Williams David R, Reeves Jonathan T
Department of Chemistry, Indiana University, Bloomington, Indiana 47405-7102, USA.
J Am Chem Soc. 2004 Mar 24;126(11):3434-5. doi: 10.1021/ja049353e.
A powerful cascade reaction process for the construction of functionalized cis-bicyclo[3.3.0]octenes has been developed. Carbolithiation of 3-methylene-1,4-cyclooctadiene with 1 degrees , 2 degrees , or 3 degrees alkyllithium reagents leads to cyclooctadienyl anions, which undergo disrotatory electrocyclization and subsequent trapping with carbon, oxygen, sulfur, or silicon electrophiles to provide functionalized cis-bicyclo[3.3.0]octenes. Transmetalation of the allyllithium intermediates allowed access to the cuprate manifold of reactivity. The rapid construction of a linear triquinane using this methodology demonstrates the potential for synthetic applications.
已开发出一种用于构建官能化顺式双环[3.3.0]辛烯的强大级联反应过程。3-亚甲基-1,4-环辛二烯与一级、二级或三级烷基锂试剂进行碳锂化反应生成环辛二烯基阴离子，这些阴离子发生对旋电环化反应，随后与碳、氧、硫或硅亲电试剂捕获，以提供官能化顺式双环[3.3.0]辛烯。烯丙基锂中间体的转金属化反应使得能够进入铜酸盐反应活性体系。使用这种方法快速构建线性三醌烷证明了其在合成应用中的潜力。
