State Key Laboratory of Physical Chemistry of Solid Surfaces, Key Laboratory for Chemical Biology of Fujian Province, and College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, China.
State Key Laboratory of Physical Chemistry of Solid Surfaces, Key Laboratory for Theoretical and Computational Chemistry of Fujian Province, and College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, China.
Angew Chem Int Ed Engl. 2019 Nov 4;58(45):16252-16259. doi: 10.1002/anie.201908495. Epub 2019 Sep 18.
Described herein is an organocatalytic enantioselective desymmetrizing cycloisomerization of arylsulfonyl-protected ynamide cyclohexanones, representing the first metal-free asymmetric Conia-ene-type carbocyclization. This method allows the highly efficient and atom-economical construction of a range of valuable morphans with wide substrate scope and excellent enantioselectivity (up to 97 % ee). In addition, such a cycloisomerization of alkylsulfonyl-protected ynamide cyclohexanones can lead to the divergent synthesis of normorphans as the main products with high enantioselectivity (up to 90 % ee). Moreover, theoretical calculations are employed to elucidate the origins of regioselectivity and enantioselectivity.
本文描述了一种芳磺酰基保护的炔酰胺环己酮的有机催化对映选择性去对称环化异构化反应，代表了首例无金属的不对称 Conia-ene 型碳环化反应。该方法能够高效、原子经济地构建一系列具有广泛底物范围和优异对映选择性（高达 97%ee）的有价值的吗啡烷。此外，烷基磺酰基保护的炔酰胺环己酮的环化异构化可以导致主要产物为高对映选择性（高达 90%ee）的诺吗啡烷的发散合成。此外，还采用理论计算阐明了区域选择性和对映选择性的起源。
