铱催化的MBH乙酸酯与吲哚酮类化合物的烯丙基化反应

doi:10.7503/cjcu20200519

摘要/Abstract

摘要：

研究了一种新的铱催化的Morita-Baylis-Hillman(MBH)乙酸酯与3-苯基取代的吲哚酮的烯丙基烷基化反应, 发现铱催化的区域选择明显不同于钯催化的反应, 直接、高效地合成了一类未见报道的具有新结构的 3,3-二取代的吲哚酮类化合物. 通过对亚磷酰胺、双膦及单膦等配体、金属源、溶剂、碱以及反应温度的筛选, 获得了适合该反应的催化体系及最优条件: 以[Ir(COD)Cl]₂(摩尔分数5%)和亚磷酰胺配体(L6, 摩尔分数10%)为催化剂, CH₃CN为溶剂, Cs₂CO₃为碱, 于?30 ℃反应25 h. 在最优条件下, 对不同类型取代基的底物进行了考察, 发现底物普适性良好, 产率最低为84%, 最高可达98%. 同时还发现, 底物取代基的电性对反应产率影响不大, 一些其它类型的双膦和单膦配体对催化反应也有较好的催化效果.

关键词: MBH乙酸酯, 烯丙基化反应, 铱, 亚磷酰胺, 膦

Abstract:

A new iridium-catalyzed allyllic alkylation of Morita-Baylis-Hillman（MBH） acetates with 3-（substituted phenyl）-2-oxindole derivatives was explored. It was found that the regioselection catalyzed by iridium was significantly different from that catalyzed by palladium. A class of 3，3′-disubstituted-2-oxindoles with new structures were synthesized directly and efficiently. By screening the ligands such as phosphoramidites， bisphosphine and monophosphines， metal sources， solvents， bases and reaction temperature， the optimized catalytic system and conditions for the reaction were obtained：［Ir（COD）Cl］₂（molar fraction of 5%） and phosphoramidite ligand L6（molar fraction of 10%） as the catalyst， CH₃CN as the solvent， Cs₂CO₃ as the base， and reaction temperature of -30 ℃， reaction time of 25 h. Under the optimized conditions， the substrates with different types of substituents were investigated. It was found that the substrates had good universality. The lowest yield of the products reached 84%， and the best one was 98%. The electronic effect of substituents was not obvious on the yield. Some other types of bisphosphine and monophosphine ligands along with iridium also had good catalytic performance.

Key words: Morita-Baylis-Hillman acetate, Allylation, Iridium, Phosphoramidite, Phosphine

中图分类号:

O621

TrendMD:

陈相孟, 张雅琪, 梁豪, 陈彬, 欧阳嘉盛, 和晓波, 钱旭, 普晓云, 潘本都, 邱立勤. 铱催化的MBH乙酸酯与吲哚酮类化合物的烯丙基化反应. 高等学校化学学报, 2020, 41(10): 2216.

CHEN Xiangmeng, ZHANG Yaqi, LIANG Hao, CHEN Bin, OUYANG Jiasheng, HE Xiaobo, QIAN Xu, PU Xiaoyun, PAN Bendu, QIU Liqin. Iridium-catalyzed Allylation of Morita-Baylis-Hillman Acetates with Indolinone Compounds^†. Chem. J. Chinese Universities, 2020, 41(10): 2216.

图/表 4

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Compound	R¹	R²	R³	Yield^b(%)	HRMS[M+H]⁺
3a	H	H	Ph	98%	488.2219
3b	H	H	2?NO₂Ph	93%	533.2057
3c	H	H	3,4?Cl₂Ph	91%	556.1433
3d	H	H	3?BrPh	93%	566.1335
3e	H	H	3?ClPh	94%	522.1822
3f	H	H	3?FPh	92%	506.2127
3g	H	H	4?CF₃Ph	92%	556.2082
3h	H	H	4?CNPh	93%	513.2169
3i	H	H	3?MePh	96%	502.2371
3j	H	H	2?Thiofuran	94%	494.1783
3k	H	3,5?(OMe)₂	Ph	96%	548.2436
3l	H	4?OMe	Ph	98%	518.2320
3m	5?Cl	H	Ph	95%	522.1831
3n	5?F	H	Ph	95%	506.2131
3o	5?OMe	H	Ph	97%	518.2330
3p	5?Me	H	Ph	96%	502.2368
3q	6?F	H	Ph	90%	506.2114
3r	7?F	H	Ph	84%	506.2134

