TY - JOUR
T1 - Late-Stage Molecular Editing Enabled by Ketone Chain-Walking Isomerization
AU - Brägger, Yannick
AU - Green, Ori
AU - Bhawal, Benjamin N.
AU - Morandi, Bill
N1 - Publisher Copyright:
© 2023 The Authors. Published by American Chemical Society.
PY - 2023/9/13
Y1 - 2023/9/13
N2 - Herein, a method for the isomerization of ketones in a manner akin to the chain-walking reaction of alkenes is described. Widely available and inexpensive pyrrolidine and elemental sulfur are deployed as catalysts to achieve this reversible transformation. Key to the utility of this approach was the elucidation of a stereochemical model to determine the thermodynamically favored product of the reaction and the kinetic selectivity observed. With the distinct selectivity profile of our ketone chain-walking process, the isomerization of various steroids was demonstrated to rapidly access novel steroids with “unnatural” oxidation patterns.
AB - Herein, a method for the isomerization of ketones in a manner akin to the chain-walking reaction of alkenes is described. Widely available and inexpensive pyrrolidine and elemental sulfur are deployed as catalysts to achieve this reversible transformation. Key to the utility of this approach was the elucidation of a stereochemical model to determine the thermodynamically favored product of the reaction and the kinetic selectivity observed. With the distinct selectivity profile of our ketone chain-walking process, the isomerization of various steroids was demonstrated to rapidly access novel steroids with “unnatural” oxidation patterns.
UR - http://www.scopus.com/inward/record.url?scp=85171202263&partnerID=8YFLogxK
U2 - 10.1021/jacs.3c05680
DO - 10.1021/jacs.3c05680
M3 - ???researchoutput.researchoutputtypes.contributiontojournal.article???
C2 - 37640367
AN - SCOPUS:85171202263
SN - 0002-7863
VL - 145
SP - 19496
EP - 19502
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 36
ER -