Enantioselective Hydrothiolation: Diverging Cyclopropenes through Ligand Control.

Autor:	Nie S; Department of Chemistry, University of California, Irvine, Irvine, California 92697, United States., Lu A; Department of Chemistry, University of California, Irvine, Irvine, California 92697, United States., Kuker EL; Department of Chemistry, University of California, Irvine, Irvine, California 92697, United States., Dong VM; Department of Chemistry, University of California, Irvine, Irvine, California 92697, United States.
Jazyk:	angličtina
Zdroj:	Journal of the American Chemical Society [J Am Chem Soc] 2021 Apr 28; Vol. 143 (16), pp. 6176-6184. Date of Electronic Publication: 2021 Apr 15.
DOI:	10.1021/jacs.1c00939
Abstrakt:	In this article, we advance Rh-catalyzed hydrothiolation through the divergent reactivity of cyclopropenes. Cyclopropenes undergo hydrothiolation to provide cyclopropyl sulfides or allylic sulfides. The choice of bisphosphine ligand dictates whether the pathway involves ring-retention or ring-opening. Mechanistic studies reveal the origin for this switchable selectivity. Our results suggest the two pathways share a common cyclopropyl-Rh(III) intermediate. Electron-rich Josiphos ligands promote direct reductive elimination from this intermediate to afford cyclopropyl sulfides in high enantio- and diastereoselectivities. Alternatively, atropisomeric ligands (such as DTBM-BINAP) enable ring-opening from the cyclopropyl-Rh(III) intermediate to generate allylic sulfides with high enantio- and regiocontrol.
Databáze:	MEDLINE
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