Understanding the controlled living behavior of the polyhomologation of alkylboranes with Corey’s ylide through mechanistic density functional theory calculations
Oscar F. González-Belman (Data curation Formal analysis Investigation Methodology Validation Writing – original draft Writing – review & editing) , José Oscar C. Jiménez-Halla (Methodology Resources Supervision) , Kenneth J. Shea (Conceptualization Supervision Visualization) , José E. Báez (Conceptualization Formal analysis Investigation Supervision Visualization Writing – original draft Writing – review & editing)
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引用次数: 0
Abstract
We investigated the polyhomologation of trialkylborane using dimethyl sulfoxonium methylide (Corey’s ylide) as a methylene source. This reaction mechanism produces a linear aliphatic polymer called polymetylene (PM). Our theoretical calculations using density functional theory (DFT) suggest that this polymerization involves two reaction steps: ylide coordination into trialkylborane (BR3) (ate complex) and insertion (1,2-migration) of the methylene unit into a B-R bond, along with the liberation of dimethyl sulfoxide (DMSO) as a by-product. The mechanistic routes of the single-arm, arm-per-arm, and asymmetric propagation of the alkyl chains in the borane were explored, which revealed that the route of symmetric polyhomogation (arm-per-arm) of alkyl borane was favored over the others, leading to polyhomologated boranes with symmetric alkyl chains. With further oxidative treatment, this gave rise to PM with narrow dispersity (ÐM) involving living polymerization as in experimental reports.
期刊介绍:
Phosphorus, Sulfur, and Silicon and the Related Elements is a monthly publication intended to disseminate current trends and novel methods to those working in the broad and interdisciplinary field of heteroatom chemistry.