Desilylative allylation of 3,3-borylsilylpropene under metallaphotoredox catalysis.
basic_science · Level V
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- Record sourced from PubMed, PMID 41526397.
- Also identified by DOI 10.1038/s41467-025-68269-0 and PMC identifier 12895009.
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Abstract
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 Cr<sup>III</sup> allyl intermediate. Moreover, γ-functionalization products bearing CF<sub>2</sub> 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.