Synthesis of Chiral Phenylbenzothiazole Methanol via Transfer Hydrogenation Catalyzed by Ruthenium Complexes†

doi:10.7503/cjcu20200246

Abstract

Abstract:

A series of chiral phenylbenzothiazole methanol was obtained with up to 99% e.e. value via transfer hydrogenation from phenylbenzothiazolone， with readily available chiral diamine-derived ruthenium complex as a catalyst and sodium formate as a hydrogen source in a mixture of i-PrOH/H₂O（volume ratio 1：1） under ambient conditions. In addition， the reduction of other aryl N-heteroaryl ketones was also attempted. This method has the advantages of mild rection conditions， readily available and inexpensive catalysts， simple operation.

Key words: Asymmetric transfer hydrogenation, Chiral diamine ruthenium complex, Phenylbenzothiazole methanol

CLC Number:

O626.25

TrendMD:

CHEN Danyi, ZHANG Fumei, HE Dan, ZHANG Zimei, ZHONG Fen, WEN Simiaomiao, LIU Qixing, ZHOU Haifeng. Synthesis of Chiral Phenylbenzothiazole Methanol via Transfer Hydrogenation Catalyzed by Ruthenium Complexes^†[J]. Chem. J. Chinese Universities, 2020, 41(10): 2264.

Figures/Tables 4

References 26

1	Yang Z. Y.， Cheng Y. Y.， Zhou L.， Chin. J. Syn. Chem.， 2020， 28（1），84—90（杨志勇，成园园，周亮. 合成化学， 2020， 28（1）， 84—90）
2	Kida T.， Fujii A.， Sakai O.， Iemura M.， Atsumi I.， Wada T.， Sakaki H.， Exp. Eye Res.， 2010， 91（1）， 85—91
3	Hellbom E.， Med. Hypotheses，2006， 66（4）， 689—690
4	Rizzetto M.， Ciancio A.， Lancet Infect. Dis.， 2015， 15（10）， 1119—1120
5	Slaughter S. R.， Hearns⁃Stokes R.， van der Vlugt T.， Joffe H. V.， New Engl. J. Med.， 2014， 370（12）， 1081—1083
6	Xu G. C.， Wang Y.， Tang M. H.， Zhou J. Y.， Zhao J.， Han R. Z.， Ni Y.， ACS Catal.，2018， 8（9）， 8336—8345
7	Liu B. B.， Qu G.， Li J. K.， Fan W. C.， Ma J. A.， Xu Y.， Nie Y.， Sun Z. T.， Adv. Synth. Catal.，2019， 361（13）， 3182—3190
8	Liu Y. L.， Lin X. T.， Adv. Synth. Catal.， 2019， 361（5）， 876—918
9	Xie X. M.， Lu B.， Li W. F.， Zhang Z. G.， Coordin. Chem. Rev.，2018， 355， 39—53
10	Zassinovich G.， Mestroni G.， Gladiali S.， Chem. Rev.，1992， 92（5）， 1051—1069
11	Hashiguchi S.， Fujii A.， Takehara J.， Ikariya T.， Noyori R.， J. Am. Chem. Soc.， 1995， 117（28）， 7562—7563
12	Zhao J. F.， Dou H. J.， Zhou Y. H.， Qu J. P.， Chem. J. Chinese Universities， 2011， 32（10）， 2331—2334（赵金凤，窦海建，周宇涵，曲景平. 高等学校化学学报， 2011， 32（10）， 2331—2334）
13	Wang B. G.， Zhou H. F.， Lu G. R.， Liu Q. X.， Jiang X. L.， Org. Lett.，2017， 19（8）， 2094—2097
14	Liu Q. X.， Wang C. Q.， Zhou H. F.， Wang B. G.， Lv J. L.， Cao L.， Fu Y. G.， Org. Lett.，2018， 20（4）， 971—974
15	Zhang K. L.， Yang Y. P.， Liu H.， Liu Q. X.， Lv J. L.， Zhou H. F.， Adv. Synth. Catal.，2019， 361（17）， 4106—4110
16	Cui P.， Liu Q. X.， Wang J.， Liu H.， Zhou H. F.， Green Chem.，2019， 21（3）， 634—639
17	Liu S. S.， Cui P.， Wang J.， Zhou H. F.， Liu Q. X.， Lv J. L.， Org. Biomol. Chem.，2019， 17（2）， 264—267
18	Liu S. S.， Liu H.， Zhou H. F.，Liu Q. X.， Lv J. L.， Org. Lett.，2018， 20（4）， 1110—1113
19	Liu H.， Liu S. S.， Zhou H. F.，Liu Q. X.， Wang C. Q.， RSC Adv.，2018， 8（27）， 14829—14832
20	Sui Y. Z.， Zhang X. C.， Wu J. W.， Li S. J.， Zhou J. N.， Li M.， Fang W. J.， Chan A. S. C.， Wu J.， Chem. Eur. J.，2012， 18（24）， 7486—7492
21	Tao X. M.， Li W. F.， Ma X.， Li X. M.， Fan W. Z.， Xie X. M.， Ayad T.， Ratovelomanana⁃Vidal V.， Zhang Z. G.， J. Org. Chem.，2012， 77（1）， 612—616
22	Yang H. L.， Huo N. N.， Yang P.， Pei H.， Lv H.， Zhang X. M.， Org. Lett.，2015， 17（17）， 4144—4147
23	Chen F. M.， He D. X.， Chen L.， Chang X. Y.， Wang D. Z.， Xu C.， Xing X. Y.， ACS Catal.，2019， 9（6）， 5562—5566
24	Nian S. F.， Ling F.， Chen J. C.， Wang Z.， Shen H. W.， Yi X.， Yang Y. F.， She Y. B.， Zhong W. H.， Org. Lett.，2019， 21（14）， 5392—2396
25	Chen C. Y.， Reamer R. A.， Chilenski J. R.， McWilliams C. J.， Org. Lett.， 2003， 5（26）， 5039—5042
26	Lebedev Y.， Polishchuk I.， Maity B.， Guerreiro M. D. V.， Cavallo L.， Rueping M.， J. Am. Chem. Soc.， 2019， 141（49）， 19415—19423

