使用二膦亚基环丁烯配位的钯催化剂实现烯丙基醚的简便且选择性脱烯丙基化反应。

Facile and selective deallylation of allyl ethers using diphosphinidenecyclobutene-coordinated palladium catalysts.

作者信息

Murakami Hiromi, Minami Tatsuya, Ozawa Fumiyuki

机构信息

Research Center for Elements Science, Institute for Chemical Research, Kyoto University, Uji, Kyoto 611-0011, Japan.

出版信息

J Org Chem. 2004 Jun 25;69(13):4482-6. doi: 10.1021/jo049732q.

DOI:10.1021/jo049732q

PMID:15202905

Abstract

(pi-Allyl)palladium triflate bearing a 1,2-bis(4-methoxyphenyl)-3,4-bis(2,4,6-tri-tert-butylphenylphosphinidene)cyclobutene ligand (DPCB-OMe), [Pd(eta(3)-C(3)H(5))(DPCB-OMe)]OTf, efficiently catalyzes deallylation of a variety of allyl ethers in aniline to give corresponding alcohols in high yields under mild conditions. The reactions can be performed in air without loss of a variety of functionalities including vinyl, alkynyl, hydroxy, acetoxy, silyloxy, and acetal groups. Allyl 2-allyloxybenzoate selectively undergoes deallylation of the allyloxy group to give allyl salicylate in quantitative yield.

摘要

带有1,2-双(4-甲氧基苯基)-3,4-双(2,4,6-三叔丁基苯基亚膦基)环丁烯配体（DPCB-OMe）的三氟甲磺酸(π-烯丙基)钯，[Pd(η(3)-C(3)H(5))(DPCB-OMe)]OTf，能在温和条件下高效催化苯胺中多种烯丙基醚的脱烯丙基反应，以高收率得到相应的醇。反应可在空气中进行，包括乙烯基、炔基、羟基、乙酰氧基、硅氧基和缩醛基在内的多种官能团不会损失。烯丙基2-烯丙氧基苯甲酸酯选择性地发生烯丙氧基的脱烯丙基反应，以定量收率得到烯丙基水杨酸酯。