Anions as catalysts: from organosilanes as pro-nucleophiles to base-embedding electrophiles.
- 1Institute of Organic Chemistry and Biochemistry of the Czech Academy of Sciences, Prague 160 00, Czech Republic. [email protected].
- 2Department of Organic Chemistry, Faculty of Science, Charles University, Prague 128 40, Czech Republic.
Abstract
The catalytic activity of neutral and anionic Lewis base catalysts depends on several factors. One is catalyst turnover, which may explain why neutral Lewis bases, such as tertiary amines and phosphines, are widely employed as catalysts in organic synthesis. In this review, we discuss less common strategies by which fluorides, alkoxides, amide anions and related anionic species can be rendered efficient catalysts, including for stereoselective synthesis. We give historical context and highlight recent examples that exploit organosilanes as pro-nucleophiles for challenging bond formation and enantioselective synthesis. The primary emphasis, however, is placed on the use of organosilanes as pro-bases, specifically referred to herein as base-embedding electrophiles (BEE), as part of an idea we wish to conceptualize, as we believe the concept holds substantial yet underappreciated potential in organic synthesis. We focus on how the BEE reagents disentangle traditional Brønsted acid-base considerations from catalyst turnover in substitutions and additions. Existing examples are discussed with particular attention to their conceptual significance. Drawing on these principles, we and others have leveraged base-embedding electrophiles to develop catalytic and stereoselective reactions toward difficult-to-access organic molecules. By sharing this perspective, we hope that readers will also be able to recognize the opportunities and challenges associated with anionic catalysis enabled by organosilanes.
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BibTeX
@article{kejani2026anions,
title = {{Anions as catalysts: from organosilanes as pro-nucleophiles to base-embedding electrophiles.}},
author = {Alireza Abbasi Kejani and Allya Larroza and Arnaldo X Torres-Hernandez and Paulo H S Paioti},
journal = {Chemical Society reviews},
year = {2026},
month = nov,
doi = {10.1039/d6cs00804f},
url = {https://europepmc.org/article/MED/42969410},
note = {CC BY},
}
RIS
TY - JOUR
TI - Anions as catalysts: from organosilanes as pro-nucleophiles to base-embedding electrophiles.
AU - Alireza Abbasi Kejani
AU - Allya Larroza
AU - Arnaldo X Torres-Hernandez
AU - Paulo H S Paioti
PY - 2026
DA - 2026/11/02
JO - Chemical Society reviews
DO - 10.1039/d6cs00804f
UR - https://europepmc.org/article/MED/42969410
AB - The catalytic activity of neutral and anionic Lewis base catalysts depends on several factors. One is catalyst turnover, which may explain why neutral Lewis bases, such as tertiary amines and phosphines, are widely employed as catalysts in organic synthesis. In this review, we discuss less common strategies by which fluorides, alkoxides, amide anions and related anionic species can be rendered efficient catalysts, including for stereoselective synthesis. We give historical context and highlight recent examples that exploit organosilanes as pro-nucleophiles for challenging bond formation and enantioselective synthesis. The primary emphasis, however, is placed on the use of organosilanes as pro-bases, specifically referred to herein as base-embedding electrophiles (BEE), as part of an idea we wish to conceptualize, as we believe the concept holds substantial yet underappreciated potential in organic synthesis. We focus on how the BEE reagents disentangle traditional Brønsted acid-base considerations from catalyst turnover in substitutions and additions. Existing examples are discussed with particular attention to their conceptual significance. Drawing on these principles, we and others have leveraged base-embedding electrophiles to develop catalytic and stereoselective reactions toward difficult-to-access organic molecules. By sharing this perspective, we hope that readers will also be able to recognize the opportunities and challenges associated with anionic catalysis enabled by organosilanes.
SN - 0306-0012
SN - 1460-4744
ER -