Iridium-catalyzed Allylation of Morita-Baylis-Hillman Acetates with Indolinone Compounds†

doi:10.7503/cjcu20200519

Abstract

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

CLC Number:

O621

TrendMD:

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^†[J]. Chem. J. Chinese Universities, 2020, 41(10): 2216.

Figures/Tables 4

References 33

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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