hz, 1H), 6.86(t, J=4.9 Hz, 1H), 6.40(t, J=54.4 Hz, 1H), 3.86(s, 3H), 2.79(t, J=8.2 Hz, 2H), 2.41(td, J=8.2, 5.0 Hz, 2H)	156.8, 136.7, 129.4, 127.2, 125.5, 123.1, 115.0, 111.6, 110.2(t, J=2.8 Hz), 109.9(d, J=259.1 Hz), 55.7, 47.1(t, J=24.8 Hz), 23.0, 18.9	-119.3(d, J=54.5 Hz)
Compd.	¹H NMR(500 MH_Z, CDCl₃), δ	¹³C NMR(126 MH_Z, CDCl₃), δ	¹⁹F NMR(471 MH_Z, CDCl₃), δ
3c	7.50(d, J=8.3 Hz, 1H), 6.82(d, J=8.1 Hz, 2H), 6.73(t, J=4.9 Hz, 1H), 6.39(t, J=54.3 Hz, 1H), 3.85(s, 3H), 2.79(t, J=8.0 Hz, 2H), 2.46(td, J=8.0, 4.9 Hz, 2H)	159.8, 139.4, 133.5, 123.9, 122.9, 121.4, 115.3, 111.3, 110.2(t, J=2.9 Hz), 109.9(t, J=259.3 Hz), 55.4, 46.8(t, J=24.7 Hz), 27.9, 23.4	-118.6(d, J=53.9 Hz)
3d	7.18(d, J=8.3 Hz, 1H), 7.13(d, J=1.7 Hz, 1H), 6.87(t, J=4.8 Hz, 1H), 6.83(dd, J=8.3, 2.1 Hz, 1H), 6.40(t, J=54.3 Hz, 1H), 3.82(s, 3H), 2.72(t, J=7.9 Hz, 2H), 2.47—2.41(m, 2H)	158.5, 137.3, 129.7, 129.4, 129.1, 123.2, 113.5, 110.2(t, J=2.7 Hz), 110.0(t, J=259.4 Hz), 109.9, 55.6, 47.0(t, J=24.7 Hz), 26.5, 24.0	-119.1(d, J=54.3 Hz)
3e	7.15(s, 1H), 6.77(s, 1H), 6.71(t, J=4.9 Hz, 1H), 6.32(t, J=54.3 Hz, 1H), 3.91(s, 3H), 3.89(s, 3H), 2.72(t, J=8.1 Hz, 2H), 2.43(td, J=8.1, 7.7, 5.0 Hz, 2H)	149.2, 147.4, 133.8, 130.6, 122.9, 120.9, 112.1, 110.3(t, J=259.8 Hz), 110.2(t, J=2.8 Hz), 107.2, 56.3, 56.0, 46.7(t, J=24.7 Hz), 27.1, 23.6	-118.6(d, J=54.4 Hz)
3f	7.65(s, 1H), 7.43(dd, J=8.0, 1.7 Hz, 1H), 7.14(d, J=8.0 Hz, 1H), 6.92(t, J=4.9 Hz, 1H), 6.35(t, J=54.1 Hz, 1H), 2.75(t, J=8.0 Hz, 2H), 2.47(td, J=8.0, 5.0 Hz, 2H)	138.2, 136.2, 132.1, 130.6, 130.5, 125.8, 122.6, 120.6, 109.9(t, J=259.8 Hz), 109.9(d, J=4.7 Hz), 26.9, 23.5	-118.8(d, J=54.1 Hz)
