Regio‐ and Enantioselective Synthesis of Sulfone‐Bearing Quaternary Carbon Stereocenters by Pd‐Catalyzed Allylic Substitution

Chiral sulfones are of great importance in medicinal chemistry and chemical synthesis. Efficient methods for preparing enantiomerically enriched sulfone‐containing molecules can therefore be of significant value; such methods, however, are uncommon. Herein, we report the first general palladium‐cata...

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Bibliographic Details
Published in:	Angewandte Chemie International Edition Vol. 59; no. 3; pp. 1340 - 1345
Main Authors:	Khan, Ajmal, Zhao, Heng, Zhang, Meina, Khan, Shahid, Zhao, Depeng
Format:	Journal Article
Language:	English
Published:	WEINHEIM Wiley 13.01.2020 Wiley Subscription Services, Inc
Edition:	International ed. in English
Subjects:	Aliphatic compounds allylic substitution Aromatic compounds asymmetric catalysis Carbon Carbonates Chemical synthesis Chemistry Chemistry, Multidisciplinary cyclic carbonates Enantiomers Organic chemistry Palladium Physical Sciences Science & Technology Sodium Substitution reactions Substrates Sulfones tertiary sulfones ASYMMETRIC-SYNTHESIS DECARBOXYLATIVE CYCLOADDITION ALKYLATION SULFUR asymmetric catalysis CENTERS cyclic carbonates CHIRAL SULFONES S BOND FORMATION VINYLETHYLENE CARBONATES AMINES tertiary sulfones CONSTRUCTION palladium allylic substitution
ISSN:	1433-7851, 1521-3773, 1521-3773
Online Access:	Get full text
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Summary:	Chiral sulfones are of great importance in medicinal chemistry and chemical synthesis. Efficient methods for preparing enantiomerically enriched sulfone‐containing molecules can therefore be of significant value; such methods, however, are uncommon. Herein, we report the first general palladium‐catalyzed sulfonylation of vinyl cyclic carbonates with sodium sulfinates. A series of enantiomerically enriched tertiary allylic sulfones were synthesized in good yields with excellent enantiomeric ratios. Both aliphatic‐ and aryl‐substituted vinyl cyclic carbonates are suitable reactants with excellent results. This reaction features broad substrates scope, readily available starting materials, excellent regio‐ and enantioselectivity, and synthesis of sulfone‐bearing quaternary carbon stereocenters. Through the sulfonylation of geranyl derived cyclic carbonate 1 h, we achieve the formal total synthesis of (+)‐agelasidine A. The first general example of regio‐ and enantioselective palladium catalyzed allylic sulfonylation of vinyl cyclic carbonates provides an efficient and direct way to construct sulfone‐bearing quaternary carbon stereocenters. A three steps formal total synthesis of (+)‐agelasidine A is achieved which exemplifies the practical use of this protocol in a synthetic setting.
Bibliography:	ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 14 content type line 23
ISSN:	1433-7851 1521-3773 1521-3773
DOI:	10.1002/anie.201910378