Rhodium-catalyzed carbonylation of cyclopropyl substituted propargyl esters: a tandem 1,3-acyloxy migration [5 + 1] cycloaddition.
We have developed two different types of tandem reactions for the synthesis of highly functionalized cyclohexenones from cyclopropyl substituted propargyl esters. Both reactions were initiated by rhodium-catalyzed Saucy-Marbet 1,3-acyloxy migration. The resulting cyclopropyl substituted allenes derived from acyloxy migration then underwent [5 + 1] cycloaddition with CO. The acyloxy group not only eased the access to allene intermediates but also provided a handle for further selective functionalizations.
School of Pharmacy, University of Wisconsin, Madison, Wisconsin 53705, USA.
Dongxu
D
Shu
Xiaoxun
X
Li
Min
M
Zhang
Patrick J
PJ
Robichaux
Ilia A
IA
Guzei
Weiping
W
Tang
D002248:Carbon Monoxide / Q000737:chemistry; D002384:Catalysis; D003500:Cyclization; D003521:Cyclopropanes / Q000737:chemistry*; D004952:Esters / Q000737:chemistry*; D007659:Ketones / Q000138:chemical synthesis* / Q000737:chemistry; D015394:Molecular Structure; D012238:Rhodium / Q000737:chemistry*
D003521:Cyclopropanes; D004952:Esters; D007659:Ketones; D002248:Carbon Monoxide; D012238:Rhodium