Compound	R¹	R²	R³	Yield^b(%)	HRMS[M+H]⁺
3a	H	H	Ph	98%	488.2219
3b	H	H	2?NO₂Ph	93%	533.2057
3c	H	H	3,4?Cl₂Ph	91%	556.1433
3d	H	H	3?BrPh	93%	566.1335
3e	H	H	3?ClPh	94%	522.1822
3f	H	H	3?FPh	92%	506.2127
3g	H	H	4?CF₃Ph	92%	556.2082
3h	H	H	4?CNPh	93%	513.2169
3i	H	H	3?MePh	96%	502.2371
3j	H	H	2?Thiofuran	94%	494.1783
3k	H	3,5?(OMe)₂	Ph	96%	548.2436
3l	H	4?OMe	Ph	98%	518.2320
3m	5?Cl	H	Ph	95%	522.1831
3n	5?F	H	Ph	95%	506.2131
3o	5?OMe	H	Ph	97%	518.2330
3p	5?Me	H	Ph	96%	502.2368
3q	6?F	H	Ph	90%	506.2114
3r	7?F	H	Ph	84%	506.2134

Compound	¹H NMR(400 MHz, CDCl₃), δ	¹³C NMR(101 MHz, CDCl₃), δ
3a	7.47(m, 3H, PhH), 7.35—7.21(m, 12H, PhH), 7.20—7.08(m, 5H, PhH), 6.96—6.70(m, 2H, PhH, CH), 4.97—4.78(m, 2H, Ph—CH₂), 3.89(t, J=7.0 Hz, 2H, CH₂), 3.87—3.78(m, 2H, CH₂), 1.22—1.06(m, 3H, CH₃)	177.83, 168.67, 143.09, 140.58, 140.02, 135.97, 135.27, 130.20, 129.93, 128.84, 128.70, 128.65, 128.40, 128.37, 128.15, 127.89, 127.44, 127.28, 127.21, 126.94, 126.85, 122.01, 109.09, 60.82, 56.06, 43.90, 34.91, 14.06
3b	8.19—8.16(m, 1H, PhH), 7.87(s, 1H, PhH), 7.67—7.63(m, 2H, PhH), 7.31—7.23(m, 8H, PhH, Ph—CH), 7.21—7.13(m, 6H, PhH), 7.00—6.96(m, 1H), 6.71(d, J=8 Hz, 1H, PhH), 4.99—4.66(dd, J=116, 16 Hz, 2H, BnH₂), 4.01—3.83(m, 2H), 3.75—3.60(dd, J=48, 12 Hz, 2H), 1.11(t, J=7.1 Hz, 3H)	177.41, 167.99, 146.91, 143.01, 139.06, 138.82, 135.92, 133.76, 132.44, 130.78, 129.83, 129.39, 128.93, 128.64, 128.59, 128.33, 128.29, 127.40, 127.20, 127.16, 126.92, 126.85, 125.34, 121.98, 109.38, 61.07, 56.29, 43.64, 33.92, 14.01
3c	7.49—7.43(m, 2H, PhH), 7.35—7.25(m, 11H, PhH), 7.22—7.13(m, 3H, PhH), 7.01—6.94(m, 2H, PhH), 6.93—6.86(m, 1H, PhH), 6.89—6.73(m, 1H, PhH), 4.91—4.80(q, J=16 Hz, 2H, PhH), 3.97—3.86(m, 2H, CH₂), 3.74(s, 2H, CH₂),1.15(t, J=7.1 Hz, 3H, CH₃)	177.46, 168.24, 143.05, 139.26, 137.93, 135.92, 135.28, 132.51, 132.08, 131.91, 130.51, 130.28, 129.74, 128.70, 128.45, 128.36, 127.72, 127.58, 127.48, 127.26, 127.20, 126.85, 122.05, 109.24, 61.11, 56.01, 43.89, 34.88, 14.01
3d	7.49—7.42(m, 2H, PhH), 7.41—7.35(m, 2H, PhH), 7.34—7.22(m, 8H, PhH, CH), 7.22—7.16(m, 1H, PhH), 7.16—7.10(m, 2H, PhH), 7.07(d, J=8.1 Hz, 1H, PhH), 7.03(dd, J=9.9, 2.8 Hz, 1H), 6.99— 6.93(m, 3H, PhH ), 6.72(d, J=7.8 Hz, 1H, PhH), 4.91—4.79(m, 2H, BnH), 3.97—3.87(m, 2H, CH₂), 3.77(s, 2H), 1.15(t, J=7.1 Hz, 3H, CH₃)	177.53, 168.33, 143.04, 139.45, 138.88, 137.38, 135.93, 131.54, 131.50, 130.97, 129.83, 129.76, 128.67, 128.40, 128.26, 127.48, 127.39, 127.21, 127.03, 126.83, 122.44, 122.06, 109.20, 61.01, 56.01, 43.91, 34.86, 14.02
