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Molybdenum‐Catalyzed Dehydrogenative Synthesis of Imines from Alcohols and Amines
ChemCatChem ( IF 4.5 ) Pub Date : 2018-07-04 , DOI: 10.1002/cctc.201800677
Kobra Azizi 1 , Robert Madsen 1
Affiliation  

A molybdenum N‐heterocyclic carbene catalyst has been developed for the synthesis of imines from primary alcohols and amines with the liberation of dihydrogen. The catalyst is generated in situ from molybdenum hexacarbonyl, 1,3‐dicyclohexylimidazolium chloride and potassium tert‐butoxide and is further stabilized by the phosphine ligand dppe. Imines are formed in moderate to good isolated yields and a variety of alcohols and amines can be employed in the reaction including anilines. The transformation constitutes the first example of a homogeneous molybdenum‐catalyzed acceptorless dehydrogenative coupling with alcohols and is believed to proceed by formation of a cis‐coordinated molybdenum bis‐N‐heterocyclic carbene complex, which performs an oxidative addition to the alcohol, β‐hydride elimination and reductive elimination of dihydrogen.

中文翻译:

醇和胺的钼催化脱氢合成亚胺

已开发出一种钼N-杂环卡宾催化剂,用于在释放二氢的情况下从伯醇和胺合成亚胺。该催化剂是由六羰基钼,1,3-二环己基咪唑鎓氯化物和丁醇钾原位生成的,并通过膦配体dppe进一步稳定。亚胺以中等至良好的分离产率形成,反应中可以使用多种醇和胺,包括苯胺。该转变构成了与醇进行均相钼催化的无受体脱氢偶合的第一个例子,并且据信是通过形成顺式而进行的。钼双N杂环卡宾配合物,可对醇进行氧化加成,β-氢化物消除和二氢还原性消除。
更新日期:2018-07-04
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