P-Chiral Phosphine Sulfide Synthesis by Combination of Enzymatic Desymmetrization and Successive Deformylative P–C Cross-Couplings

Abstract

A process for the synthesis of P-chiral triarylphosphine sulfides via sequential Pd-catalyzed stereospecific P–C coupling reactions of P-chiral precursors prepared by enzymatic desymmetrization was developed. Three independent aryl substituents could be introduced onto the P atom by the sequential P–C couplings under mild conditions while retaining the high enantiopurity.

Key words

P-chiral phosphine - phosphine sulfide - P–C coupling - palladium - enzymatic desymmetrization

Publication History

Received: 10 March 2022

Accepted after revision: 10 June 2022

Accepted Manuscript online:
10 June 2022

Article published online:
20 July 2022

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• 11 General Procedure and Characterization Data for the Enzymatic Desymmetrization of 3a (Table 1, entry 1) CALB (500 mg, 100 wt% for 3a) was added to the mixture of 3a (500 mg, 2.47 mmol) and vinyl acetate (18 mL). After stirring at 25 °C for 7 h, the reaction mixture was diluted with CHCl₃, filtered, and evaporated to dryness. The residue was purified by column chromatography on silica gel (eluent: ethyl acetate/CHCl₃ = 1/15) to give 4a as a colorless oil (555 mg, 2.27 mmol, 92%, >99% ee). The optical purity was determined by chiral HPLC (Daicel CHIRALPAK IA, 0.46 × 25 cm, rt, eluent: 2-propanol/n-hexane = 5/95, 0.5 mL/min, detection: UV 254 nm, t = 49.2 min). Compound 4a: ¹H NMR (400 MHz, CDCl₃): δ = 2.14 (s, 3 H, CH₃), 3.17 (br, 1 H, OH), 4.07–4.37 (m, 2 H, CH₂OH), 4.56–4.88 (m, 2 H, CH₂OAc), 7.51–7.55 (m, 2 H, Ph), 7.59–7.62 (m, 1 H, Ph), 7.91–7.96 (m, 2 H, Ph). ¹³C{¹H} NMR (100 MHz, CDCl₃): δ = 20.7 (s, CH₃), 61.56 (d, J = 58.4 Hz, CH₂OAc), 61.63 (d, J = 61.4 Hz, CH₂OH), 127.3 (d, J = 74.5 Hz, ipso-C of Ph), 129.0 (d, J = 12.1 Hz, meta-C of Ph), 131.6 (d, J = 10.1 Hz, ortho-C of Ph), 133.0 (d, J = 3.0 Hz, para-C of Ph), 170.5 (d, J = 5.0 Hz, C = O). ³¹P{¹H} NMR (162 MHz, CDCl₃): δ = 40.7. HRMS (FAB+, 3-NBA): m/z calcd for C₁₀H₁₄O₃PS: 245.0401 [M + H]⁺; found: 245.0390.
• 12 The stability of 4h toward racemization was investigated (Scheme S2 in the Supporting Information). As a result, 4h was found to be stable toward racemization at 25 °C for 24 h in the absence of added acid or base, while the enantiopurity decreased under thermal and acidic/basic conditions.
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• 14 The reduction of 10 with (Me₃Si)₃SiH/AIBN gave the corresponding trivalent phosphine without loss of enantiopurity (Scheme S3 in the Supporting Information).