Department of Chemistry and Biochemistry, University of California, Los Angeles, California 90095-1569, USA.
J Org Chem. 2010 Feb 5;75(3):762-6. doi: 10.1021/jo902283a.
The origins of different stereoselectivities observed experimentally in the alkylations of azulenone precursors in the guanacastepene A synthesis have been determined through density functional theory investigations. The optimized transition structures of methylation of two different guanacastepene A precursors show that steric effects, rather than torsional factors that often determine such stereoselectivities, dictate the preferred products observed.
通过密度泛函理论研究,确定了在瓜纳卡特烯 A 合成中薁酮前体的烷基化反应中实验观察到的不同立体选择性的起源。两种不同瓜纳卡特烯 A 前体甲基化的优化过渡态结构表明,决定观察到的优先产物的是空间效应,而不是通常决定这种立体选择性的扭转因素。