3e	7.47—7.44(m, 2H, PhH), 7,38(s, 1H, PhH), 7.30—7.13(m, 10H, PhH), 6.99—6.95(m, 5H, PhH), 6.93(d, J=1.9 Hz, 1H, PhH), 4.91—4.79(m, 2H, BnH₂), 4.01—3.84(m, 2H, CH₂), 3.84—3.74(m, 2H, CH₂), 1.15(t, J=7.1 Hz, 3H, CH₃)	177.58, 168.38, 143.07, 139.50, 139.01, 137.11, 135.95, 134.25, 131.48, 129.81, 129.59, 128.68, 128.42, 128.27, 128.09, 127.50, 127.40, 127.22, 126.85, 126.63, 122.07, 109.20, 61.02, 56.03, 43.90, 34.87, 14.02
3f	7.46—7.40(m, 3H, PhH), 7.30—7.25(m, 9H, PhH, CH), 7.22—7.13(m, 3H), 6.98—6.94(m, 2H, PhH), 6.88(d, J=7.7 Hz, 1H, PhH), 6.72—6.69(m, 2H, PhH), 4.85(s, 2H, BnH), 3.95—3.90(m, 2H, CH₂), 3.79(q, J=13.6 Hz, 2H, CH₂), 1.14(t, J=7.1 Hz, 3H, CH₃)	177.58, 168.41, 163.78, 161.33, 143.08, 139.61, 139.16, 137.48, 137.40, 135.91, 131.35, 129.89, 129.83, 129.80, 128.65, 128.41, 128.24, 127.48, 127.37, 127.18, 126.93, 126.85, 124.37, 124.34, 122.03, 115.67, 115.45, 115.08, 114.87, 109.16, 60.98, 56.03, 43.88, 34.84, 14.01
3g	7.49—7.42(m, 5H, PhH), 7.32—7.26(m, 9H, PhH, CH), 7.19—7.10(m, 5H, PhH), 6.97—6.93(m, 1H, PhH), 6.74—6.72(m, 1H, PhH), 4.86(dd, J=42.4, 15.8 Hz, 2H, BnH), 3.97—3.86(m, 2H, CH₂), 3.77(s, 2H, CH₂), 1.15(t, J=7.1 Hz, 3H, CH₃)	177.53, 168.32, 143.01, 139.35, 138.93, 138.86, 135.89, 132.12, 129.77, 128.82, 128.68, 128.44, 128.33, 127.58, 127.44, 127.25, 127.17, 126.83, 125.28, 125.25, 122.13, 109.21, 77.38, 77.06, 76.74, 61.10, 55.99, 43.89, 34.84, 14.00
3h	7.52—7.50(m, 2H, PhH), 7.43—7.39(m, 3H, PhH), 7.32—7.27(m, 8H, PhH), 7.19—7.16(m, 3H, PhH), 7.12—7.02(m, 3H, PhH), 6.99—6.96(m, 1H, PhH), 6.75—6.73(m, 1H), 4.85(dd, J=52, 16 Hz, 2H, BnH), 3.92—3.88(m, 2H, CH₂), 3.9—3.71(m, 2H, CH₂), 1.14(t, J=7.1 Hz, 3H, CH₃)	177.35, 168.13, 143.06, 140.01, 139.25, 138.28, 135.88, 132.78, 132.04, 131.67, 129.63, 129.20, 128.77, 128.69, 128.61, 128.50, 128.43, 127.64, 127.51, 127.25, 127.08, 126.91, 126.75, 122.13, 118.65, 111.49, 109.23, 61.19, 56.02, 43.86, 34.74, 13.99
