Cp(*)RuCl催化的三种不对称炔烃通过硼临时连接基进行的形式分子间环三聚反应：邻苯二甲酸酯的区域选择性四组分偶联合成。

Cp(*)RuCl-catalyzed formal intermolecular cyclotrimerization of three unsymmetrical alkynes through a boron temporary tether: regioselective four-component coupling synthesis of phthalides.

作者信息

Yamamoto Yoshihiko, Ishii Jun-Ichi, Nishiyama Hisao, Itoh Kenji

机构信息

Department of Applied Chemistry, Graduate School of Engineering, Nagoya University, Chikusa, Nagoya 464-8603, Japan.

出版信息

J Am Chem Soc. 2005 Jul 6;127(26):9625-31. doi: 10.1021/ja051377d.

DOI:10.1021/ja051377d

PMID:15984890

Abstract

Highly substituted phthalides were efficiently synthesized by sequential Cp(*)RuCl-catalyzed cyclotrimerization of alkynylboronates, propargyl alcohols, and terminal alkynes and palladium(II)-catalyzed carbonylation of the resultant arylboronates. The intermediate arylboronate was isolated and unambiguously characterized by X-ray crystallography. The perfect regioselectivity of the ruthenium-catalyzed formal intermolecular cyclotrimerization was discussed on the basis of the density functional calculations of a boraruthenacycle intermediate.

摘要

通过依次进行Cp(*)RuCl催化的硼酸炔酯、炔丙醇和末端炔烃的环三聚反应以及钯(II)催化的所得芳基硼酸酯的羰基化反应，高效合成了高度取代的邻苯二甲酸酯。分离出中间产物芳基硼酸酯，并通过X射线晶体学对其进行了明确表征。基于硼钌环中间体的密度泛函计算，讨论了钌催化的形式分子间环三聚反应的完美区域选择性。