Organocatalytic Enantioselective Conia‐Ene‐Type Carbocyclization of Ynamide Cyclohexanones: Regiodivergent Synthesis of Morphans and Normorphans

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 rang...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2019-11, Vol.58 (45), p.16252-16259
Main Authors: Xu, Yin, Sun, Qing, Tan, Tong‐De, Yang, Ming‐Yang, Yuan, Peng, Wu, Shao‐Qi, Lu, Xin, Hong, Xin, Ye, Long‐Wu
Format: Article
Language:English
Subjects:
asymmetric catalysis
cyclizations
Cyclohexanone
desymmetrization
Enantiomers
heterocycles
Isomerization
organocatalysis
Regioselectivity
Substrates
Synthesis
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Summary: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. An organocatalytic enantioselective desymmetrizing cycloisomerization of arylsulfonyl‐protected ynamide cyclohexanones is disclosed for practical and atom‐economical assembly of morphans with excellent enantioselectivities. It represents the first metal‐free asymmetric Conia‐ene‐type carbocyclization. In addition, cycloisomerization of the alkylsulfonyl‐protected ynamide cyclohexanones leads to normorphans with high enantioselectivities.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201908495