3i	7.49—7.47(m, 3H, PhH), 7.31—7.26(m, 8H, PhH, CH), 7.17—7.16(m, 3H, PhH), 7.09—6.94(m, 2H), 6.83(s, 1H, PhH), 6.73—6.71(m, 1H, PhH), 4.87(q, J=15.8 Hz, 2H, BnH), 3.93—3.86(m, 2H, CH₂), 3.83(s, 2H, CH₂), 2.23(s, 3H, CH₃), 1.13(t, J=7.1 Hz, 3H, CH₃)	177.99, 168.65, 143.14, 140.77, 140.10, 137.89, 136.02, 135.19, 130.06, 129.98, 129.49, 128.94, 128.65, 128.36, 128.25, 128.08, 127.43, 127.30, 127.26, 127.23, 127.21, 127.00, 125.92, 121.98, 109.07, 60.76, 55.95, 43.93, 35.31, 21.32, 14.06
Compound	¹H NMR(400 MHz, CDCl₃), δ	¹³C NMR(101 MHz, CDCl₃), δ
3j	7.60—7.59(m, 3H, PhH), 7.35—7.26(m, 11H, PhH), 7.16—7.12(m, 1H, PhH), 6.99—6.91(m, 2H),, 6.71(d, J=7.7 Hz, 1H, CH), 4.97—4.81(m, 2H, BnH), 3.92(s, 2H, CH₂), 3.90—3.79(m, 2H, CH₂), 1.09(t, J=7.1 Hz, 3H, CH₃)	178.08, 168.44, 143.14, 140.08, 137.95, 136.00, 133.37, 132.20, 129.81, 128.71, 128.60, 128.38, 128.22, 127.43, 127.40, 127.34, 127.11, 126.97, 126.43, 121.84, 109.08, 77.38, 77.06, 76.74, 60.72, 55.88, 44.01, 36.70, 14.05
3k	7.47(s, 1H, PhH), 7.32—7.28(m, 8H, PhH), 7.19—7.09(m, 4H, PhH), 7.04—6.97(m, 2H), 6.95—6.88(m, 4H, PhH), 6.71—6.69(m, 1H), 4.93—4.80(m, 2H, CH₂), 3.91—3.83(m, 2H, PhH), 3.84(d, J=8.3 Hz, 2H), 2.25(s, 6H, CH₃), 1.14(t, J=7.1 Hz, 3H, CH₃)	177.97, 168.72, 143.02, 140.44, 140.28, 137.80, 136.11, 135.36, 130.58, 130.28, 128.98, 128.91, 128.60, 128.34, 128.13, 127.94, 127.42, 127.31, 126.73, 124.81, 121.99, 108.92, 60.77, 56.14, 43.88, 34.47, 21.51, 14.05
3l	7.47(s, 1H, PhH), 7.37—7.26(m, 10H), 7.15—7.10 (m, 4H, PhH), 6.96—6.92(m, 1H, PhH), 6.81—6.79 (m, 2H, PhH), 6.69(d, J=7.7 Hz, 1H, PhH), 4.92—4.78(m, 2H, CH₂), 3.91—3.88(q, J=4 Hz, 2H, CH₂), 3.79(s, 3H, CH₃), 3.78(s, 2H, CH₂), 1.13(t, J=7.1 Hz, 3H, CH₃)	178.07, 168.69, 158.72, 143.04, 140.51, 136.00, 135.33, 131.85, 130.25, 130.11, 128.81, 128.63, 128.39, 128.33, 128.08, 127.40, 127.17, 126.86, 121.95, 113.69, 109.07, 60.80, 55.37, 55.25, 43.84, 35.05, 14.03
3m	7.52(s, 1H, PhH), 7.39—7.28(m, 12H), 7.24—7.12(m, 3H, PhH), 7.00(s, 1H, PhH), 6.59—6.57(d, J=8 Hz, 1H), 4.81(dd, J=48, 16 Hz, 2H, CH₂), 4.07—3.96(m, 2H, CH₂), 3.86(dd, J=44, 12 Hz, 2H, CH₂), 1.23(t, J=7.1 Hz, 3H, CH₃)	177.24, 168.53, 141.66, 141.19, 139.49, 135.49, 135.13, 131.97, 129.64, 128.74, 128.68, 128.60, 128.49, 128.31, 128.19, 127.63, 127.54, 127.43, 127.17, 126.98, 110.00, 61.06, 56.56, 44.01, 34.30, 14.11
