Xu Zhaoqing, Negishi Ei-Ichi
Herbert C. Brown Laboratories of Chemistry, Purdue University, 560 Oval Drive, West Lafayette, Indiana 47907-2084, USA.
Org Lett. 2008 Oct 2;10(19):4311-4. doi: 10.1021/ol8017566. Epub 2008 Sep 3.
A Pd-catalyzed reaction of allylzincs with the 1-octyne bromoboration product gives the desired allyl-alkenyl coupling products in good yields except with H 2CCHCH 2ZnBr. This reaction is suitable for converting an alkyne bromoboration product 3 into 4 with no isomerization or beta-elimination. The Pd-catalyzed isoalkyl-alkenyl coupling of 4 with the isoalkylzinc reagent derived from 2 provides yellow scale pheromone ( 1) of >/=98% isomeric purity in 34% in six steps from TBDPS-protected homoallyl alcohol.
钯催化烯丙基锌与1-辛炔硼溴化产物的反应,除了与H₂CCHCH₂ZnBr反应外,能以良好的产率得到所需的烯丙基-烯基偶联产物。该反应适用于将炔烃硼溴化产物3转化为4,且无异构化或β-消除反应。钯催化4与由2衍生的异烷基锌试剂进行异烷基-烯基偶联反应,从叔丁基二苯基硅烷基保护的高烯丙醇出发,经过六步反应,以34%的产率得到异构体纯度≥98%的黄色鳞翅目昆虫信息素(1)。