Compd.	Appearance	Yield(%)	m.p./℃	Compd.	Appearance	Yield(%)	m.p./℃
2a	White solid	89	110—113	2n	Yellow solid	88	130—132
2b	White solid	77	119—121	2o	White solid	55	93—95
2c	White solid	73	111—113	2p	White solid	74	153—155
2d	White solid	89	110—112	2q	Yellow solid	81	123—125
2e	White solid	75	63—65	2r	Yellow solid	83	131—133
2f	Yellow solid	78	114—116	2s	White solid	75	86—88
2g	White solid	81	108—110	2t	White solid	85	75—77
2h	White solid	69	115—117	2u	White solid	84	136—138
2i	Yellow solid	74	145—147	2v	White solid	52	135—137
2j	Yellow solid	70	126—128	2w	White solid	74	151—153
2k	White solid	82	125—127	2x	White solid	76	72—74
2l	White solid	83	100—102	2y	White solid	77	123—125
2m	Yellow solid	77	179—181	2z	White solid	88	107—109

Compd.	Appearance	Yield(%)	m.p./℃	Compd.	Appearance	Yield(%)	m.p./℃
2a	White solid	89	110—113	2n	Yellow solid	88	130—132
2b	White solid	77	119—121	2o	White solid	55	93—95
2c	White solid	73	111—113	2p	White solid	74	153—155
2d	White solid	89	110—112	2q	Yellow solid	81	123—125
2e	White solid	75	63—65	2r	Yellow solid	83	131—133
2f	Yellow solid	78	114—116	2s	White solid	75	86—88
2g	White solid	81	108—110	2t	White solid	85	75—77
2h	White solid	69	115—117	2u	White solid	84	136—138
2i	Yellow solid	74	145—147	2v	White solid	52	135—137
2j	Yellow solid	70	126—128	2w	White solid	74	151—153
2k	White solid	82	125—127	2x	White solid	76	72—74
2l	White solid	83	100—102	2y	White solid	77	123—125
2m	Yellow solid	77	179—181	2z	White solid	88	107—109

