TY - JOUR
T1 - Catalyst-Controlled Diastereoselective Synthesis of Cyclic Amines via C-H Functionalization
AU - Munnuri, Sailu
AU - Adebesin, Adeniyi Michael
AU - Paudyal, Mahesh P.
AU - Yousufuddin, Muhammed
AU - Dalipe, Alfonso
AU - Falck, John R.
N1 - Publisher Copyright:
© 2017 American Chemical Society.
PY - 2017/12/20
Y1 - 2017/12/20
N2 - Reliable regio- and stereochemical techniques applicable to nonactivated aliphatic systems remain largely elusive due to the challenges of discriminating between multiple, relatively strong sp3 C-H bonds whose chemical behavior often differ only subtly. Nevertheless, approaches that employ directing groups and/or auxiliaries have emerged, but impose practical restrictions, especially in complex molecule synthesis. This report describes a catalyst-controlled regio- and diastereoselective synthesis of N-unprotected pyrrolidines via dirhodium catalyzed intramolecular nitrene insertion into sp3 C-H bonds. The reaction proceeds at rt without external oxidants, nitrene stabilizing groups, or directing functionality. The insights that emerged from the conformational/stereoselectivity relationships (CSR) between catalysts and substrates provide a framework for rational catalyst design that can accommodate a broader range of aliphatic C-H chemistry.
AB - Reliable regio- and stereochemical techniques applicable to nonactivated aliphatic systems remain largely elusive due to the challenges of discriminating between multiple, relatively strong sp3 C-H bonds whose chemical behavior often differ only subtly. Nevertheless, approaches that employ directing groups and/or auxiliaries have emerged, but impose practical restrictions, especially in complex molecule synthesis. This report describes a catalyst-controlled regio- and diastereoselective synthesis of N-unprotected pyrrolidines via dirhodium catalyzed intramolecular nitrene insertion into sp3 C-H bonds. The reaction proceeds at rt without external oxidants, nitrene stabilizing groups, or directing functionality. The insights that emerged from the conformational/stereoselectivity relationships (CSR) between catalysts and substrates provide a framework for rational catalyst design that can accommodate a broader range of aliphatic C-H chemistry.
UR - http://www.scopus.com/inward/record.url?scp=85038599691&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85038599691&partnerID=8YFLogxK
U2 - 10.1021/jacs.7b09901
DO - 10.1021/jacs.7b09901
M3 - Article
C2 - 29182870
AN - SCOPUS:85038599691
SN - 0002-7863
VL - 139
SP - 18288
EP - 18294
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 50
ER -