3g	7.57(d, J=7.5 Hz, 1H), 7.37—7.27(m, 3H), 6.82—6.74(m, 1H), 6.41(t, J=54.3 Hz, 1H), 3.00—2.92(m, 1H), 2.61(ddd, J=17.3, 6.6, 4.2 Hz, 1H), 2.32(dt, J=17.2, 6.1 Hz, 1H), 1.21(d, J=7.0 Hz, 3H)	142.2, 135.0, 129.5, 127.8, 127.6, 126.8, 122.6, 122.5, 110.1(dd, J=51.3, 4.3 Hz), 109.8(t, J=259.2 Hz), 46.8(t, J=24.8 Hz), 31.5, 31.0, 19.5	-118.2(d, J=54.1 Hz), -118.8(d, J=54.6 Hz), -118.9(d, J=54.4 Hz), -119.5(d, J=54.0 Hz)
3h	7.67(dd, J=5.6, 3.5 Hz, 1H), 7.35(dt, J=7.4, 3.7 Hz, 2H), 7.32—7.28(m, 1H), 7.00(t, J=7.6 Hz, 1H), 5.87(t, J=54.1 Hz, 1H), 2.53(t, J=7.1 Hz, 2H), 2.15(p, J=7.1 Hz, 2H), 1.98(q, J=7.3 Hz, 2H)	141.9, 138.6, 132.8, 129.9, 129.6, 127.1, 126.4, 125.2, 110.9(t, J=258.9 Hz), 110.3(t, J=3.0 Hz),47.7(t, J=24.9 Hz), 33.6, 31.4, 24.7	-120.8(d, J=53.9 Hz)
3i	6.41(s, 1H), 5.94(t, J=54.4 Hz, 1H), 2.22(qd, J=8.5, 7.4, 3.2 Hz, 4H), 1.80—1.73(m, 2H), 1.69—1.62(m, 2H)	134.5, 123.2, 111.2(t, J=260.1 Hz), 109.7(t, J=3.1 Hz), 48.7(t, J=24.2 Hz), 25.7, 25.5, 22.2, 20.9	-118.8(d, J=54.3 Hz)
3j	7.62(d, J=2.1 Hz, 1H), 7.42(dd, J=8.7, 2.2 Hz, 1H), 6.88(d, J=8.6 Hz, 1H), 6.59(t, J=4.1 Hz, 1H), 6.34(t, J=54.0 Hz, 1H), 4.89(d, J=4.1 Hz, 2H)	153.7, 134.3, 129.4, 125.6, 120.2, 119.5, 119.2, 114.2, 109.61(t, J=260.6 Hz), 108.97(t, J=2.9 Hz), 64.6, 45.71(t, J=25.7 Hz)	-117.7(d, J=54.0 Hz)
3k	7.73—7.69(m, 1H), 7.52—7.46(m, 1H), 7.30—7.25(m, 2H), 6.87(t, J=6.1 Hz, 1H), 6.24(t, J=54.1 Hz, 1H), 3.39(d, J=6.1 Hz, 2H)	135.8, 129.9, 129.5, 129.12, 128.4, 126.3, 124.8, 124.5, 110.1(t, J=260.1 Hz), 109.9(t, J=2.9 Hz), 47.1(t, J=25.2 Hz), 24.9	-118.4(d, J=54.0 Hz)
3l	7.52—7.44(m, 2H), 7.04(td, J=8.3, 2.5 Hz, 1H), 6.94(t, J=6.1 Hz, 1H), 6.23(t, J=54.1 Hz, 1H), 3.38(d, J=6.1 Hz, 2H)	160.8(d, J=247.0 Hz), 131.6, 130.9(d, J=3.3 Hz), 130.6(d, J=7.9 Hz), 129.8(d, J=7.4 Hz), 124.6, 117.0(d, J=21.8 Hz), 112.3(d, J=24.9 Hz), 110.2(t, J=260.5 Hz), 109.7(t, J=2.9 Hz), 108.1, 47.1(t, J=25.5 Hz), 25.1	-113.1(m, F), -118.5(d, J=54.1 Hz, 2F)
