镍催化炔烃和醛还原偶联反应中区域选择性和烯烃导向效应的起源。
Origins of regioselectivity and alkene-directing effects in nickel-catalyzed reductive couplings of alkynes and aldehydes.
机构信息
Department of Chemistry and Biochemistry, University of California, Los Angeles, California 90095, USA.
出版信息
J Am Chem Soc. 2010 Feb 17;132(6):2050-7. doi: 10.1021/ja909562y.
Abstract
The origins of reactivity and regioselectivity in nickel-catalyzed reductive coupling reactions of alkynes and aldehydes were investigated with density functional calculations. The regioselectivities of reactions of simple alkynes are controlled by steric effects, while conjugated enynes and diynes are predicted to have increased reactivity and very high regioselectivities, placing alkenyl or alkynyl groups distal to the forming C-C bond. The reactions of enynes and diynes involve 1,4-attack of the Ni-carbonyl complex on the conjugated enyne or diyne. The consequences of these conclusions on reaction design are discussed.
摘要
用密度泛函理论计算研究了镍催化炔烃和醛还原偶联反应中反应性和区域选择性的起源。简单炔烃反应的区域选择性受空间效应控制，而共轭烯炔和二炔预计具有更高的反应活性和非常高的区域选择性，使烯基或炔基基团位于形成的 C-C 键的远端。烯炔和二炔的反应涉及 Ni-羰基配合物对共轭烯炔或二炔的 1,4-进攻。这些结论对反应设计的影响进行了讨论。
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