Compd.	¹H NMR(400 Hz), δ	¹³C NMR(100 Hz), δ
2a	8.00(d, J=8.0 Hz, 1H), 7.86(d, J=8.0 Hz, 1H), 7.61—7.59(m, 1H), 7.51—7.48(m, 1H), 7.42—7.37(m, 1H), 7.31—7.28(m, 2H), 7.24—7.22(m, 1H), 6.38(s, 1H), 4.72(s, 1H), 2.44(s, 3H)	175.4, 152.6, 139.1, 136.1, 135.3, 130.9, 128.6, 126.9, 126.5, 126.1, 125.2, 123.1, 121.8, 71.4, 19.5
2b	8.02(d, J=8.0 Hz, 1H), 7.87(d, J=8.0 Hz, 1H), 7.61(dd, J₁=J₂=7.6 Hz,1H), 7.50(dd, J₁=J₂=7.6 Hz,1H), 7.42—7.34(m, 2H), 7.20(dd, J₁=J₂=7.6 Hz,1H), 7.13(dd, J₁=J₂=7.6 Hz,1H), 6.51(s, 1H), 4.66(s, 1H)	173.9, 161.4(d, J=246.4 Hz), 152.5, 135.3, 130.4(d, J=8.2 Hz), 128.4(d, J=3.7 Hz), 128.2(d, J=14.0 Hz), 126.2, 125.3, 124.7(d, J=3.4 Hz), 123.1, 121.8, 115.8(d, J=21.1 Hz), 68.2(d, J=3.8 Hz)
2c	8.03(d, J=8.4 Hz, 1H), 7.86(d, J=8.0 Hz, 1H), 7.70—7.68(m, 1H), 7.52—7.47(m, 1H), 7.46—7.43(m, 1H), 7.40(d, J=7.2 Hz, 1H), 7.36—7.30(m, 2H), 6.64(s, 1H), 4.83(s, 1H)	173.6, 152.3, 138.6, 135.3, 132.9, 129.8, 129.7, 128.6, 127.4, 126.2, 125.3, 123.1, 121.8, 70.8
2d	8.06(d, J=8.0 Hz, 1H), 7.87(d, J=8.0 Hz, 1H), 7.68—7.63(m, 2H), 7.54—7.49(m, 1H), 7.44—7.38(m, 2H), 7.28—7.24(m, 1H), 6.60(d, J=4.0 Hz, 1H), 4.57(d, J=4.4 Hz, 1H)	173.3, 152.3, 140.2, 135.5, 133.0, 130.2, 128.9, 128.1, 126.2, 125.4, 123.2, 122.9, 121.8, 73.1
2e	8.07(d, J=8.0 Hz, 1H), 7.87(d, J=8.0 Hz, 1H), 7.77(d, J=8.0 Hz, 2H), 7.64—7.59(m,1H), 7.55—7.49(m, 2H), 7.45—7.40(m, 1H), 6.58(d, J=3.6 Hz, 1H), 4.59(d, J=4.0 Hz, 1H)	173.4, 152.2, 139.6, 135.6, 132.6, 129.7, 128.8, 128.2(q, J=30.2 Hz), 126.3, 125.9(q, J=5.5 Hz), 125.6(q, J=254.4 Hz), 125.4, 123.3, 121.8, 69.4(q, J=3.6 Hz)
2f	9.17(s, 1H), 7.99(d, J=8.0 Hz, 1H), 7.87(d, J=7.6 Hz, 1H), 7.53—7.48(m, 1H), 7.44—7.40(m, 2H), 7.31—7.24(m, 1H), 7.02—6.95(m, 2H), 6.40(s, 1H), 4.51(s, 1H)	175.9, 154.7, 152.0, 134.5, 130.0, 126.7, 126.6, 126.5, 125.4, 122.7, 121.9, 120.7, 118.6, 72.1
2g	8.02(d, J=8.0 Hz, 1H), 7.90(d, J=8.0 Hz, 1H), 7.57—7.50(m, 3H), 7.44—7.39(m, 1H), 7.14—7.10(m, 2H), 6.17(s, 1H), 4.04(s, 1H)	174.6, 164.1(d, J=246.2 Hz), 152.6, 136.8, 135.3, 128.7(d, J=8.3 Hz), 126.3, 125.3, 123.1, 121.9, 116.0(d, J=21.6 Hz), 73.8
2h	8.02(d, J=7.6 Hz, 1H), 7.89(d, J=7.6 Hz, 1H), 7.54—7.50(m, 3H), 7.44—7.39(m, 3H), 6.17(s, 1H), 3.98(s, 1H)	174.2, 152.5, 139.4, 135.3, 134.6, 129.0, 128.1, 126.3, 125.4, 123.2, 121.9, 73.8
2i	8.30(d, J=8.4 Hz, 2H), 8.04(d, J=8.0 Hz, 1H), 7.91(d, J=8.0 Hz, 1H), 7.82(d, J=8.4 Hz, 2H), 7.56—7.52(m, 1H), 7.46—7.42(m, 1H), 6.31(s, 1H), 4.21(s, 1H)	173.0, 152.4, 147.9, 147.5, 135.1, 127.5, 126.5, 125.7, 124.0, 123.3, 122.0, 73.4
