Open AccessEnantioselective Hydrothiolation: Diverging Cyclopropenes through Ligand Control
Author(s) -
ShaoZhen Nie,
Alexander Lu,
Erin L. Kuker,
Vy M. Dong
Publication year - 2021
Publication title -
journal of the american chemical society
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 7.115
H-Index - 612
eISSN - 1520-5126
pISSN - 0002-7863
DOI - 10.1021/jacs.1c00939
Subject(s) - chemistry , allylic rearrangement , enantioselective synthesis , ligand (biochemistry) , ring (chemistry) , reactivity (psychology) , combinatorial chemistry , stereochemistry , migratory insertion , medicinal chemistry , catalysis , organic chemistry , receptor , medicine , biochemistry , alternative medicine , pathology
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.