Chemo- and regioselective intermolecular cyclotrimerization of terminal alkynes catalyzed by cationic rhodium(I)/modified BINAP complexes: Application to one-step synthesis of paracyclophanes

被引：139

作者：

Tanaka, K ^{[1
]}

Toyoda, K ^{[1
]}

Wada, A ^{[1
]}

Shirasaka, K ^{[1
]}

Hirano, M ^{[1
]}

机构：

[1] Tokyo Univ Agr & Technol, Dept Appl Chem, Grad Sch Engn, Koganei, Tokyo 1848588, Japan

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2005年 / 11卷 / 04期

关键词：

alkynes; cyclotrimerization; N ligands; paracyclophane; rhodium;

D O I：

10.1002/chem.200401017

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

A highly regioselective intermolecular cyclotrimerization of terminal alkynes has been developed based on the use of the cationic rhodium(i)/ DTBM-Segpbos complex. This method can be applied to a variety of terminal alkynes to provide 1,2,4-trisubstituted benzenes in high yield and with high regioselectivity. A chemo- and regioselective intermolecular crossed-cyclotfimerization of dialkyl acetylenedicarboxylates with a variety of terminal alkynes has also been developed based on the use of the cationic rhodium(i)/H8-BINAP complex, furnishing 3,6-disubstituted phthalates in high yields. It constitutes a highly efficient new method for intermolecular crossed-cyclotrimerization of two different monoynes in terms of catalytic activity, chemo- and regioselectivity, scope of substrates, and ease of operation. The versatility of this new crossed-alkyne cyclotrimerization procedure is demonstrated through its application to one-step synthesis of a [6]metacyclophane and [7]-[12]paracyclophanes from the corresponding terminal alpha,omega-diynes. Mechanistic studies have revealed that the chemo- and regioselectivity of this crossed-alkyne cyclotrimerization are determined by the preferential formation of a specific rhodium metallacycle derived from a terminal alkyne and a dialkyl acetylenedicarboxylate.

引用

页码：1145 / 1156

页数：12

共 145 条

[11] Cobalt-mediated macrocyclizations.: Facile synthesis of 2-oxo pyridinophanes via [2+2+2] cycloaddition of α,ω-diynes and isocyanates [J].