2j	8.03(d, J=8.4 Hz, 1H), 7.89(d, J=8.0 Hz, 1H), 7.74—7.67(m, 4H), 7.55—7.50(m, 1H), 7.45—7.40(m, 1H), 6.26(s, 1H), 4.16(s, 1H)	173.7, 152.5, 144.6, 135.2, 130.9(q, J=36.3 Hz), 127.0, 126.4, 125.9(q, J=3.8 Hz), 125.5, 125.4(q, J=271.8 Hz), 123.2, 121.9, 73.8
2k	8.03(d, J=8.0 Hz, 1H), 7.87(d, J=8.0 Hz, 1H), 7.52—7.47(m, 1H), 7.46(d, J=8.0 Hz, 2H), 7.42—7.37(m, 1H), 7.23(d, J=8.0 Hz, 2H), 6.15(s, 1H), 3.97(s, 1H), 2.39(s, 3H)	175.2, 152.7, 138.6, 138.1, 135.3, 129.6, 126.7, 126.1, 125.1, 123.1, 121.8, 74.3, 21.3
2l	8.03(d, J=8.0 Hz, 1H), 7.88(d, J=8.0 Hz, 1H), 7.53—7.46(m, 3H), 7.43—7.38(m, 1H), 6.96(d, J=8.8 Hz, 2H), 6.14(s, 1H), 3.84(s, 3H), 3.80(s, 1H)	175.2, 159.9, 152.7, 133.2, 133.2, 128.2, 126.1, 125.1, 123.1, 121.8, 114.2, 74.1, 55.3
2m	9.45(s, 1H), 8.09(d, J=8.0 Hz, 1H), 7.91(d, J=8.0 Hz, 1H), 7.50—7.45(m, 1H), 7.42—7.38(m, 1H), 7.30(d, J=8.4 Hz, 2H), 6.82(d, J=4.0 Hz, 1H), 6.75(d, J=8.4 Hz, 2H), 5.95(d, J=4.4 Hz, 1H)	178.6, 157.4, 153.5, 134.7, 133.2, 128.3, 126.4, 125.2, 122.9, 122.7, 115.5, 73.1
2n	8.03(d, J=8.0 Hz, 1H), 7.88(d, J=8.0 Hz, 1H), 7.53(m, 3H), 7.16—7.12(m, 2H), 6.92(d, J=8.0 Hz, 1H), 6.16(s, 1H), 3.91(s, 1H), 3.84(s, 3H)	174.7, 160.0, 152.6, 142.5, 135.4, 129.9, 126.2, 125.2, 123.1, 121.8, 119.0, 114.4, 112.1, 74.4, 55.3
2o	8.01(d, J=8.4 Hz, 1H), 7.90—7.87(m, 2H), 7.76(d, J=8.0 Hz, 1H), 7.64(d, J=7.6 Hz, 1H), 7.55—7.49(m, 2H), 7.44—7.39(m, 1H), 6.26(d, J=1.6 Hz, 1H), 4.51(s, 1H)	174.0, 152.4, 141.8, 135.2, 131.3(q, J=32.2 Hz), 130.1, 129.3, 126.4, 125.5, 125.4(q, J=3.6 Hz), 125.3(q, J=270.7 Hz), 123.5(q, J=4.0 Hz), 123.1, 121.9, 73.7
Compd.	¹H NMR(400 Hz), δ	¹³C NMR(100 Hz), δ
2p	8.49(s, 1H), 8.22(d, J=8.0 Hz, 1H), 8.01(d, J=8.0 Hz, 1H), 7.93(d, J=8.0 Hz, 1H), 7.89(d, J=8.0 Hz, 1H), 7.59(dd, J₁=J₂=7.6 Hz,1H), 7.54—7.50(m, 1H), 7.45—7.41(m, 1H), 6.31(d, J=2.4 Hz, 1H), 4.55(d, J=3.2 Hz, 1H)	173.4, 152.4, 148.5, 142.8, 135.1, 132.8, 129.8, 126.5, 125.6, 123.5, 123.2, 122.0, 121.7, 73.2
2q	8.04(d, J=8.0 Hz, 1H), 7.87(d, J=8.0 Hz, 1H), 7.75(d, J=2.8 Hz, 1H), 7.54—7.49(m, 1H), 7.44—7.40(m, 1H), 7.36(d, J=8.4 Hz, 1H), 7.32—7.29(m, 1H), 6.58(d, J=3.2 Hz, 1H), 5.15(d, J=3.6 Hz, 1H)	172.7, 152.1, 140.2, 135.3, 133.5, 130.9, 130.8, 129.9, 128.6, 126.4, 125.6, 123.2, 121.9, 70.3
