Rhodium-catalyzed cycloaddition reaction was calculated by density functional theory M06-2X method to directly synthesize benzoxepine and coumarin derivatives.In this work,we conducted a computational study of two com...Rhodium-catalyzed cycloaddition reaction was calculated by density functional 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 inserted 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.展开更多
A series of benzoxepin-5-ones were designed and synthesized by the cyclization of chalcones which were previously found as FXR antagonists. The cellular FXR antagonism of benzoxepines was investigated,among which the ...A series of benzoxepin-5-ones were designed and synthesized by the cyclization of chalcones which were previously found as FXR antagonists. The cellular FXR antagonism of benzoxepines was investigated,among which the most potent compound 10 l was able to reduce the plasma and hepatic triglyceride and plasma ALT levels in mice.展开更多
基金This work was supported by the Natural Science Foundation of Gansu Province(20JR5RA479)the Outstanding Youth Research Program of Lanzhou University of Arts and Sciences(2018JCQN008).
文摘Rhodium-catalyzed cycloaddition reaction was calculated by density functional 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 inserted 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.
基金supported by the Hong Kong,Macao and Taiwan Science & Technology Cooperation Program,MOST of China(No. 2012DFH30030)
文摘A series of benzoxepin-5-ones were designed and synthesized by the cyclization of chalcones which were previously found as FXR antagonists. The cellular FXR antagonism of benzoxepines was investigated,among which the most potent compound 10 l was able to reduce the plasma and hepatic triglyceride and plasma ALT levels in mice.