3m	7.69(d, J=7.6 Hz, 1H), 7.60(d, J=7.3 Hz, 1H), 7.44(t, J=7.3 Hz, 1H), 7.42—7.38(m, 1H), 7.13(t, J=2.1 Hz, 1H), 6.31(t, J=54.2 Hz, 1H), 3.65—3.59(m, 2H)	144.2, 139.1, 138.2, 128.3, 127.1, 126.9, 124.8, 120.0, 110.5(t, J=260.7 Hz), 109.2(t, J=3.0 Hz), 43.1(t, J=25.8 Hz), 38.3	-117.8(d, J=54.1 Hz)
3n	7.46—7.41(m, 2H), 7.18(d, J=7.8 Hz, 1H), 7.07(t, J=1.9 Hz, 1H), 6.29(t, J=54.2 Hz, 1H), 3.53(s, 2H), 2.45(s, 3H).	141.4, 139.4, 138.6, 137.1, 128.2, 128.0, 124.6, 120.6, 110.5(t, J=260.6 Hz), 109.4(t, J=2.7 Hz), 43.3(t, J=25.9 Hz), 38.1, 21.8	-118.0(d, J=54.2 Hz)
Compd.	¹H NMR(500 MH_Z, CDCl₃), δ	¹³C NMR(126 MH_Z, CDCl₃), δ	¹⁹F NMR(471 MH_Z, CDCl₃), δ
3o	7.68(d, J=7.8 Hz, 1H), 7.45(d, J=7.4 Hz, 1H), 7.34(t, J=7.6 Hz, 1H), 7.26(t, J=7.8 Hz, 1H), 6.23(t, J=54.4 Hz, 1H), 3.54(s, 2H), 2.47(s, 3H)	150.5, 140.8, 140.7, 126.9, 125.8, 123.9, 119.2, 118.1, 110.6(t, J=260.4 Hz), 109.7(t, J=3.2 Hz), 45.6, 41.7(t, J=26.1 Hz), 15.3	-118.9(d, J=54.4 Hz)
5a	7.49—7.42(m, 3H), 7.41—7.37(m, 2H), 6.14(s, 1H), 5.86(t, J=53.9 Hz, 1H), 5.73(s, 1H)	134.9, 134.4, 130.0, 129.2, 128.7, 125.4, 110.5(t, J=259.2 Hz), 109.5(t, J=2.9 Hz),48.2(t, J=25.1 Hz)	-120.4(d, J=54.3 Hz)
5b	7.59(d, J=8.4 Hz, 2H), 7.27(d, J=8.3 Hz, 2H), 6.15(s, 1H), 5.87(t, J=53.9 Hz, 1H), 5.75(s, 1H)	134.0, 133.2, 132.4, 130.3, 126.0, 124.6, 110.5(t, J=259.6 Hz), 109.3(t, J=2.9 Hz), 48.0(t, J=25.3 Hz)	-120.5(d, J=53.8 Hz)
5c	7.66—7.60(m, 2H), 7.17—7.10(m, 2H), 6.65(q, J=6.8 Hz, 1H), 5.78(t, J=53.9 Hz, 1H), 1.63(d, J=6.8 Hz, 3H)	136.2, 132.8, 131.6, 131.0, 125.7, 124.2, 110.6(t, J=258.8 Hz), 109.5(t, J=2.9 Hz), 48.9(t, J=25.0 Hz), 15.3	-120.8(d, J=53.8 Hz)
5d	7.46(dd, J=5.1, 1.9 Hz, 3H), 7.23(dd, J=6.6, 2.8 Hz, 2H), 6.52(t, J=7.4 Hz, 1H), 5.76(t, J=54.0 Hz, 1H), 1.93(p, J=7.5 Hz, 2H), 0.99(t, J=7.5 Hz, 3H)	141.9, 132.2, 129.9, 129.6, 129.4, 125.5, 110.6(t, J=258.4 Hz), 109.7(t, J=2.8 Hz), 49.2(t, J=24.9 Hz), 22.9, 13.2	-121.7(d, J=53.8 Hz)