2r	8.01(d, J=7.6 Hz, 1H), 7.91(d, J=8.0 Hz, 1H), 7.52(dt, J₁=7.6 Hz, J₂=1.2 Hz, 1H), 7.44—7.32(m, 2H), 7.00—6.93(m, 2H), 6.53(s, 1H), 4.26(s, 1H)	173.1(d, J=2.8 Hz), 162.4(dd, J₁=256.9 Hz, J₂=7.5 Hz), 152.7, 135.3, 131.0(t, J=10.5 Hz), 126.2, 125.2, 123.2, 121.8, 117.2, 112.2(dd, J₁=19.3 Hz, J₂=5.7 Hz), 65.7(t, J=3.7 Hz)
2s	8.03(d, J=8.0 Hz, 1H), 7.89(d, J=8.0 Hz, 1H), 7.60—7.49(m, 2H), 7.44—7.40(m, 1H), 6.97—6.86(m, 2H), 6.45(s, 1H), 4.52(s, 1H)	173.4, 164.4(dd, J₁=248.8 Hz, J₂=11.9 Hz), 161.5(dd, J₁=247.2 Hz, J₂=12.0 Hz), 152.4, 135.2, 129.5(dd, J₁=9.7 Hz, J₂=4.9 Hz), 126.3, 125.4, 124.4(d, J=17.0 Hz), 123.2, 121.8, 111.8(dd, J₁=21.3 Hz, J₂=3.7 Hz), 104.2(dd, J₁=J₂=25.2 Hz), 67.8(d, J=3.5 Hz)
2t	8.02(d, J=8.0 Hz, 1H), 7.87(d, J=8.0 Hz, 1H), 7.51—7.38(m, 3H), 6.73(d, J=8.0 Hz, 1H), 6.68(d, J=8.0 Hz, 1H) 6.41(s, 1H), 4.53(s, 1H), 3.82(s, 3H)	174.5, 162.1(d, J=246.1 Hz), 161.2(d, J=11.0 Hz), 152.6, 135.3, 129.2(d, J=5.4 Hz), 126.2, 125.2, 123.1, 121.8, 120.4(d, J=13.5 Hz), 110.4(d, J=2.9 Hz), 101.9(d, J=24.9 Hz), 68.1, 55.6
2u	9.25(s, 1H), 7.99(d, J=8.4 Hz, 1H), 7.93(d, J=8.4 Hz, 1H), 7.55—7.51(m, 1H), 7.46—7.42(m, 1H), 7.23(dd, J₁=9.6 Hz, J₂=2.4 Hz, 1H), 6.99—6.92(m, 2H), 6.42(s, 1H), 3.93(s, 1H)	175.8, 158.3(d, J=237.4 Hz), 151.9, 150.2, 134.1, 128.8(d, J=7.1 Hz), 126.6, 125.5, 122.7, 122.0, 119.9(d, J=7.7 Hz), 116.2(d, J=22.9 Hz), 112.6(d, J=24.7 Hz), 70.8
2v	8.04—8.00(m, 2H), 7.89—7.84(m, 4H), 7.63(dd, J₁=8.8 Hz, J₂=2.0 Hz, 1H), 7.55—7.51(m, 2H), 7.49—7.45(m, 1H), 7.40—7.36(m, 1H), 6.34(s, 1H), 4.66(s, 1H)	175.2, 152.6, 138.3, 135.3, 133.4, 133.2, 128.8, 128.3, 127.8, 126.5, 126.4, 126.2, 126.0, 125.2, 124.3, 123.1, 121.8, 74.5
2w	8.25—8.22(m, 1H), 8.02(d, J=8.0 Hz, 1H), 7.93—7.90(m, 2H), 7.82—7.79(m, 2H), 7.56—7.46(m, 4H), 7.38(dd, J₁=J₂=7.6 Hz, 1H), 6.86(d, J=3.6 Hz, 1H), 4.87(d, J=3.2 Hz, 1H)	175.3, 152.5, 136.3, 135.5, 134.0, 130.7, 129.6, 128.9, 126.6, 126.2, 125.9, 125.4, 125.3, 125.2, 123.8, 123.1, 121.8, 72.2
2x	7.58—7.38(m, 7H), 7.34—7.24(m, 2H), 6.58(s, 1H), 5.99(d, J=4.0 Hz, 1H), 2.76(d, J=4.0 Hz, 1H)	158.5, 155.1, 140.3, 128.7, 128.4, 128.1, 126.8, 124.4, 122.9, 121.2, 111.4, 140.1, 70.7
2y	7.75—7.70(m, 1H), 7.60—7.56(m, 2H), 7.53—7.49(m, 1H), 7.45—7.34(m, 5H), 6.09(d, J=4.8 Hz, 1H), 4.29(d, J=5.2 Hz, 1H)	166.6, 151.0, 140.3, 138.9, 128.9, 128.8, 126.9, 125.3, 124.6, 120.2, 110.9, 70.6
2z	7.68—7.66(m, 1H), 7.52—7.49(m, 2H), 7.43—7.33(m, 3H), 7.31—7.29(m, 1H), 6.07(s, 1H), 4.90(s, 1H)	175.0, 142.2, 141.6, 128.7, 128.4, 126.6, 119.6, 73.6

