Departamento de Química, Instituto de Ciências Exatas, Universidade Federal de Minas Gerais, UFMG, 31270-901, Belo Horizonte, MG, Brazil.
Org Biomol Chem. 2010 Apr 7;8(7):1619-22. doi: 10.1039/b923414d. Epub 2010 Feb 1.
A computational investigation on the origin of the stereoselectivity of 6-exo-trig radical cyclization of alpha,beta-unsaturated ester-tethered sugars has revealed that a boat-like transition state, which keeps the ester in a planar conformation, holds the chiral information. Following this model, the stereocenter to which the ester functionality is connected reports the chirality to the newly formed stereocenter via a 1,4-transfer mechanism.
对 α，β-不饱和酯键合糖的 6-endo-trig 自由基环化立体选择性起源的计算研究表明，保持酯处于平面构象的船型过渡态保留了手性信息。根据该模型，酯官能团所连接的立体中心通过 1,4-转移机制向新形成的立体中心报告手性。