5e	7.48—7.44(m, 3H), 7.23(dd, J=6.6, 2.9 Hz, 2H), 6.30(d, J=10.1 Hz, 1H), 5.75(t, J=54.0 Hz, 1H), 2.15(dp, J=10.1, 6.6 Hz, 1H), 0.97(d, J=6.6 Hz, 6H)	146.9, 132.3, 129.8, 129.6, 129.3, 123.9, 110.6(t, J=258.4 Hz), 109.7(t, J=2.9 Hz), 49.2(t, J=24.8 Hz), 29.0, 22.0, 21.7	-121.8(d, J=54.0 Hz)
5f	7.57—7.50(m, 3H), 7.40—7.33(m, 3H), 7.26(t, J=7.3 Hz, 1H), 7.19(t, J=7.6 Hz, 2H), 6.97(d, J=7.6 Hz, 2H), 5.89(t, J=53.9 Hz, 1H)	137.3, 133.2, 132.7, 130.1, 130.1, 130.0, 129.8, 129.3, 128.5, 125.4, 110.8(t, J=258.9 Hz),109.7(t, J=2.8 Hz), 50.2(t, J=25.0 Hz)	-121.5(d, J=54.0 Hz)
5g	8.76(s, 1H), 8.69(d, J=8.2 Hz, 1H), 7.99(d, J=8.2 Hz, 1H), 7.96(d, J=7.8 Hz, 1H), 7.87(d, J=8.8 Hz, 1H), 7.79(d, J=8.8 Hz, 1H), 7.74(t, J=7.6 Hz, 1H), 7.69(t, J=7.0 Hz, 1H), 7.63(dd, J=8.2, 1.5 Hz, 2H), 6.31(s, 1H), 5.95(t, J=53.8 Hz, 1H), 5.92(s, 1H)	135.2, 132.6, 132.4, 132.3, 130.3, 129.8, 129.6, 128.9, 128.8, 127.5, 127.3, 126.3, 126.1, 125.8, 123.3, 122.6, 110.7(t, J=259.3 Hz), 109.7(t, J=2.9 Hz), 48.5(t, J=25.1 Hz)	-120.8(d, J=53.8 Hz)
5h	7.91(d, J=8.5 Hz, 1H), 7.90—7.87(m, 3H), 7.61—7.54(m, 2H), 7.47(dd, J=8.4, 1.9 Hz, 1H), 6.22(d, J=1.0 Hz, 1H), 5.90(t, J=53.9 Hz, 1H), 5.83(s, 1H)	135.0, 133.5, 132.9, 131.7, 129.2, 128.5, 128.4, 127.8, 127.6, 127.3, 125.7, 125.5, 110.6(t, J=259.3 Hz), 109.6(t, J=2.9 Hz), 48.3(t, J=25.2 Hz)	-120.8(d, J=53.9 Hz)
5i	7.43—7.39(m, 1H), 7.35(d, J=3.6 Hz, 1H), 7.10(dd, J=5.2, 3.7 Hz, 1H), 6.09(s, 1H), 6.08(t, J=54.2 Hz, 1H), 5.95(d, J=1.5 Hz, 1H)	135.0, 128.2, 128.0, 127.9, 127.8, 124.9, 110.4(t, J=260.0 Hz), 109.4(t, J=2.9 Hz), 48.1(d, J=25.3 Hz)	-119.5(d, J=54.5 Hz)
5j	7.47—7.33(m, 5H), 6.17(t, J=54.2 Hz, 1H), 5.67—5.53(m, 1H), 2.47(d, J=1.4 Hz, 3H)	150.9, 140.6, 129.4, 128.8, 126.1, 111.3(t, J=259.1 Hz), 109.7(t, J=3.1 Hz), 109.2(t, J=2.7 Hz), 40.1(t, J=25.1 Hz), 18.5	-120.5(d, J=54.0 Hz)