Compd.	¹H NMR(400 Hz), δ	¹³C NMR(100 Hz), δ
2a	8.00(d, J=8.0 Hz, 1H), 7.86(d, J=8.0 Hz, 1H), 7.61—7.59(m, 1H), 7.51—7.48(m, 1H), 7.42—7.37(m, 1H), 7.31—7.28(m, 2H), 7.24—7.22(m, 1H), 6.38(s, 1H), 4.72(s, 1H), 2.44(s, 3H)	175.4, 152.6, 139.1, 136.1, 135.3, 130.9, 128.6, 126.9, 126.5, 126.1, 125.2, 123.1, 121.8, 71.4, 19.5
2b	8.02(d, J=8.0 Hz, 1H), 7.87(d, J=8.0 Hz, 1H), 7.61(dd, J₁=J₂=7.6 Hz,1H), 7.50(dd, J₁=J₂=7.6 Hz,1H), 7.42—7.34(m, 2H), 7.20(dd, J₁=J₂=7.6 Hz,1H), 7.13(dd, J₁=J₂=7.6 Hz,1H), 6.51(s, 1H), 4.66(s, 1H)	173.9, 161.4(d, J=246.4 Hz), 152.5, 135.3, 130.4(d, J=8.2 Hz), 128.4(d, J=3.7 Hz), 128.2(d, J=14.0 Hz), 126.2, 125.3, 124.7(d, J=3.4 Hz), 123.1, 121.8, 115.8(d, J=21.1 Hz), 68.2(d, J=3.8 Hz)
2c	8.03(d, J=8.4 Hz, 1H), 7.86(d, J=8.0 Hz, 1H), 7.70—7.68(m, 1H), 7.52—7.47(m, 1H), 7.46—7.43(m, 1H), 7.40(d, J=7.2 Hz, 1H), 7.36—7.30(m, 2H), 6.64(s, 1H), 4.83(s, 1H)	173.6, 152.3, 138.6, 135.3, 132.9, 129.8, 129.7, 128.6, 127.4, 126.2, 125.3, 123.1, 121.8, 70.8
2d	8.06(d, J=8.0 Hz, 1H), 7.87(d, J=8.0 Hz, 1H), 7.68—7.63(m, 2H), 7.54—7.49(m, 1H), 7.44—7.38(m, 2H), 7.28—7.24(m, 1H), 6.60(d, J=4.0 Hz, 1H), 4.57(d, J=4.4 Hz, 1H)	173.3, 152.3, 140.2, 135.5, 133.0, 130.2, 128.9, 128.1, 126.2, 125.4, 123.2, 122.9, 121.8, 73.1
2e	8.07(d, J=8.0 Hz, 1H), 7.87(d, J=8.0 Hz, 1H), 7.77(d, J=8.0 Hz, 2H), 7.64—7.59(m,1H), 7.55—7.49(m, 2H), 7.45—7.40(m, 1H), 6.58(d, J=3.6 Hz, 1H), 4.59(d, J=4.0 Hz, 1H)	173.4, 152.2, 139.6, 135.6, 132.6, 129.7, 128.8, 128.2(q, J=30.2 Hz), 126.3, 125.9(q, J=5.5 Hz), 125.6(q, J=254.4 Hz), 125.4, 123.3, 121.8, 69.4(q, J=3.6 Hz)
2f	9.17(s, 1H), 7.99(d, J=8.0 Hz, 1H), 7.87(d, J=7.6 Hz, 1H), 7.53—7.48(m, 1H), 7.44—7.40(m, 2H), 7.31—7.24(m, 1H), 7.02—6.95(m, 2H), 6.40(s, 1H), 4.51(s, 1H)	175.9, 154.7, 152.0, 134.5, 130.0, 126.7, 126.6, 126.5, 125.4, 122.7, 121.9, 120.7, 118.6, 72.1
2g	8.02(d, J=8.0 Hz, 1H), 7.90(d, J=8.0 Hz, 1H), 7.57—7.50(m, 3H), 7.44—7.39(m, 1H), 7.14—7.10(m, 2H), 6.17(s, 1H), 4.04(s, 1H)	174.6, 164.1(d, J=246.2 Hz), 152.6, 136.8, 135.3, 128.7(d, J=8.3 Hz), 126.3, 125.3, 123.1, 121.9, 116.0(d, J=21.6 Hz), 73.8
2h	8.02(d, J=7.6 Hz, 1H), 7.89(d, J=7.6 Hz, 1H), 7.54—7.50(m, 3H), 7.44—7.39(m, 3H), 6.17(s, 1H), 3.98(s, 1H)	174.2, 152.5, 139.4, 135.3, 134.6, 129.0, 128.1, 126.3, 125.4, 123.2, 121.9, 73.8
2i	8.30(d, J=8.4 Hz, 2H), 8.04(d, J=8.0 Hz, 1H), 7.91(d, J=8.0 Hz, 1H), 7.82(d, J=8.4 Hz, 2H), 7.56—7.52(m, 1H), 7.46—7.42(m, 1H), 6.31(s, 1H), 4.21(s, 1H)	173.0, 152.4, 147.9, 147.5, 135.1, 127.5, 126.5, 125.7, 124.0, 123.3, 122.0, 73.4
