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Chemical Consequences of the Mechanical Bond: A Tandem Active Template-Rearrangement Reaction.

ABSTRACT: We report the unexpected discovery of a tandem active template CuAAC-rearrangement process, in which N₂ is extruded on the way to the 1,2,3-triazole product to give instead acrylamide rotaxanes. Mechanistic investigations suggest this process is dictated by the mechanical bond, which stabilizes the Cu^I -triazolide intermediate of the CuAAC reaction and diverts it down the rearrangement pathway; when no mechanical bond is formed, the CuAAC product is isolated.

SUBMITTER: Modicom F

PROVIDER: S-EPMC6589916 | biostudies-literature | 2019 Mar

REPOSITORIES: biostudies-literature

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Chemical Consequences of the Mechanical Bond: A Tandem Active Template-Rearrangement Reaction.

Modicom Florian F Jamieson Ellen M G EMG Rochette Elise E Goldup Stephen M SM

Angewandte Chemie (International ed. in English) 20190214 12

We report the unexpected discovery of a tandem active template CuAAC-rearrangement process, in which N<sub>2</sub> is extruded on the way to the 1,2,3-triazole product to give instead acrylamide rotaxanes. Mechanistic investigations suggest this process is dictated by the mechanical bond, which stabilizes the Cu<sup>I</sup> -triazolide intermediate of the CuAAC reaction and diverts it down the rearrangement pathway; when no mechanical bond is formed, the CuAAC product is isolated. ...[more]

PMID: 30600892

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