Synthesis of substituted oxa- and aza[3.2.1] and [4.3.1]bicyclics via an unprecedented molybdenum-mediated 1,5-"Michael-type" reaction.
The direct internal nucleophilic functionalization of a pi-bound carbon of neutral TpMo(CO)2(5-oxo-eta3-pyranyl) and TpMo(CO)2(5-oxo-eta3-pyridinyl) complexes by enolates represents a new reaction profile for neutral TpMo(CO)2(eta3-allyl) complexes. This Mo-mediated "1,5-Michael reaction" proceeds in good to excellent yields and provides, after demetalation, a new and efficient synthetic approach to oxa- and aza[3.2.1]bicyclics of high enantiomeric purity.
Zhang
Yongqiang
Y
Sanford S. Atwood Chemistry Center, Emory University, 1515 Dickey Drive, Atlanta, Georgia 30322, USA.
Liebeskind
Lanny S
LS