2j	8.03(d, J=8.4 Hz, 1H), 7.89(d, J=8.0 Hz, 1H), 7.74—7.67(m, 4H), 7.55—7.50(m, 1H), 7.45—7.40(m, 1H), 6.26(s, 1H), 4.16(s, 1H)	173.7, 152.5, 144.6, 135.2, 130.9(q, J=36.3 Hz), 127.0, 126.4, 125.9(q, J=3.8 Hz), 125.5, 125.4(q, J=271.8 Hz), 123.2, 121.9, 73.8
2k	8.03(d, J=8.0 Hz, 1H), 7.87(d, J=8.0 Hz, 1H), 7.52—7.47(m, 1H), 7.46(d, J=8.0 Hz, 2H), 7.42—7.37(m, 1H), 7.23(d, J=8.0 Hz, 2H), 6.15(s, 1H), 3.97(s, 1H), 2.39(s, 3H)	175.2, 152.7, 138.6, 138.1, 135.3, 129.6, 126.7, 126.1, 125.1, 123.1, 121.8, 74.3, 21.3
2l	8.03(d, J=8.0 Hz, 1H), 7.88(d, J=8.0 Hz, 1H), 7.53—7.46(m, 3H), 7.43—7.38(m, 1H), 6.96(d, J=8.8 Hz, 2H), 6.14(s, 1H), 3.84(s, 3H), 3.80(s, 1H)	175.2, 159.9, 152.7, 133.2, 133.2, 128.2, 126.1, 125.1, 123.1, 121.8, 114.2, 74.1, 55.3
2m	9.45(s, 1H), 8.09(d, J=8.0 Hz, 1H), 7.91(d, J=8.0 Hz, 1H), 7.50—7.45(m, 1H), 7.42—7.38(m, 1H), 7.30(d, J=8.4 Hz, 2H), 6.82(d, J=4.0 Hz, 1H), 6.75(d, J=8.4 Hz, 2H), 5.95(d, J=4.4 Hz, 1H)	178.6, 157.4, 153.5, 134.7, 133.2, 128.3, 126.4, 125.2, 122.9, 122.7, 115.5, 73.1
2n	8.03(d, J=8.0 Hz, 1H), 7.88(d, J=8.0 Hz, 1H), 7.53(m, 3H), 7.16—7.12(m, 2H), 6.92(d, J=8.0 Hz, 1H), 6.16(s, 1H), 3.91(s, 1H), 3.84(s, 3H)	174.7, 160.0, 152.6, 142.5, 135.4, 129.9, 126.2, 125.2, 123.1, 121.8, 119.0, 114.4, 112.1, 74.4, 55.3
2o	8.01(d, J=8.4 Hz, 1H), 7.90—7.87(m, 2H), 7.76(d, J=8.0 Hz, 1H), 7.64(d, J=7.6 Hz, 1H), 7.55—7.49(m, 2H), 7.44—7.39(m, 1H), 6.26(d, J=1.6 Hz, 1H), 4.51(s, 1H)	174.0, 152.4, 141.8, 135.2, 131.3(q, J=32.2 Hz), 130.1, 129.3, 126.4, 125.5, 125.4(q, J=3.6 Hz), 125.3(q, J=270.7 Hz), 123.5(q, J=4.0 Hz), 123.1, 121.9, 73.7
Compd.	¹H NMR(400 Hz), δ	¹³C NMR(100 Hz), δ
2p	8.49(s, 1H), 8.22(d, J=8.0 Hz, 1H), 8.01(d, J=8.0 Hz, 1H), 7.93(d, J=8.0 Hz, 1H), 7.89(d, J=8.0 Hz, 1H), 7.59(dd, J₁=J₂=7.6 Hz,1H), 7.54—7.50(m, 1H), 7.45—7.41(m, 1H), 6.31(d, J=2.4 Hz, 1H), 4.55(d, J=3.2 Hz, 1H)	173.4, 152.4, 148.5, 142.8, 135.1, 132.8, 129.8, 126.5, 125.6, 123.5, 123.2, 122.0, 121.7, 73.2
2q	8.04(d, J=8.0 Hz, 1H), 7.87(d, J=8.0 Hz, 1H), 7.75(d, J=2.8 Hz, 1H), 7.54—7.49(m, 1H), 7.44—7.40(m, 1H), 7.36(d, J=8.4 Hz, 1H), 7.32—7.29(m, 1H), 6.58(d, J=3.2 Hz, 1H), 5.15(d, J=3.6 Hz, 1H)	172.7, 152.1, 140.2, 135.3, 133.5, 130.9, 130.8, 129.9, 128.6, 126.4, 125.6, 123.2, 121.9, 70.3
2r	8.01(d, J=7.6 Hz, 1H), 7.91(d, J=8.0 Hz, 1H), 7.52(dt, J₁=7.6 Hz, J₂=1.2 Hz, 1H), 7.44—7.32(m, 2H), 7.00—6.93(m, 2H), 6.53(s, 1H), 4.26(s, 1H)	173.1(d, J=2.8 Hz), 162.4(dd, J₁=256.9 Hz, J₂=7.5 Hz), 152.7, 135.3, 131.0(t, J=10.5 Hz), 126.2, 125.2, 123.2, 121.8, 117.2, 112.2(dd, J₁=19.3 Hz, J₂=5.7 Hz), 65.7(t, J=3.7 Hz)
