Department Chemie, Ludwig-Maximilians-Universität München, Butenandtstr. 5-13, 81377 München (Germany).
Angew Chem Int Ed Engl. 2015 Feb 23;54(9):2754-7. doi: 10.1002/anie.201409165. Epub 2015 Jan 12.
Secondary alkyllithium reagents bearing an OTBS group (TBS=tert-butyldimethylsilyl) at the 3-position can be prepared stereoconvergently through an I/Li exchange from a diastereomeric mixture of the corresponding secondary alkyl iodides. These lithium reagents react with a range of electrophiles, including carbon electrophiles, with retention of configuration to yield various 1,3-difunctionalized derivatives with good diastereoselectivities. Kinetic studies show that the 3-siloxy group strongly accelerates the epimerization at the lithium-substituted carbon atom. This method offers a new way to construct chiral open-chain molecules with excellent stereoselectivity.
带有 OTBS 基团（TBS=叔丁基二甲基硅基）的 3-位仲烷基锂试剂可以通过相应的仲烷基碘化物的非对映异构体混合物的 I/Li 交换立体收率制备。这些锂试剂与各种亲电试剂反应，包括碳亲电试剂，构型保持，以高产率和良好的非对映选择性得到各种 1,3-二官能化衍生物。动力学研究表明，3-硅氧基基团强烈加速了取代碳原子的差向异构化。该方法为构建具有优异立体选择性的手性开链分子提供了一种新途径。
