Lilly Michael J, Miller Natalie A, Edwards Alison J, Willis Anthony C, Turner Peter, Paddon-Row Michael N, Sherburn Michael S
Institute of Fundamental Sciences, Massey University Private Bag 11222, Palmerston North, New Zealand.
Chemistry. 2005 Apr 8;11(8):2525-36. doi: 10.1002/chem.200401215.
The stereochemical outcome of the intramolecular Diels-Alder reaction of ester-linked 1,3,8-nonatrienes can be controlled by substituents about a stereogenic center attached to C1. The scope and limitations of this approach have been investigated, with variation in substrate structure about the allylic stereocenter and the dienophile. The stereochemical outcomes of these reactions are explained by reference to B3 LYP/6-31G(d) transition structures. New insights into the conformational preferences of allylic alcohol derivatives are reported, results which allow an explanation of the differing levels of pi-diastereofacial selectivity and cis/trans (i.e. endo/exo) selectivity from the reaction.
酯连接的1,3,8-壬三烯分子内狄尔斯-阿尔德反应的立体化学结果可通过连接在C1上的手性中心周围的取代基来控制。已经研究了这种方法的范围和局限性，研究了烯丙基立体中心和亲双烯体周围底物结构的变化。通过参考B3 LYP/6-31G(d)过渡结构解释了这些反应的立体化学结果。报道了关于烯丙醇衍生物构象偏好的新见解，这些结果能够解释反应中不同水平的π-非对映面选择性和顺式/反式（即内型/外型）选择性。
