Zhou Quan-Quan, Zou You-Quan, Kar Sayan, Diskin-Posner Yael, Ben-David Yehoshoa, Milstein David
Department of Molecular Chemistry and Materials Science and Chemical Research Support, Weizmann Institute of Science, Rehovot 76100, Israel.
ACS Catal. 2021 Aug 20;11(16):10239-10245. doi: 10.1021/acscatal.1c01748. Epub 2021 Aug 3.
A simple and efficient system for the hydration and α-deuteration of nitriles to form amides, α-deuterated nitriles, and α-deuterated amides catalyzed by a single pincer complex of the earth-abundant manganese capable of metal-ligand cooperation is reported. The reaction is selective and tolerates a wide range of functional groups, giving the corresponding amides in moderate to good yields. Changing the solvent from -butanol to toluene and using DO results in formation of α-deuterated nitriles in high selectivity. Moreover, α-deuterated amides can be obtained in one step directly from nitriles and DO in THF. Preliminary mechanistic studies suggest the transformations contributing toward activation of the nitriles via a metal-ligand cooperative pathway, generating the manganese ketimido and enamido pincer complexes as the key intermediates for further transformations.
报道了一种简单高效的体系，用于腈的水合和α-氘代反应，以形成酰胺、α-氘代腈和α-氘代酰胺，该反应由一种能够进行金属-配体协同作用的、地球上储量丰富的锰的单钳形配合物催化。该反应具有选择性，能耐受多种官能团，以中等至良好的产率得到相应的酰胺。将溶剂从叔丁醇改为甲苯并使用D₂O，可高选择性地形成α-氘代腈。此外，α-氘代酰胺可在四氢呋喃中由腈和D₂O一步直接制得。初步机理研究表明，这些转化过程通过金属-配体协同途径促进腈的活化，生成锰酮亚胺和烯胺基钳形配合物作为进一步转化的关键中间体。
