Department of Chemistry, Dartmouth College, Hanover, New Hampshire 03755, USA.
J Am Chem Soc. 2010 Mar 31;132(12):4104-6. doi: 10.1021/ja100747n.
A mild two-step process for the regioselective, transition-metal-free preparation of carbon-carbon bonds from allylic alcohols/ethers and Grignard reagents is described. This process obviates the need for the harsh deprotection conditions usually required for removal of methyl ethers. The synthesis is accomplished by photochemically promoted allylic substitution reactions of allylic alcohols and ethers with diethylphosphorothioic acid followed by sp(3)-sp(3) or sp(2)-sp(3) bond formation with various Grignard reagents under transition-metal-free conditions. Depending on the nature of the nucleophile, the regioselectivity of the carbon-carbon bond-forming event can be controlled to furnish either quaternary or tertiary carbon centers.
描述了一种温和的两步法，用于从烯丙基醇/醚和格氏试剂进行区域选择性、无过渡金属的碳-碳键制备。该过程避免了通常需要苛刻的脱保护条件来去除甲基醚。合成通过烯丙基醇和醚与二乙基硫代膦酸的光促进烯丙基取代反应来完成，然后在无过渡金属条件下与各种格氏试剂进行 sp(3)-sp(3)或 sp(2)-sp(3)键形成。根据亲核试剂的性质，可以控制碳-碳键形成事件的区域选择性，以提供季碳或叔碳中心。
