Mechanism, chemoselectivity and enantioselectivity for the rhodium-catalyzed desymmetric synthesis of hydrobenzofurans: a theoretical study

文献情報

出版日 2015-12-03

DOI 10.1039/C5QO00334B

インパクトファクター 5.281

著者

Zhaoyuan Yu, Xiaotian Qi, Yingzi Li, Song Liu, Yu Lan

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要旨

Rhodium-catalyzed desymmetrization of cyclohexadienones is an efficient method for the asymmetric synthesis of hydrobenzofurans. The newly reported density functional theory (DFT) method MN12-L is used to investigate the mechanism, chemoselectivity and enantioselectivity for this type of reaction. Computational results indicate that the preferred pathway involves transmetallation to form an aryl–rhodium compound, alkyne insertion, intramolecular olefin insertion, and protonation to generate the hydrobenzofuran product. The enantioselectivity is controlled by the intramolecular olefin insertion step, which is ascribed to the steric repulsions between the ligand and substrate. In addition, the generation of a side product via a second intermolecular alkyne insertion has also been considered in calculations.

掲載誌

Organic Chemistry Frontiers

CiteScore: 7.8

自己引用率: 8.7%

年間論文数: 724

Organic Chemistry Frontiers publishes high-quality research from across organic chemistry. Emphases are placed on studies that make significant contributions to the field of organic chemistry by reporting either new or significantly improved protocols or methodologies. Topics include, but are not limited to the following: Organic synthesis Development of synthetic methodologies Catalysis Natural products Functional organic materials Supramolecular and macromolecular chemistry Physical and computational organic chemistry