What does this research mean for the field?

A transition-metal-free method for forming C(sp 3 )-Si bonds from malononitriles and silyl chlorides is established. Novelty: ClaimNovelty.NOVEL_FINDING. Consensus alignment: ConsensusAlignment.NEUTRAL.

What question did this study set out to answer?

This research aims to explore a new method for forming C(sp3)-Si bonds through silyl umpolung.

February 19, 2026

Tertiary C(sp 3 )–Si Bond Formation via Reactivity Umpolung of Silyl Reagents

Key Points

This research aims to explore a new method for forming C(sp3)-Si bonds through silyl umpolung.
Employs a transition-metal-free decyanative silylation approach.
Utilizes NaOtBu to promote the addition of silylboranes to malononitriles.
Generates intermediates including electrophilic silyl cyanide and nucleophilic ketenimine.
Successful formation of sterically congested C(sp3)-Si bonds.
Demonstrated expansion of silylborane reactivity.
Provided a general synthetic route to alkylsilanes.

Abstract

A transition-metal-free decyanative silylation of malononitriles with silyl chlorides enabled by a silyl umpolung strategy is described. This reaction involves NaOtBu-promoted silylboranes addition to malononitriles to generate electrophilic silyl cyanide and nucleophilic ketenimine intermediates in situ, which recombine to form sterically congested C(sp3)-Si bonds. This method expands silylborane reactivity and provides a general route to alkylsilanes.

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Cite This Study

Zheng et al. (Tue,) studied this question.

synapsesocial.com/papers/6996a8efecb39a600b3f0261 https://doi.org/https://doi.org/10.1021/acs.orglett.6c00035

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