镍杂环丁烷的卡宾转移反应活性
Carbene transfer reactivity from a nickelacyclobutane.
作者信息
Sansores-Paredes María L G, Lutz Martin, Moret Marc-Etienne
机构信息
Organic Chemistry and Catalysis, Institute for Sustainable and Circular Chemistry, Faculty of Science, Utrecht University, Universiteitsweg 99, 3584 CG, Utrecht, The Netherlands.
Structural Biochemistry, Bijvoet Centre for Biomolecular Research, Utrecht University, 3584 CG, Utrecht, The Netherlands.
出版信息
Chem Commun (Camb). 2024 Oct 22;60(85):12397-12400. doi: 10.1039/d4cc04273e.
A formal carbene-transfer reaction from an isolated nickelacyclobutane to an isocyanide to form a ketenimine is reported. DFT calculations support a stepwise 1,1-insertion/fragmentation pathway without a carbene intermediate. This unusual reactivity suggests a potential new role as "carbene reservoir" for nickelacyclobutanes, which are typically seen as intermediates in catalytic cyclopropanation.
报道了一种从分离出的镍杂环丁烷到异腈的正式卡宾转移反应，以形成烯酮亚胺。密度泛函理论计算支持一种逐步的1,1-插入/碎片化途径，且没有卡宾中间体。这种不寻常的反应性表明镍杂环丁烷作为“卡宾储存库”具有潜在的新作用，而镍杂环丁烷通常被视为催化环丙烷化反应中的中间体。
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