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A mechanochemical [2+2+2] cycloaddition facilitated by a cobalt(ii) catalyst and piezoelectric materials
Kalipada Jana1, Koji Kubota1,2, Hajime Ito1,2
1Institute for Chemical Reaction Design and Discovery (WPI-ICReDD), Hokkaido University Sapporo Hokkaido Japan kbt@eng.hokudai.ac.jp hajito@eng.hokudai.ac.jp.
None:
In this study, we present the first general mechanochemical protocol for the catalytic [2+2+2] cycloaddition of alkynes via a simple and inexpensive cobalt(ii)-based catalytic system. The key to achieving the high efficiency of this mechanochemical transformation is the use of piezoelectric BaTiO3 as a reductant in combination with an amine additive to facilitate the generation of a catalytically active low-valent cobalt species. This method is characterized by a broad substrate scope, short reaction times, solvent-less conditions, and the feasibility of reacting poorly soluble substrates. Thus, we provide a more efficient, broadly applicable, and sustainable alternative to existing solution-based protocols.
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Conjugated systems containing an even number of π-electron pairs undergo a conrotatory ring closure. For example, thermal electrocyclization of (2E,4E)-2,4-hexadiene, a conjugated diene containing two π-electron pairs, gives trans-3,4-dimethylcyclobutene.