3n	7.52(s, 1H, PhH), 7.40—7.42(m, 2H, PhH), 7.32—7.25(m, 12H, PhH), 7.15—7.12(m, 2H, PhH), 6.87—6.77(m, 2H, PhH), 6.64—6.54(m, 1H, PhH), 4.83(dd, J=36, 16 Hz, 2H, BnH), 4.06—3.95(m, 2H, CH₂), 3.87(dd, J=40, 12 Hz, 2H, CH₂), 1.21(t, J=7.1 Hz, 3H, CH₃)	177.46, 168.52, 159.84, 157.45, 141.03, 139.61, 139.03, 135.65, 135.17, 131.88, 131.80, 129.75, 128.77, 128.72, 128.70, 128.66, 128.56, 128.46, 128.44, 128.42, 128.40, 128.27, 127.58, 127.51, 127.19, 127.15, 127.01, 114.79, 114.65, 114.54, 114.42, 109.54, 109.46, 60.99, 56.67, 44.07, 34.49, 14.09
3o	7.49(s, 1H, PhH), 7.47—7.49(m, 2H, PhH), 7.31—7.25(m, 12H, PhH, CH), 7.13—7.11(m, 2H, PhH), 6.73—6.67(m, 2H), 6.58(d, J=6 Hz, 1H), 4.83(q, J=12 Hz, 2H, PhH), 4.97—3.94(m, 2H, CH₂), 3.86(q, J=12 Hz, 2H, CH₂), 3.69(s, 3H, CH₃), 1.17(t, J=7.1 Hz, 3H, CH₃)	177.50, 168.73, 155.36, 140.58, 139.98, 136.59, 136.08, 135.31, 131.29, 130.21, 128.77, 128.64, 128.42, 128.37, 128.10, 127.43, 127.30, 127.23, 113.89, 112.94, 109.42, 60.87, 56.62, 55.61, 43.99, 34.73, 14.06
3p	7.47—7.42(m, 3H, PhH) 7.29—7.26(m, 11H, PhH), 6.95(t, J=10.0 Hz, 1H), 7.12—7.10(m, 2H, PhH), 6.86—6.94(m, 2H, PhH), 6.57(d, J=8 Hz, 1H, PhH), 4.83(dd, J=36, 16 Hz, 2H, CH₂), 3.95(q, J=4.0 Hz, 2H, CH₂), 3.84(q, J=13.6 Hz, 2H), 2.22(s, 3H, CH₃), 1.18(t, J=7.1 Hz, 3H, CH₃)	177.63, 168.75, 140.68, 140.57, 140.20, 136.10, 135.39, 131.33, 130.20, 130.15, 128.78, 128.61, 128.48, 128.38, 128.33, 128.03, 127.49, 127.38, 127.21, 108.82, 60.82, 56.34, 43.90, 34.54, 21.18, 14.07
3q	7.50(s, 1H, PhH), 7.43—7.40(m, 2H, PhH), 7.33—7.26(m, 11H, PhH), 7.14—7.13(d, J=4 Mz, 2H, PhH), 7.04—7.00(m, 1H, PhH), 6.66—6.60(m, 1H, PhH), 6.44—6.41(m, 1H, PhH), 4.89—4.73(m, 2H, CH₂), 3.98—3.78(m, 4H, CH₂, CH₂), 1.17(t, J=7.1 Hz, 3H, CH₃)	178.11, 168.56, 164.06, 161.62, 144.67, 144.56, 140.72, 139.92, 135.42, 135.19, 129.97, 128.77, 128.50, 128.43, 128.26, 127.67, 127.44, 127.20, 127.06, 108.33, 108.11, 97.81, 97.54, 60.93, 55.76, 44.09, 34.81, 14.08
3r	7.51(s, 1H, PhH), 7.43—7.26(m, 14H), 7.14—7.13(d, J=4 Mz, 2H), 6.63—6.61(m, 1H), 6.41—6.44(m, 1H), 4.82(dd, J=28, 16 Mz, 2H, CH₂), 3.98—3.78(m, 4H, CH₂, CH₂), 1.17(t, J=7.1 Hz, CH₃)	177.55, 168.50, 148.55, 146.12, 140.90, 139.72, 137.28, 135.20, 133.10, 133.08, 129.78, 128.82, 128.49, 128.42, 128.25, 127.47, 127.34, 127.06, 122.79, 122.76, 122.55, 122.49, 116.27, 116.08, 60.89, 56.38, 45.44, 34.76, 14.07

