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<p>Stereoselective nucleophilic additions to <i>α</i>-substituted carbonyl compounds are a crucial area of contemporary research in organic chemistry. Of the various advancements in π-facial selectivity in addition reactions of carbonyl compounds, the (polar) Felkin-Anh model and the chelation model are well recognized for accurately explaining the selectivity of the allylic products. For reactions that involve <i>α</i>-oxy carbonyl groups - known for their broad applications in natural-product synthesis and as effective building blocks in organic synthesis - the stereoselective reaction typically follows the chelation model, favoring <i>syn</i>-selective addition. In contrast to the well-established <i>syn</i>-selective additions of <i>α</i>-oxy carbonyls, <i>anti</i>-selective additions through a non-chelation pathway remain largely unexplored. In this study, we present the <i>anti</i>-selective allylation of <i>α</i>-oxy ketones using allylatranes that feature a highly coordinated group-14-element center. These atranes demonstrate high nucleophilicity and low chelating ability due to their transannular interactions and rigid framework, facilitating <i>anti</i>-selective allylations. A combined experimental and theoretical approach has been used to highlight the unique electronic properties of these atranes. This method is applicable to a wide variety of substrates, producing <i>anti</i>-1,2-diols with a homoallylic moiety in high yield and excellent diastereoselectivity compared to traditional methods.</p>

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Non-chelation control in allylations of α-oxy ketones using group-14 allylatranes

  • 期刊论文

  • 出版模式：

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  • 发表日期：

    2026年3月3日

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  • Yuya Tsutsui,
  • Kokoro Shiga,
  • Akihito Konishi,
  • Makoto Yasuda

摘要

Stereoselective nucleophilic additions to α-substituted carbonyl compounds are a crucial area of contemporary research in organic chemistry. Of the various advancements in π-facial selectivity in addition reactions of carbonyl compounds, the (polar) Felkin-Anh model and the chelation model are well recognized for accurately explaining the selectivity of the allylic products. For reactions that involve α-oxy carbonyl groups - known for their broad applications in natural-product synthesis and as effective building blocks in organic synthesis - the stereoselective reaction typically follows the chelation model, favoring syn-selective addition. In contrast to the well-established syn-selective additions of α-oxy carbonyls, anti-selective additions through a non-chelation pathway remain largely unexplored. In this study, we present the anti-selective allylation of α-oxy ketones using allylatranes that feature a highly coordinated group-14-element center. These atranes demonstrate high nucleophilicity and low chelating ability due to their transannular interactions and rigid framework, facilitating anti-selective allylations. A combined experimental and theoretical approach has been used to highlight the unique electronic properties of these atranes. This method is applicable to a wide variety of substrates, producing anti-1,2-diols with a homoallylic moiety in high yield and excellent diastereoselectivity compared to traditional methods.