Highly Enantioselective Addition of Phenylacetylene to Ketones Catalyzed by Bis(hydroxycamphorsulfonamide)-Copper(II) Complex

Lei Liu; Rui Wang; Yong-Feng Kang; Hua-Qing Cai; Chao Chen

doi:10.1055/s-2006-932473

LETTER

Highly Enantioselective Addition of Phenylacetylene to Ketones Catalyzed by Bis(hydroxycamphorsulfonamide)-Copper(II) Complex

Lei Liu^a, Rui Wang*^a,b, Yong-Feng Kang^a,c, Hua-Qing Cai^a, Chao Chen^a
^a Department of Biochemistry and Molecular Biology, School of Life Sciences, Lanzhou University, Lanzhou, Gansu 730000, P. R. of China
^b State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou, Gansu 730000, P. R. of China
^c College of Food Science, Shanghai Fisheries University, Shanghai 200090, P. R. of China
Fax: +86(931)8912561; e-Mail: wangrui@lzu.edu.cn;

Abstract

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Abstract

A chiral copper complex, generated from a C ₂-symmetric bis(hydroxycamphorsulfonamide) ligand (8 mol%) and Cu(OTf)₂, has been discovered to effect high enantioselectivities in the addition of alkynylzinc to a series of simple ketones. The alkynylation of a variety of aromatic and aliphatic ketones resulted in excellent yields and enantioselectivities (83-98% ee). Even when the loadings of the catalyst is 5 mol%, up to 94% ee was obtained.

Key words

alkynylation - simple ketones - asymmetric catalysis - C ₂-symmetric bis(hydroxycamphorsulfonamide)

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References

References and Notes

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Selected data for 9: white solid, mp 141-142 °C; [α]_D ²⁸
-51.0 (c 1.0, EtOAc). ¹H NMR (200 MHz, CDCl₃): δ = 0.77 (6 H, s), 0.97 (6 H, s), 1.10-1.78 (14 H, m), 2.78 (2 H, d, J = 13.8 Hz), 3.25 (2 H, d, J = 13.6 Hz), 4.03-4.08 (2 H, m), 4.30 (4 H, d, J = 5.6 Hz), 5.38 (2 H, b), 7.28-7.39 (4 H, m). ¹³C NMR (50 MHz, CDCl₃): δ = 19.81 (2 C), 20.47 (2 C), 27.30 (2 C), 30.43 (2 C), 39.00 (2 C), 44.31 (2 C), 47.10 (2 C), 48.68 (2 C), 50.36 (2 C), 52.97 (2 C), 76.42 (2 C), 127.98 (2 C), 129.47 (2 C), 137.57 (2 C). IR (KBr): 3529, 3283, 2956, 2882, 2253, 1706, 1612, 1472, 1453, 1394, 1370, 1317, 1259, 1235, 1209, 1140, 1073, 1054, 1028, 991, 911, 883, 846, 795, 773, 733, 704 cm^-1.

Selected data for 11: white solid, mp 101-102 °C; [α]_D ²⁸
-24.0 (c 1.11, EtOH). ¹H NMR (200 MHz, CDCl₃): δ = 0.80 (6 H, s), 1.03 (6 H, s), 1.07-1.80 (14 H, m), 3.04 (2 H, d, J = 12.0 Hz), 3.61 (2 H, d, J = 14.0 Hz), 4.09-4.15 (2 H, m), 7.27-7.52 (4 H, m). ¹³C NMR (50 MHz, CDCl₃): δ = 19.89 (2 C), 20.50 (2 C), 27.27 (2 C), 30.43 (2 C), 39.36 (2 C), 44.37 (2 C), 48.93 (2 C), 50.51 (2 C), 52.12 (2 C), 76.36 (2 C), 125.27 (2 C), 127.62 (2 C), 130.68 (2 C). IR (KBr): 3544, 3266, 2957, 2833, 2253, 1732, 1598, 1500, 1475, 1458, 1395, 1327, 1262, 1209, 1146, 1103, 1074, 1027, 911, 883, 800, 733, 703, 647 cm^-1.

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General Procedures for Addition of Phenylacetylene to Ketones.
Compound 9 (11.36 mg, 0.02 mmol) and Cu(OTf)₂ (7.2 mg, 0.02 mmol) were mixed in dry toluene (0.5 mL) under Ar atmosphere. Then, Et₂Zn in toluene (1.0 M, 1.0 mL) was added. After that, phenylacetylene (108 µL) was added. After 2 h, the solution was cooled to 0 °C and treated with ketones (0.25 mmol). The resulting mixture was stirred at 0 °C for 16-60 h. After the reaction was complete (monitoring with TLC), it was quenched with aq HCl (5%). Then, the mixture was extracted with Et₂O. The organic layer was washed with brine, dried over Na₂SO₄, and concentrated under vacuum. The residue was purified by flash column chromatography to obtain the product.