Enantioselective [2,3]-Wittig Rearrangement of Carboxylic Acid Derived Enolates by Tetradentate Chiral Lithium Amide

Abstract

A chiral lithium amide mediated enantioselective [2,3]-Wittig rearrangement of carboxylic acid enolate has been developed. The reaction proceeds through the formation of a chiral mixed aggregate that shields one enantioface of enolate anion to give a highly functionalized chiral α-hydroxycarboxylic acid.

Key words

[2,3]-Wittig rearrangement - α-hydroxycarboxylic acids - chiral lithium amide - enantioselectivity - rearrangement

Publication History

Received: 23 January 2023

Accepted after revision: 21 February 2023

Accepted Manuscript online:
21 February 2023

Article published online:
13 March 2023

• References and Notes

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• 23 General Procedure for Enantioselective [2,3]-Wittig Rearrangement with HMPAA solution of (S,S)-3 (493 mg, 1.1 mmol) in THF (32 mL) was cooled to –78 °C, then to the solution was added dropwise n-BuLi in hexane (1.55 M; 2.83 mL, 4.4 mmol) over 2 min at –78 °C. After being stirred for 20 min at the same temperature, to the solution was added HMPA (2.30 mL, 13 mmol), and the mixture was stirred for 15 min at –78 °C. To the mixture was added a solution of α-allyloxycarboxylic acid (1.0 mmol) in THF (2 mL) at –78 °C by cannulation. After 24 h, the reaction was quenched with H₂O (15 mL) at –78 °C, and the mixture was acidified with 1 M HCl aq. (10 mL). The mixture was concentrated in vacuo to remove THF, and the residual solution was extracted with AcOEt (3 × 40 mL). The combined organic layer was dried with MgSO₄ and filtered off. The filtrate was concentrated in vacuo. The crude product was used esterification without further purification. The crude rearrangement product was dissolved in CHCl₃/MeOH (7:2; 9 mL). To the solution was added TMSCHN₂ in hexane (0.6 M; 2.17 mL, 1.3 mmol), and the resulting solution was stirred for overnight. The solution was concentrated in vacuo. The residue was purified by silica gel column chromatography to afford α-allyl-α-hydroxycarboxylic acid methyl ester
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