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<p>The catalytic asymmetric Michael addition of α,β-unsaturated carbonyl compounds is one of the most valuable methods for constructing the β-carbon chirality centre because of its atom economy and efficiency. However, the catalytic asymmetric reverse α-addition of a nucleophile to an α,β-unsaturated carbonyl compound is much less common. Here we realize a palladium-catalysed asymmetric α-carboranylation of α,β-unsaturated carboxylic acids via an inverse electron-demand nucleophilic addition. The reaction features good B(9)-site selectivity of <i>o</i>/<i>m</i>-carboranes, precise α-regioselectivity towards α,β-unsaturated carboxylic acids, wide functional group tolerance and excellent enantioselectivities. A detailed reaction mechanism is proposed based on experimental and computational results that elucidates the origin of the enantioselectivity and α-selectivity. This finding has a guiding significance for the catalytic asymmetric <i>anti</i>-Michael-type addition of α,β-unsaturated carbonyl compounds and provides a different avenue for synthesizing α-chiral carboxylic acids.</p><p></p>

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Palladium-catalysed asymmetric anti-Michael-type addition of α,β-unsaturated carboxylic acids with carboranes

  • 期刊论文

  • 发表日期：

    2026年1月30日

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  • Chao Lei,
  • Wen Lu,
  • Tingting Shen,
  • Meng Huang,
  • Yan-Xuan Wu,
  • Donghui Wei,
  • Yan-Na Ma,
  • Xuenian Chen

摘要

The catalytic asymmetric Michael addition of α,β-unsaturated carbonyl compounds is one of the most valuable methods for constructing the β-carbon chirality centre because of its atom economy and efficiency. However, the catalytic asymmetric reverse α-addition of a nucleophile to an α,β-unsaturated carbonyl compound is much less common. Here we realize a palladium-catalysed asymmetric α-carboranylation of α,β-unsaturated carboxylic acids via an inverse electron-demand nucleophilic addition. The reaction features good B(9)-site selectivity of o/m-carboranes, precise α-regioselectivity towards α,β-unsaturated carboxylic acids, wide functional group tolerance and excellent enantioselectivities. A detailed reaction mechanism is proposed based on experimental and computational results that elucidates the origin of the enantioselectivity and α-selectivity. This finding has a guiding significance for the catalytic asymmetric anti-Michael-type addition of α,β-unsaturated carbonyl compounds and provides a different avenue for synthesizing α-chiral carboxylic acids.