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Synthesis with perfect atom economy: generation of furan derivatives by 1,3-dipolar cycloaddition of acetylenedicarboxylates at cyclooctynes.

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.

SUBMITTER: Banert K

PROVIDER: S-EPMC6271402 | biostudies-literature | 2014 Sep

REPOSITORIES: biostudies-literature

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Synthesis with perfect atom economy: generation of furan derivatives by 1,3-dipolar cycloaddition of acetylenedicarboxylates at cyclooctynes.

Banert Klaus K Bochmann Sandra S Ihle Andreas A Plefka Oliver O Taubert Florian F Walther Tina T Korb Marcus M Rüffer Tobias T Lang Heinrich H

Molecules (Basel, Switzerland) 20140905 9

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 v ...[more]

PMID: 25197937

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