Regio- and stereocontrol elements in Rh(II)-catalyzed intramolecular C-H insertion of alpha-diazo-alpha-(phenylsulfonyl)acetamides.
[reaction: see text]. Intramolecular C-H insertion reaction of alpha-diazo-alpha-(phenylsulfonyl)acetamides proceeded with high regio- and stereoselectivities to afford highly functionalized gamma-lactams predominantly or exclusively. The high regioselectivity was attributed to the use of the phenylsulfonyl moiety, which altered electron density at the carbenoid center and exerted a steric effect during the insertion reaction. Also described herein are three control elements to determine regioselectivity, which are amide conformational, stereoelectronic, and substituent effects.
Yoon
C H
CH
Department of Chemistry, University of South Florida, 4202 E. Fowler Avenue, Tampa, Florida 33620-5250, USA.
Zaworotko
M J
MJ
Moulton
B
B
Jung
K W
KW
D000081:Acetamides / Q000138:chemical synthesis*; D001391:Azo Compounds / Q000138:chemical synthesis*; D002384:Catalysis; D007202:Indicators and Reagents; D008958:Models, Molecular; D011760:Pyrrolidinones / Q000138:chemical synthesis* / Q000737:chemistry; D012238:Rhodium; D013237:Stereoisomerism
D000081:Acetamides; D001391:Azo Compounds; D007202:Indicators and Reagents; D011760:Pyrrolidinones; D012238:Rhodium