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羧酸盐催化的末端炔烃的硅氢化反应

Carboxylate-Catalyzed -Silylation of Terminal Alkynes.

作者信息

Bannykh Anton, Pihko Petri M

机构信息

Department of Chemistry and NanoScience Center, University of Jyväskylä, P.O.B. 35, FI-40014 University of Jyväskylä, Finland.

出版信息

Org Lett. 2024 Mar 15;26(10):1991-1995. doi: 10.1021/acs.orglett.3c04213. Epub 2024 Mar 1.

DOI:10.1021/acs.orglett.3c04213
PMID:38428925
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC10949233/
Abstract

A carboxylate-catalyzed, metal-free -silylation protocol for terminal alkynes is reported using a quaternary ammonium pivalate as the catalyst and commercially available ,-bis(silyl)acetamides as silylating agents. The reaction proceeds under mild conditions, tolerates a range of functionalities, and enables concomitant - or -silylation of acidic OH or NH groups. A Hammett ρ value of +1.4 ± 0.1 obtained for -substituted 2-arylalkynes is consistent with the proposed catalytic cycle involving a turnover-determining deprotonation step.

摘要

报道了一种用于末端炔烃的羧酸盐催化、无金属的硅氢化反应方案，该方案使用新戊酸季铵盐作为催化剂，市售的α,α-双（硅基）乙酰胺作为硅氢化试剂。该反应在温和条件下进行，能耐受多种官能团，并能使酸性OH或NH基团同时进行α-或β-硅氢化。对于α-取代的2-芳基炔烃获得的哈米特ρ值为+1.4±0.1，这与所提出的涉及周转决定去质子化步骤的催化循环一致。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7265/10949233/82d6cf1aa104/ol3c04213_0004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7265/10949233/ffb0541724f5/ol3c04213_0001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7265/10949233/f20f6a1874a3/ol3c04213_0002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7265/10949233/761b7046c936/ol3c04213_0003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7265/10949233/82d6cf1aa104/ol3c04213_0004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7265/10949233/ffb0541724f5/ol3c04213_0001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7265/10949233/f20f6a1874a3/ol3c04213_0002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7265/10949233/761b7046c936/ol3c04213_0003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7265/10949233/82d6cf1aa104/ol3c04213_0004.jpg

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本文引用的文献

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