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

Klaus Banert, Sandra Bochmann, Andreas Ihle, Oliver Plefka, Florian Taubert, Tina Walther, Marcus Korb, Tobias Rueffer, Heinrich Lang

Research output: Contribution to journalArticle

2 Citations (Scopus)

Abstract

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.

Original languageEnglish
Pages (from-to)14022-14035
Number of pages14
JournalMolecules
Volume19
Issue number9
DOIs
Publication statusPublished - Sep 2014
Externally publishedYes

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