Pd-Catalyzed Asymmetric Hydrogenation of C=C Bond of α,β-Unsaturated Ketones

Abstract

Homogenous palladium-catalyzed asymmetric hydrogenation of C=C double bond of α,β-unsaturated ketones has been ­developed by using palladium(II) trifluoroacetate/(S)-7,7′-bis-[di(4-methoxyphenyl]phosphino)-1,1′-spirobiindane complex [Pd(OCOCF₃)₂-(S)-An-SDP] as the catalyst under ambient hydrogen pressure and room temperature with up to 89% ee.

Key words

palladium - hydrogenation - unsaturated ketones - SDP ligand

References and Notes

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10

Typical Procedure for the Asymmetric Hydrogenation of β,β-Disubstituted Unsaturated Ketones (S)-An-SDP (4.2 mg, 0.006 mmol) and Pd(OCOCF₃)₂ (1.7 mg, 0.005 mmol) were placed in a dried Schlenk tube under nitrogen atmosphere, and degassed anhyd acetone was added. The mixture was stirred at r.t. for 1 h. The solvent was removed under vacuum to give the catalyst. To this catalyst was added substrate 1a (0.25 mmol) and dry TFE (2 mL) under a hydrogen atmosphere, then the mixture was stirred at r.t. After confirmation of consumption of substrate by GC, the hydrogen gas was slowly released from the reaction vessel. The ee was determined by HPLC after purification on silica gel using PE and EtOAc. ( S )-1,3-Diphenylbutan-1-one (2a)
Yield 95%, 86% ee; [α]_D ^r.t. +0.70 (c 1.87, CHCl₃). ^¹H NMR (400 MHz, CDCl₃): δ =1.36 (d, J = 6.9 Hz, 3 H), 3.21 (dd, J = 16.4, 8.2 Hz, 1 H), 3.32 (dd, J = 16.5, 5.8 Hz, 1 H), 3.49-3.58 (m, 1 H), 7.20-7.24 (m, 1 H), 7.28-7.36 (m, 4 H), 7.42-7.50 (m, 2 H), 7.53-7.56 (m, 1 H), 7.93-7.96 (m, 2 H). ^¹³C NMR (100 MHz, CDCl₃): δ = 22.1, 35.7, 47.2, 126.5, 127.0, 128.2, 128.5, 128.7, 133.1, 137.4, 146.7, 199.2. HPLC (AD-H, eluent: hexanes-i-PrOH = 95:5, detector: 230 nm, flow rate: 0.8 mL/min), t _R1 (S) = 7.6 min (major); t _R2 (R) = 8.7 min.