Palladium‐Mediated Dynamic Kinetic Resolution: Stereoselective Synthesis of Vicinal Diamines
Palladium‐Mediated Dynamic Kinetic Resolution: Stereoselective Synthesis of Vicinal Diamines
复制标题
DOI：
10.1002/(sici)1521-3773(19990115)38:1/2
复制
发表时间：
1999-01
影响因子：
--
通讯作者：
Gregory R. Cook;P. Shanker;Ketheeswaran Pararajasingham
中科院分区：
文献类型：
--
作者：
Gregory R. Cook;P. Shanker;Ketheeswaran Pararajasingham
在钯催化的烯丙基取代反应中，相邻的立体中心能控制选择性吗？如果中间体π-烯丙基钯络合物能够快速转化，答案是肯定的(见反应方案)。从手性5-乙烯基恶唑烷酮开始，用含氮亲核试剂捕获处于动态平衡的中间体1和2，导致二胺以单一非对映异构体的形式定量形成。
Can an adjacent stereocenter control selectivity in the palladium-catalyzed allylic substitution reaction? If the intermediate π-allyl palladium complex can undergo rapid inversion, the answer is yes (see reaction scheme). Starting from chiral 5-vinyloxazolidinones, trapping of intermediates 1 and 2, which are in a dynamic equilibrium, with nitrogen-containing nucleophiles leads to the quantitative formation of diamines as single diastereomers.