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. 2022 Jun 17;12(12):7377-7385.
doi: 10.1021/acscatal.2c01232. Epub 2022 Jun 7.

Enantioselective Inter- and Intramolecular Sulfenofunctionalization of Unactivated Cyclic and (Z)-Alkenes

Anastassia Matviitsuk  1 , Jesse Lee Panger  1 , Scott E Denmark  1
Affiliations

Enantioselective Inter- and Intramolecular Sulfenofunctionalization of Unactivated Cyclic and (Z)-Alkenes

Anastassia Matviitsuk et al. ACS Catal. .

Abstract

A method for the enantioselective, Lewis base-catalyzed sulfenofunctionalization of cyclic and (Z)-alkenes is reported. The intermediate thiiranium ion generated in the presence of a selenophosphoramide catalyst is intercepted by a variety of nucleophiles. A diverse array of inter- and intramolecular functionalizations proceed in high yield and good to high enantioselectivity (86:14-98:2 er). Prior experimental and computational studies indicated such enantiotopic face discrimination to be poor; however, the results disclosed herein remediate the previous findings. Control experiments were performed to investigate the different behavior of (Z)-alkenes and their more established (E)-counterparts.

Keywords: Lewis base; organocatalysis; sulfenium; sulfenofunctionalization; thiiranium.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Figure 1.
Figure 1.
Steric interactions of thiiranium ions.
Scheme 1.
Scheme 1.
Generalized Asymmetric Sulfenofunctionalizations of Alkenes
Scheme 2.
Scheme 2.
Sulfenofunctionalization of 1,2-Disubstituted (E)- vs (Z)-Alkenes
Scheme 3.
Scheme 3.. Rationale for exo-Selective Cyclization of (Z)-Alkenesa
aAll reactions performed on a 0.1 mmol scale. Yields in parentheses determined by 1H NMR analysis of the crude reaction mixture using 1,1,2,2-tetrachloroethane as the internal standard. *Enantiomeric ratio determined on the corresponding sulfone.
Scheme 4.
Scheme 4.
Competition Experiment between (E)- and (Z)-β-Methylstyrene
See this image and copyright information in PMC

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