通过炔烃卤硼化、锆催化的烯烃不对称碳铝化反应（ZACA反应）以及钯催化的串联根岸偶联反应高效立体选择性合成黄粉虫性信息素。
Efficient and stereoselective synthesis of yellow scale pheromone via alkyne haloboration, Zr-catalyzed asymmetric carboalumination of alkenes (ZACA reaction), and Pd-catalyzed tandem Negishi coupling.
作者信息
Xu Zhaoqing, Negishi Ei-Ichi
机构信息
Herbert C. Brown Laboratories of Chemistry, Purdue University, 560 Oval Drive, West Lafayette, Indiana 47907-2084, USA.
出版信息
Org Lett. 2008 Oct 2;10(19):4311-4. doi: 10.1021/ol8017566. Epub 2008 Sep 3.
Abstract
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.
摘要
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）。
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3
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4
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