Rhodium-catalyzed cycloaddition re-action was calculated by density func-tional theory M06-2X method to directly synthesize benzoxepine and coumarin derivatives.In this work,we conducted a computational study of two competitive mechanisms in which the carbon atom of acetylene or carbon monoxide attacked and in-serted from two different directions of the six-membered ring reactant to clarify the principle characteristics of this transformation.The calculation results reveal that:(i)the insertion process of alkyne or carbon monoxide is the key step of the reaction;(ii)for the(5+2)cycloaddition reaction of acetylene,higher energy is required to break the Rh-O bond of the reactant,and the reaction tends to complete the insertion from the side of the Rh-C bond;(iii)for the(5+1)cycloaddition of carbon monoxide,both reaction paths have lower activation free energy,and the two will generate a competition mechanism.

Xing-hui Zhang;Xi Wu;Hai-xiong Shi

College of Chemical Engineering,Lanzhou University of Arts and Science,Lanzhou 730010,China;School of Foreign Languages,Lanzhou University of Arts and Science,Lanzhou 730010,China

化学物理学报（英文版）

[1]Xing-hui Zhang;Xi Wu;Hai-xiong Shi-.Mechanistic Investigation on Rhodium(Ⅲ)-Catalyzed Cycloaddition of 2-Vinylphenol Derivatives with Ethyne or Carbon Monoxide by DFT Study)[J].化学物理学报（英文版）,2022(04):685-696

Cycloaddition,Vinylphenol,Ethyne,Monoxide,benzoxepine

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