Divergent Construction of α,α-Difunctionalized Ketones via [1,2]-Sigmatropic Rearrangement/Alkylation-Hydroxylation/Dialkylation of I (III) /S (VI) Ylides

作者：Shang‐Shi Zhang, Jiaohang Wei, Qiong Hu, Zifeng Yang, Wen‐Xuan Zou, Dan‐Ting Shen, Mei-Zhu Bao, Xiang Liu · 发表于：Organic Letters · 年份：2025 · DOI：10.1021/acs.orglett.5c00852 · 被引用次数：4 · 研究领域：Cyclopropane Reaction Mechanisms、Synthesis and Catalytic Reactions、Catalytic C–H Functionalization Methods

The rare [1,2]-sigmatropic rearrangement of sulfoxonium-iodonium hybrid ylides is described, which enables the efficient sulfoxidation/sulfonylation-alkylation of I (III) /S (VI) ylides with 1,3-dicarbonyls. By slight modification of the reaction conditions, controllable alkylation-hydroxylation and dialkylation of I (III) /S (VI) ylides were achieved. This strategy affords a diverse array of α,α-difunctionalized ketones in moderate to good yields, demonstrating broad substrate scope. These findings provide an important advancement in the [1,2]-sigmatropic rearrangement of sulfoxonium ylides and highlight the divergent reactivity of I (III) /S (VI) ylides.