Zhang Yongqiang, Liebeskind Lanny S
Sanford S. Atwood Chemistry Center, Emory University, 1515 Dickey Drive, Atlanta, Georgia 30322, USA.
J Am Chem Soc. 2005 Aug 17;127(32):11258-9. doi: 10.1021/ja0538132.
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.
烯醇盐对中性TpMo(CO)2(5-氧代-η3-吡喃基)和TpMo(CO)2(5-氧代-η3-吡啶基)配合物中π键合碳的直接内部亲核官能化反应,代表了中性TpMo(CO)2(η3-烯丙基)配合物的一种新反应模式。这种钼介导的“1,5-迈克尔反应”产率良好至优异,脱金属后,为高对映体纯度的氧杂和氮杂[3.2.1]双环化合物提供了一种新的有效合成方法。