Synthesis with Perfect Atom Economy: Generation of Furan Derivatives by 1,3-Dipolar Cycloaddition of Acetylenedicarboxylates at Cyclooctynes

被引：8

作者：

Banert, Klaus ^{[1
]}

Bochmann, Sandra ^{[1
]}

Ihle, Andreas ^{[1
]}

Plefka, Oliver ^{[1
]}

Taubert, Florian ^{[1
]}

Walther, Tina ^{[1
]}

Korb, Marcus ^{[2
]}

Rueffer, Tobias ^{[2
]}

Lang, Heinrich ^{[2
]}

机构：

[1] Tech Univ Chemnitz, D-09111 Chemnitz, Germany

[2] Tech Univ Chemnitz, D-09107 Chemnitz, Germany

来源：

MOLECULES | 2014年 / 19卷 / 09期

关键词：

cascade reactions; cyclopropenes; Diels-Alder reactions; dipolar intermediates; epoxides; orthoesters; oxygen heterocycles; reaction mechanisms; retro-Brook reactions; strained compounds; DOUBLY BRIDGED PRISMANES; DIMETHYL ACETYLENEDICARBOXYLATE; ORGANIC-SYNTHESIS; DEWAR BENZENES; TETRAMER; ALKYNES; REARRANGEMENTS; ALKENES; ESTERS;

D O I：

10.3390/molecules190914022

中图分类号：

Q5 [生物化学]; Q7 [分子生物学];

学科分类号：

071010 ; 081704 ;

摘要：

Cyclooctyne and cycloocten-5-yne undergo, at room temperature, a 1,3-dipolar cycloaddition with dialkyl acetylenedicarboxylates 1a,b to generate furan-derived short-lived intermediates 2, which can be trapped by two additional equivalents of 1a, b or alternatively by methanol, phenol, water or aldehydes to yield polycyclic products 3b-d, orthoesters 4a-c, ketones 5 or epoxides 6a,b, respectively. Treatment of bis(trimethylsilyl) acetylenedicarboxylate (1c) with cyclooctyne leads to the ketone 7 via retro-Brook rearrangement of the dipolar intermediate 2c. In all cases, the products are formed with perfect atom economy.

引用

页码：14022 / 14035

页数：14

共 32 条

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