Efficient Rhodium-Catalyzed installation of unsaturated ester functions onto porphyirins: Site-specific heck-type addition versus conjugate addition

被引：24

作者：

Baba, Hiromi ^{[1
]}

Chen, Jinping ^{[1
]}

Shinokubo, Hiroshi ^{[1
]}

Osuka, Atsuhiro ^{[1
]}

机构：

[1] Kyoto Univ, Dept Chem, Grad Sch Sci, Sakyo Ku, Kyoto 6068502, Japan

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2008年 / 14卷 / 14期

关键词：

boron; C-C coupling; Heck reaction; porphyrinoids; rhodium;

D O I：

10.1002/chem.200701943

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

A facile introduction of alpha,beta-or alpha,beta,gamma,delta-unsaturated ester functions onto porphyrins was achieved through rhodium-catalyzed addition of beta-borylporphyrins to acrylate or 2,4-pentadienoate esters. The reaction of meso-borylporphyrins with acrylates exclusively afforded saturated esters by 1,4-conjugate addition under the same re-mode (Heck-type versus conjugate addition) is highly dependent on the reaction site (beta versus meso). This functionalization has a significant impact on the electronic properties of the pi system of porphyrins, which induces a substantial redshift and broadening in the absorption spectra by effective conjugation through the beta positions. The coplanar structure of the unsaturated ester moieties with respect to the porphyrin core has been unambiguously elucidated by X-ray crystallographic analysis.

引用

页码：4256 / 4262

页数：7

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