Compound	¹H NMR(400 MHz, CDCl₃), δ	¹³C NMR(101 MHz, CDCl₃), δ
3a	7.47(m, 3H, PhH), 7.35—7.21(m, 12H, PhH), 7.20—7.08(m, 5H, PhH), 6.96—6.70(m, 2H, PhH, CH), 4.97—4.78(m, 2H, Ph—CH₂), 3.89(t, J=7.0 Hz, 2H, CH₂), 3.87—3.78(m, 2H, CH₂), 1.22—1.06(m, 3H, CH₃)	177.83, 168.67, 143.09, 140.58, 140.02, 135.97, 135.27, 130.20, 129.93, 128.84, 128.70, 128.65, 128.40, 128.37, 128.15, 127.89, 127.44, 127.28, 127.21, 126.94, 126.85, 122.01, 109.09, 60.82, 56.06, 43.90, 34.91, 14.06
3b	8.19—8.16(m, 1H, PhH), 7.87(s, 1H, PhH), 7.67—7.63(m, 2H, PhH), 7.31—7.23(m, 8H, PhH, Ph—CH), 7.21—7.13(m, 6H, PhH), 7.00—6.96(m, 1H), 6.71(d, J=8 Hz, 1H, PhH), 4.99—4.66(dd, J=116, 16 Hz, 2H, BnH₂), 4.01—3.83(m, 2H), 3.75—3.60(dd, J=48, 12 Hz, 2H), 1.11(t, J=7.1 Hz, 3H)	177.41, 167.99, 146.91, 143.01, 139.06, 138.82, 135.92, 133.76, 132.44, 130.78, 129.83, 129.39, 128.93, 128.64, 128.59, 128.33, 128.29, 127.40, 127.20, 127.16, 126.92, 126.85, 125.34, 121.98, 109.38, 61.07, 56.29, 43.64, 33.92, 14.01
3c	7.49—7.43(m, 2H, PhH), 7.35—7.25(m, 11H, PhH), 7.22—7.13(m, 3H, PhH), 7.01—6.94(m, 2H, PhH), 6.93—6.86(m, 1H, PhH), 6.89—6.73(m, 1H, PhH), 4.91—4.80(q, J=16 Hz, 2H, PhH), 3.97—3.86(m, 2H, CH₂), 3.74(s, 2H, CH₂),1.15(t, J=7.1 Hz, 3H, CH₃)	177.46, 168.24, 143.05, 139.26, 137.93, 135.92, 135.28, 132.51, 132.08, 131.91, 130.51, 130.28, 129.74, 128.70, 128.45, 128.36, 127.72, 127.58, 127.48, 127.26, 127.20, 126.85, 122.05, 109.24, 61.11, 56.01, 43.89, 34.88, 14.01
3d	7.49—7.42(m, 2H, PhH), 7.41—7.35(m, 2H, PhH), 7.34—7.22(m, 8H, PhH, CH), 7.22—7.16(m, 1H, PhH), 7.16—7.10(m, 2H, PhH), 7.07(d, J=8.1 Hz, 1H, PhH), 7.03(dd, J=9.9, 2.8 Hz, 1H), 6.99— 6.93(m, 3H, PhH ), 6.72(d, J=7.8 Hz, 1H, PhH), 4.91—4.79(m, 2H, BnH), 3.97—3.87(m, 2H, CH₂), 3.77(s, 2H), 1.15(t, J=7.1 Hz, 3H, CH₃)	177.53, 168.33, 143.04, 139.45, 138.88, 137.38, 135.93, 131.54, 131.50, 130.97, 129.83, 129.76, 128.67, 128.40, 128.26, 127.48, 127.39, 127.21, 127.03, 126.83, 122.44, 122.06, 109.20, 61.01, 56.01, 43.91, 34.86, 14.02
3e	7.47—7.44(m, 2H, PhH), 7,38(s, 1H, PhH), 7.30—7.13(m, 10H, PhH), 6.99—6.95(m, 5H, PhH), 6.93(d, J=1.9 Hz, 1H, PhH), 4.91—4.79(m, 2H, BnH₂), 4.01—3.84(m, 2H, CH₂), 3.84—3.74(m, 2H, CH₂), 1.15(t, J=7.1 Hz, 3H, CH₃)	177.58, 168.38, 143.07, 139.50, 139.01, 137.11, 135.95, 134.25, 131.48, 129.81, 129.59, 128.68, 128.42, 128.27, 128.09, 127.50, 127.40, 127.22, 126.85, 126.63, 122.07, 109.20, 61.02, 56.03, 43.90, 34.87, 14.02
3f	7.46—7.40(m, 3H, PhH), 7.30—7.25(m, 9H, PhH, CH), 7.22—7.13(m, 3H), 6.98—6.94(m, 2H, PhH), 6.88(d, J=7.7 Hz, 1H, PhH), 6.72—6.69(m, 2H, PhH), 4.85(s, 2H, BnH), 3.95—3.90(m, 2H, CH₂), 3.79(q, J=13.6 Hz, 2H, CH₂), 1.14(t, J=7.1 Hz, 3H, CH₃)	177.58, 168.41, 163.78, 161.33, 143.08, 139.61, 139.16, 137.48, 137.40, 135.91, 131.35, 129.89, 129.83, 129.80, 128.65, 128.41, 128.24, 127.48, 127.37, 127.18, 126.93, 126.85, 124.37, 124.34, 122.03, 115.67, 115.45, 115.08, 114.87, 109.16, 60.98, 56.03, 43.88, 34.84, 14.01
