Department of Chemistry, Stanford University, Stanford, California 94305, United States.
Department of Chemical and Systems Biology, Stanford University, Stanford, California 94305, United States.
J Org Chem. 2022 Dec 2;87(23):15925-15937. doi: 10.1021/acs.joc.2c02047. Epub 2022 Nov 15.
We report a one-step (one-flask) generation and reaction of a bifunctional allylating reagent, a trimethylene methane dianion equivalent, that provides a route for the asymmetric 2-(trimethylsilylmethyl) allylation of aldehydes. The product of the first aldehyde allylation process is then set to engage in a second separate aldehyde allylation, providing an improved Prins macrocyclization strategy both for the scalable synthesis of bryostatin 1 and for the total synthesis of a new potent bryostatin analogue.
我们报告了一种一步（一瓶）生成和反应的双功能烯丙基化试剂，即三亚甲基甲烷二阴离子等价物，为醛的不对称 2-（三甲基甲硅烷基甲基）烯丙基化提供了一种途径。第一个醛烯丙基化反应的产物随后被设定为进行第二次单独的醛烯丙基化，为 bryostatin 1 的规模化合成以及一种新型强效 bryostatin 类似物的全合成提供了一种改进的 Prins 环化策略。
