Reductive coupling of ketones and nitriles at a geometrically constrained silanide
- 1Organic Chemistry and Catalysis, Institute for Sustainable and Circular Chemistry, Faculty of Science, Utrecht University 3584 CG Utrecht The Netherlands
- 2Department of Chemistry and Applied Biosciences, ETH Zürich CH-8093 Zürich Switzerland
- 3Structural Biochemistry, Bijvoet Centre for Biomolecular Research, Faculty of Science, Utrecht University 3584 CG Utrecht The Netherlands
Abstract
While silanides ([R3Si−]) are best known for their nucleophilic reactivity, examples have recently been shown to display biphilic reactivity akin to neutral Si(ii) compounds. In this context, we report on the reactivity of silanide [K(18-crown-6)][tmimSi] (tmimH3 = tris(3-methylindol-2-yl)methane) with carbonyl compounds and nitriles. The unusual reductive cross-coupling of a ketone and a nitrile result in the formation of 5-membered silacycles. The ketone and the nitrile coupling partners are each able to form homocoupling products, but at a slower rate. DFT calculations support an Umpolung mechanism involving initial condensation of the ketone and silanide to form an anionic oxasilirane – an analogue of which can be isolated for benzaldehyde – that readily opens at the Si–C bond to insert a nitrile molecule.
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BibTeX
@article{lantigua2026reductive,
title = {{Reductive coupling of ketones and nitriles at a geometrically constrained silanide}},
author = {Pamela Adienes Benzan Lantigua and María L. G. Sansores-Paredes and Martin Lutz and Marc-Etienne Moret},
journal = {Inorganic Chemistry Frontiers},
year = {2026},
month = oct,
doi = {10.1039/d6qi01961g},
url = {https://doi.org/10.1039/d6qi01961g},
note = {CC BY 3.0},
}
RIS
TY - JOUR
TI - Reductive coupling of ketones and nitriles at a geometrically constrained silanide
AU - Pamela Adienes Benzan Lantigua
AU - María L. G. Sansores-Paredes
AU - Martin Lutz
AU - Marc-Etienne Moret
PY - 2026
DA - 2026/10/29
JO - Inorganic Chemistry Frontiers
DO - 10.1039/d6qi01961g
UR - https://doi.org/10.1039/d6qi01961g
AB - While silanides ([R3Si−]) are best known for their nucleophilic reactivity, examples have recently been shown to display biphilic reactivity akin to neutral Si(ii) compounds. In this context, we report on the reactivity of silanide [K(18-crown-6)][tmimSi] (tmimH3 = tris(3-methylindol-2-yl)methane) with carbonyl compounds and nitriles. The unusual reductive cross-coupling of a ketone and a nitrile result in the formation of 5-membered silacycles. The ketone and the nitrile coupling partners are each able to form homocoupling products, but at a slower rate. DFT calculations support an Umpolung mechanism involving initial condensation of the ketone and silanide to form an anionic oxasilirane – an analogue of which can be isolated for benzaldehyde – that readily opens at the Si–C bond to insert a nitrile molecule.
SN - 2052-1553
ER -