3g	7.49—7.42(m, 5H, PhH), 7.32—7.26(m, 9H, PhH, CH), 7.19—7.10(m, 5H, PhH), 6.97—6.93(m, 1H, PhH), 6.74—6.72(m, 1H, PhH), 4.86(dd, J=42.4, 15.8 Hz, 2H, BnH), 3.97—3.86(m, 2H, CH₂), 3.77(s, 2H, CH₂), 1.15(t, J=7.1 Hz, 3H, CH₃)	177.53, 168.32, 143.01, 139.35, 138.93, 138.86, 135.89, 132.12, 129.77, 128.82, 128.68, 128.44, 128.33, 127.58, 127.44, 127.25, 127.17, 126.83, 125.28, 125.25, 122.13, 109.21, 77.38, 77.06, 76.74, 61.10, 55.99, 43.89, 34.84, 14.00
3h	7.52—7.50(m, 2H, PhH), 7.43—7.39(m, 3H, PhH), 7.32—7.27(m, 8H, PhH), 7.19—7.16(m, 3H, PhH), 7.12—7.02(m, 3H, PhH), 6.99—6.96(m, 1H, PhH), 6.75—6.73(m, 1H), 4.85(dd, J=52, 16 Hz, 2H, BnH), 3.92—3.88(m, 2H, CH₂), 3.9—3.71(m, 2H, CH₂), 1.14(t, J=7.1 Hz, 3H, CH₃)	177.35, 168.13, 143.06, 140.01, 139.25, 138.28, 135.88, 132.78, 132.04, 131.67, 129.63, 129.20, 128.77, 128.69, 128.61, 128.50, 128.43, 127.64, 127.51, 127.25, 127.08, 126.91, 126.75, 122.13, 118.65, 111.49, 109.23, 61.19, 56.02, 43.86, 34.74, 13.99
3i	7.49—7.47(m, 3H, PhH), 7.31—7.26(m, 8H, PhH, CH), 7.17—7.16(m, 3H, PhH), 7.09—6.94(m, 2H), 6.83(s, 1H, PhH), 6.73—6.71(m, 1H, PhH), 4.87(q, J=15.8 Hz, 2H, BnH), 3.93—3.86(m, 2H, CH₂), 3.83(s, 2H, CH₂), 2.23(s, 3H, CH₃), 1.13(t, J=7.1 Hz, 3H, CH₃)	177.99, 168.65, 143.14, 140.77, 140.10, 137.89, 136.02, 135.19, 130.06, 129.98, 129.49, 128.94, 128.65, 128.36, 128.25, 128.08, 127.43, 127.30, 127.26, 127.23, 127.21, 127.00, 125.92, 121.98, 109.07, 60.76, 55.95, 43.93, 35.31, 21.32, 14.06
Compound	¹H NMR(400 MHz, CDCl₃), δ	¹³C NMR(101 MHz, CDCl₃), δ
3j	7.60—7.59(m, 3H, PhH), 7.35—7.26(m, 11H, PhH), 7.16—7.12(m, 1H, PhH), 6.99—6.91(m, 2H),, 6.71(d, J=7.7 Hz, 1H, CH), 4.97—4.81(m, 2H, BnH), 3.92(s, 2H, CH₂), 3.90—3.79(m, 2H, CH₂), 1.09(t, J=7.1 Hz, 3H, CH₃)	178.08, 168.44, 143.14, 140.08, 137.95, 136.00, 133.37, 132.20, 129.81, 128.71, 128.60, 128.38, 128.22, 127.43, 127.40, 127.34, 127.11, 126.97, 126.43, 121.84, 109.08, 77.38, 77.06, 76.74, 60.72, 55.88, 44.01, 36.70, 14.05
3k	7.47(s, 1H, PhH), 7.32—7.28(m, 8H, PhH), 7.19—7.09(m, 4H, PhH), 7.04—6.97(m, 2H), 6.95—6.88(m, 4H, PhH), 6.71—6.69(m, 1H), 4.93—4.80(m, 2H, CH₂), 3.91—3.83(m, 2H, PhH), 3.84(d, J=8.3 Hz, 2H), 2.25(s, 6H, CH₃), 1.14(t, J=7.1 Hz, 3H, CH₃)	177.97, 168.72, 143.02, 140.44, 140.28, 137.80, 136.11, 135.36, 130.58, 130.28, 128.98, 128.91, 128.60, 128.34, 128.13, 127.94, 127.42, 127.31, 126.73, 124.81, 121.99, 108.92, 60.77, 56.14, 43.88, 34.47, 21.51, 14.05
3l	7.47(s, 1H, PhH), 7.37—7.26(m, 10H), 7.15—7.10 (m, 4H, PhH), 6.96—6.92(m, 1H, PhH), 6.81—6.79 (m, 2H, PhH), 6.69(d, J=7.7 Hz, 1H, PhH), 4.92—4.78(m, 2H, CH₂), 3.91—3.88(q, J=4 Hz, 2H, CH₂), 3.79(s, 3H, CH₃), 3.78(s, 2H, CH₂), 1.13(t, J=7.1 Hz, 3H, CH₃)	178.07, 168.69, 158.72, 143.04, 140.51, 136.00, 135.33, 131.85, 130.25, 130.11, 128.81, 128.63, 128.39, 128.33, 128.08, 127.40, 127.17, 126.86, 121.95, 113.69, 109.07, 60.80, 55.37, 55.25, 43.84, 35.05, 14.03
