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Original Articles

Origins and applications of stereoselective sulfenate anion alkylation reactions

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Pages 692-697 | Received 28 Mar 2019, Accepted 01 Apr 2019, Published online: 19 Apr 2019
 

Abstract

Selected sulfenate anions can be alkylated with diastereoselectivities near 9:1 when there is appropriately positioned carbon chirality in the sulfenate structure or in the alkylation electrophile. Both protocols represent a conceptually different approach to β-amino sulfoxides. When vinylic β-amino sulfoxides are cyclized, thiomorpholine S-oxides result, and substrate control over the stereochemistry of alkyl substituents was found. This finding facilitates the synthesis of cis and trans dialkylpyrrolidines, known ant venom alkaloids. A computational model is demonstrated to account for some of the diastereoselection results. The importance of intramolecular interactions of sulfenate constituent atoms with pendent substituents is established.

Graphical Abstract

Acknowledgements

The authors with to thank the following agencies for funding for the chemistry reported herein: Natural Sciences and Engineering Research Council (NSERC) of Canada; Petroleum Research Fund administered by the ACS; Shared Hierarchical Academic Research Computing Network (SHARCNET: www.sharcnet.ca); Compute/Calcul Canada.

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