DBU-Promoted Nucleophilic Activation of Carbonic Acid Diesters

被引：50

作者：

Carafa, Marianna ^{[1
]}

Mesto, Ernesto ^{[2
]}

Quaranta, Eugenio ^{[1
]}

机构：

[1] Univ Bari Aldo Moro, Dipartimento Chim, I-70126 Bari, Italy

[2] Univ Bari Aldo Moro, Dipartimento Geomineral, I-70126 Bari, Italy

来源：

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY | 2011年 / 2011卷 / 13期

关键词：

Organocatalysis; Reaction mechanisms; Amidine base; Carbonic acid ester; ACCELERATED GREEN CHEMISTRY; DIMETHYL CARBONATE; ALIPHATIC-AMINES; CRYSTAL-STRUCTURES; AROMATIC DIAMINES; BEHAVIOR; METHOXYCARBONYLATION; CARBOMETHOXYLATION; CARBONYLATION; METHYLATION;

D O I：

10.1002/ejoc.201001725

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The reactivity of carbonic acid diesters in the presence of the amidine base DBU (1,8-diazabicyclo[5.4.0] undec-7-ene) has been investigated for the first time. Organic carbonates can be activated by DBU through the formation of N-alkoxy-carbonyl ketene aminal 2 as the ultimate product. The latter species may form through deprotonation of the corresponding N-alkoxycarbonyl-amidinium cation 1(+) by the amidine base. We have for the first time isolated and characterized, both in the solid state (X-ray crystal structure determination, IR) and in solution (NMR), a few 1(+) chloride salts and studied their reactivity towards the organic base. The reactivity of both 1(+) and 2 with methanol has also been explored. Ketene aminal 2 behaves as a "CO2R" carrier, as it can selectively transfer the alkoxycarbonyl group to the alcohol and regenerate the amidine base.

引用

页码：2458 / 2465

页数：8

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