3m	7.52(s, 1H, PhH), 7.39—7.28(m, 12H), 7.24—7.12(m, 3H, PhH), 7.00(s, 1H, PhH), 6.59—6.57(d, J=8 Hz, 1H), 4.81(dd, J=48, 16 Hz, 2H, CH₂), 4.07—3.96(m, 2H, CH₂), 3.86(dd, J=44, 12 Hz, 2H, CH₂), 1.23(t, J=7.1 Hz, 3H, CH₃)	177.24, 168.53, 141.66, 141.19, 139.49, 135.49, 135.13, 131.97, 129.64, 128.74, 128.68, 128.60, 128.49, 128.31, 128.19, 127.63, 127.54, 127.43, 127.17, 126.98, 110.00, 61.06, 56.56, 44.01, 34.30, 14.11
3n	7.52(s, 1H, PhH), 7.40—7.42(m, 2H, PhH), 7.32—7.25(m, 12H, PhH), 7.15—7.12(m, 2H, PhH), 6.87—6.77(m, 2H, PhH), 6.64—6.54(m, 1H, PhH), 4.83(dd, J=36, 16 Hz, 2H, BnH), 4.06—3.95(m, 2H, CH₂), 3.87(dd, J=40, 12 Hz, 2H, CH₂), 1.21(t, J=7.1 Hz, 3H, CH₃)	177.46, 168.52, 159.84, 157.45, 141.03, 139.61, 139.03, 135.65, 135.17, 131.88, 131.80, 129.75, 128.77, 128.72, 128.70, 128.66, 128.56, 128.46, 128.44, 128.42, 128.40, 128.27, 127.58, 127.51, 127.19, 127.15, 127.01, 114.79, 114.65, 114.54, 114.42, 109.54, 109.46, 60.99, 56.67, 44.07, 34.49, 14.09
3o	7.49(s, 1H, PhH), 7.47—7.49(m, 2H, PhH), 7.31—7.25(m, 12H, PhH, CH), 7.13—7.11(m, 2H, PhH), 6.73—6.67(m, 2H), 6.58(d, J=6 Hz, 1H), 4.83(q, J=12 Hz, 2H, PhH), 4.97—3.94(m, 2H, CH₂), 3.86(q, J=12 Hz, 2H, CH₂), 3.69(s, 3H, CH₃), 1.17(t, J=7.1 Hz, 3H, CH₃)	177.50, 168.73, 155.36, 140.58, 139.98, 136.59, 136.08, 135.31, 131.29, 130.21, 128.77, 128.64, 128.42, 128.37, 128.10, 127.43, 127.30, 127.23, 113.89, 112.94, 109.42, 60.87, 56.62, 55.61, 43.99, 34.73, 14.06
3p	7.47—7.42(m, 3H, PhH) 7.29—7.26(m, 11H, PhH), 6.95(t, J=10.0 Hz, 1H), 7.12—7.10(m, 2H, PhH), 6.86—6.94(m, 2H, PhH), 6.57(d, J=8 Hz, 1H, PhH), 4.83(dd, J=36, 16 Hz, 2H, CH₂), 3.95(q, J=4.0 Hz, 2H, CH₂), 3.84(q, J=13.6 Hz, 2H), 2.22(s, 3H, CH₃), 1.18(t, J=7.1 Hz, 3H, CH₃)	177.63, 168.75, 140.68, 140.57, 140.20, 136.10, 135.39, 131.33, 130.20, 130.15, 128.78, 128.61, 128.48, 128.38, 128.33, 128.03, 127.49, 127.38, 127.21, 108.82, 60.82, 56.34, 43.90, 34.54, 21.18, 14.07
3q	7.50(s, 1H, PhH), 7.43—7.40(m, 2H, PhH), 7.33—7.26(m, 11H, PhH), 7.14—7.13(d, J=4 Mz, 2H, PhH), 7.04—7.00(m, 1H, PhH), 6.66—6.60(m, 1H, PhH), 6.44—6.41(m, 1H, PhH), 4.89—4.73(m, 2H, CH₂), 3.98—3.78(m, 4H, CH₂, CH₂), 1.17(t, J=7.1 Hz, 3H, CH₃)	178.11, 168.56, 164.06, 161.62, 144.67, 144.56, 140.72, 139.92, 135.42, 135.19, 129.97, 128.77, 128.50, 128.43, 128.26, 127.67, 127.44, 127.20, 127.06, 108.33, 108.11, 97.81, 97.54, 60.93, 55.76, 44.09, 34.81, 14.08
3r	7.51(s, 1H, PhH), 7.43—7.26(m, 14H), 7.14—7.13(d, J=4 Mz, 2H), 6.63—6.61(m, 1H), 6.41—6.44(m, 1H), 4.82(dd, J=28, 16 Mz, 2H, CH₂), 3.98—3.78(m, 4H, CH₂, CH₂), 1.17(t, J=7.1 Hz, CH₃)	177.55, 168.50, 148.55, 146.12, 140.90, 139.72, 137.28, 135.20, 133.10, 133.08, 129.78, 128.82, 128.49, 128.42, 128.25, 127.47, 127.34, 127.06, 122.79, 122.76, 122.55, 122.49, 116.27, 116.08, 60.89, 56.38, 45.44, 34.76, 14.07

Entry	Ligand	Yield^b(%)	Entry	Ligand	Yield^b(%)
1		94%	10		96%
	L1			L10
2		93%	11		97%
	L2			L11
3		95%	12		95%
	L3			L12
4		96%	13		95%
	L4			L13
5		95%	14		97%
	L5			L14
6		98%	15		93%
	L6			L15
7		92%	16		91%
	L7			L16
8		90%	17		93%
	L8			L17
9		94%
	L9