2s	8.03(d, J=8.0 Hz, 1H), 7.89(d, J=8.0 Hz, 1H), 7.60—7.49(m, 2H), 7.44—7.40(m, 1H), 6.97—6.86(m, 2H), 6.45(s, 1H), 4.52(s, 1H)	173.4, 164.4(dd, J₁=248.8 Hz, J₂=11.9 Hz), 161.5(dd, J₁=247.2 Hz, J₂=12.0 Hz), 152.4, 135.2, 129.5(dd, J₁=9.7 Hz, J₂=4.9 Hz), 126.3, 125.4, 124.4(d, J=17.0 Hz), 123.2, 121.8, 111.8(dd, J₁=21.3 Hz, J₂=3.7 Hz), 104.2(dd, J₁=J₂=25.2 Hz), 67.8(d, J=3.5 Hz)
2t	8.02(d, J=8.0 Hz, 1H), 7.87(d, J=8.0 Hz, 1H), 7.51—7.38(m, 3H), 6.73(d, J=8.0 Hz, 1H), 6.68(d, J=8.0 Hz, 1H) 6.41(s, 1H), 4.53(s, 1H), 3.82(s, 3H)	174.5, 162.1(d, J=246.1 Hz), 161.2(d, J=11.0 Hz), 152.6, 135.3, 129.2(d, J=5.4 Hz), 126.2, 125.2, 123.1, 121.8, 120.4(d, J=13.5 Hz), 110.4(d, J=2.9 Hz), 101.9(d, J=24.9 Hz), 68.1, 55.6
2u	9.25(s, 1H), 7.99(d, J=8.4 Hz, 1H), 7.93(d, J=8.4 Hz, 1H), 7.55—7.51(m, 1H), 7.46—7.42(m, 1H), 7.23(dd, J₁=9.6 Hz, J₂=2.4 Hz, 1H), 6.99—6.92(m, 2H), 6.42(s, 1H), 3.93(s, 1H)	175.8, 158.3(d, J=237.4 Hz), 151.9, 150.2, 134.1, 128.8(d, J=7.1 Hz), 126.6, 125.5, 122.7, 122.0, 119.9(d, J=7.7 Hz), 116.2(d, J=22.9 Hz), 112.6(d, J=24.7 Hz), 70.8
2v	8.04—8.00(m, 2H), 7.89—7.84(m, 4H), 7.63(dd, J₁=8.8 Hz, J₂=2.0 Hz, 1H), 7.55—7.51(m, 2H), 7.49—7.45(m, 1H), 7.40—7.36(m, 1H), 6.34(s, 1H), 4.66(s, 1H)	175.2, 152.6, 138.3, 135.3, 133.4, 133.2, 128.8, 128.3, 127.8, 126.5, 126.4, 126.2, 126.0, 125.2, 124.3, 123.1, 121.8, 74.5
2w	8.25—8.22(m, 1H), 8.02(d, J=8.0 Hz, 1H), 7.93—7.90(m, 2H), 7.82—7.79(m, 2H), 7.56—7.46(m, 4H), 7.38(dd, J₁=J₂=7.6 Hz, 1H), 6.86(d, J=3.6 Hz, 1H), 4.87(d, J=3.2 Hz, 1H)	175.3, 152.5, 136.3, 135.5, 134.0, 130.7, 129.6, 128.9, 126.6, 126.2, 125.9, 125.4, 125.3, 125.2, 123.8, 123.1, 121.8, 72.2
2x	7.58—7.38(m, 7H), 7.34—7.24(m, 2H), 6.58(s, 1H), 5.99(d, J=4.0 Hz, 1H), 2.76(d, J=4.0 Hz, 1H)	158.5, 155.1, 140.3, 128.7, 128.4, 128.1, 126.8, 124.4, 122.9, 121.2, 111.4, 140.1, 70.7
2y	7.75—7.70(m, 1H), 7.60—7.56(m, 2H), 7.53—7.49(m, 1H), 7.45—7.34(m, 5H), 6.09(d, J=4.8 Hz, 1H), 4.29(d, J=5.2 Hz, 1H)	166.6, 151.0, 140.3, 138.9, 128.9, 128.8, 126.9, 125.3, 124.6, 120.2, 110.9, 70.6
2z	7.68—7.66(m, 1H), 7.52—7.49(m, 2H), 7.43—7.33(m, 3H), 7.31—7.29(m, 1H), 6.07(s, 1H), 4.90(s, 1H)	175.0, 142.2, 141.6, 128.7, 128.4, 126.6, 119.6, 73.6

Compd.	Product	Yield^b(%)	e.e.^c(%)	Compd.	Product	Yield^b(%)	e.e.^c(%)
2a		89	99	2l		83	61
2b		77	90	2m		77	60
2c		73	98	2n		88	58
2d		89	99	2o		55	81
2e		75	99	2p		74	85
2f		78	31	2q		81	97
2g		81	78	2r		83	89
2h		69	77	2s		75	95
2i		74	86	2t		85	91
2j		70	70	2u		84	59
2k		82	50	2v		52	55
Compd.	Product	Yield^b(%)	e.e.^c(%)	Compd.	Product	Yield^b(%)	e.e.^c(%)
2w		74	94	2y		77	0
2x		76	52	2z		88	9