Center of Basic Molecular Science (CBMS), Department of Chemistry, Tsinghua University , Beijing 100084, China.
J Am Chem Soc. 2016 Nov 16;138(45):14872-14875. doi: 10.1021/jacs.6b10415. Epub 2016 Nov 7.
An iridium-catalyzed enantioselective hydroalkynylation of α,β-unsaturated amides was described. The selectivity of this reaction is distinct from that observed in many catalytic hydroalkynylations of α,β-unsaturated carbonyl compounds. It occurs selectively at the γ instead of the β position. Preliminary mechanistic studies suggest that the reaction proceeds through alkene isomerization followed by hydroalkynylation. This method provides a straightforward route for the synthesis of amides with a remote stereocenter at the γ position.
报道了铱催化的α,β-不饱和酰胺的对映选择性氢炔基化反应。该反应的选择性与许多α,β-不饱和羰基化合物的催化氢炔基化反应观察到的选择性不同。它选择性地发生在γ位而不是β位。初步的机理研究表明，该反应通过烯烃异构化后进行氢炔基化。该方法为在γ位具有远程立体中心的酰胺的合成提供了一种直接途径。
