Scholarlink

<p>Chemoselective functionalization of hetero-<i>gem</i>-dimetalloid represents an attractive strategy in terms of diversity-oriented synthesis. In particular, desilylative functionalization of <i>gem-</i>silylboronate esters remains a challenging task and existing solutions heavily relied on ionic reactions. Herein, we report a desilylative functionalization of allylic <i>gem</i>-silylboronate esters with aldehydes under synergistic photoredox and chromium(II) catalysis. With different substrates, both α- and γ-functionalization are realized with exclusive regioselectivity and diastereoselectivity, which is dictated by the chair-like transition state of predominant isomer of Cr<sup>III</sup> allyl intermediate. Moreover, γ-functionalization products bearing CF<sub>2</sub> unit are acquired when <i>gem</i>-difluoroalkene-containing substrates are employed. In the presence of chiral ligand, enantioselective allylation of aldehydes is successfully accomplished, affording alkenylated 1,2-diols after oxidative workup with excellent regio-, diastereo- and enantioselectivity. The current protocol displays wide substrate generality and broad functional group compatibility. In addition, diverse post-transformations converted obtained products into a variety of valuable structures.</p>

错误：搜索内容不能为空，请输入英文关键词
错误：关键词超出字数限制，请精简
高级检索

Desilylative allylation of 3,3-borylsilylpropene under metallaphotoredox catalysis

  • 期刊论文

  • 出版模式：

    开放获取

  • 发表日期：

    2026年1月12日

查看全文
  • Longfei Liu,
  • Haojie Li,
  • Minglong Zhang,
  • Renyi Diao,
  • Lifang Tian,
  • Chi Zhang,
  • Yu Zhang,
  • Zhi-Liang Shen,
  • Kai Guo,
  • Chao Feng

摘要

Chemoselective functionalization of hetero-gem-dimetalloid represents an attractive strategy in terms of diversity-oriented synthesis. In particular, desilylative functionalization of gem-silylboronate esters remains a challenging task and existing solutions heavily relied on ionic reactions. Herein, we report a desilylative functionalization of allylic gem-silylboronate esters with aldehydes under synergistic photoredox and chromium(II) catalysis. With different substrates, both α- and γ-functionalization are realized with exclusive regioselectivity and diastereoselectivity, which is dictated by the chair-like transition state of predominant isomer of CrIII allyl intermediate. Moreover, γ-functionalization products bearing CF2 unit are acquired when gem-difluoroalkene-containing substrates are employed. In the presence of chiral ligand, enantioselective allylation of aldehydes is successfully accomplished, affording alkenylated 1,2-diols after oxidative workup with excellent regio-, diastereo- and enantioselectivity. The current protocol displays wide substrate generality and broad functional group compatibility. In addition, diverse post-transformations converted obtained products into a variety of valuable structures.