Diastereoselective Palladium-Catalyzed Conjugate Addition of Arylboronic Acids to α-Substituted Cyclic Enones

Ang Gao; Xiu-Yan Liu; Chang-Hua Ding; Xue-Long Hou

doi:10.1055/s-0036-1590742

Synlett, Table of Contents

Synlett 2017; 28(20): 2829-2832
DOI: 10.1055/s-0036-1590742

letter

Diastereoselective Palladium-Catalyzed Conjugate Addition of Arylboronic Acids to α-Substituted Cyclic Enones

Ang Gao

^aState Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Ling Ling Road, Shanghai, 200032, P. R. of China Email: dingch@sioc.ac.cn Email: xlhou@sioc.ac.cn

,

Xiu-Yan Liu

^aState Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Ling Ling Road, Shanghai, 200032, P. R. of China Email: dingch@sioc.ac.cn Email: xlhou@sioc.ac.cn

,

Chang-Hua Ding*

^aState Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Ling Ling Road, Shanghai, 200032, P. R. of China Email: dingch@sioc.ac.cn Email: xlhou@sioc.ac.cn

,

Xue-Long Hou*

^aState Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Ling Ling Road, Shanghai, 200032, P. R. of China Email: dingch@sioc.ac.cn Email: xlhou@sioc.ac.cn

^bShanghai-Hong Kong Joint Laboratory in Chemical Synthesis, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Ling Ling Road, Shanghai, 200032, P. R. of China

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Abstract

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This paper is dedicated to Professor Victor Snieckus on the occasion of his 80^th birthday.

Abstract

A palladium-catalyzed conjugate addition of arylboronic acids to α-substituted cyclic enones was developed to give α,β-disubstituted ketones with high diastereoselectivity. Mechanistic investigation showed that the high diastereoselectivity was realized through epimerization.

Key words

palladium - conjugate addition - boronic acid - cyclic enone - diastereoselectivity

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References

References and Notes

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11 Typical experimental procedure: To a flame-dried 25 mL Schlenk tube were added Pd(TFA)₂ (4.2 mg, 0.0125 mmol), ligand L2 (2.3 mg, 0.015 mmol), and anhydrous DMAc (1.0 mL). The resulting mixture was stirred for 60 min. Arylboronic acid 2b (68.0 mg, 0.5 mmol) and ketone 1a (24.0 mg, 0.25 mmol) were added subsequently. The resulting reaction mixture was stirred at 80 °C for 24 h. Water (10 mL) was added and the aqueous phase was extracted with ethyl acetate (2 × 10 mL). The combined organic phase was washed with water (3 × 10 mL) and brine (10 mL). The organic phase was dried over anhydrous Na₂SO₄ and filtered. After the volatile materials were removed in vacuo, the ratio of two diastereoisomers was determined by GC chromatography. The resulting residue was then subjected to flash chromatography on silica gel with petroleum ether and ethyl acetate as eluent to give product 3b (39.9 mg, 85%) as a colorless oil. ¹H NMR (400 MHz, CDCl₃): δ = 7.33–7.01 (m, 5 H), 3.10 (td, J = 12.1, 5.2 Hz, 1 H), 2.61–2.48 (m, 1 H), 2.43–2.17 (m, 7 H), 1.87–1.71 (m, 1 H), 1.01 (dd, J = 6.8, 1.3 Hz, 3 H). ¹³C NMR (101 MHz, CDCl₃): δ = 219.7, 140.3, 136.4, 130.6, 126.5, 126.4, 124.7, 51.0, 46.0, 37.6, 29.1, 19.8, 12.1. IR (neat): 2962, 1738, 1492, 1459, 1406, 1260, 1147, 1090, 1021, 798, 761, 732. MS (EI): m/z (%) = 187 (60) [M⁺], 132 (90), 114 (100), 90 (50). HRMS (EI): m/z [M]⁺ calcd for C₁₃H₁₆O: 188.1201; found: 188.1199.
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