Skip to main page content
U.S. flag

An official website of the United States government

Dot gov

The .gov means it’s official.
Federal government websites often end in .gov or .mil. Before sharing sensitive information, make sure you’re on a federal government site.

Https

The site is secure.
The https:// ensures that you are connecting to the official website and that any information you provide is encrypted and transmitted securely.

Access keys NCBI Homepage MyNCBI Homepage Main Content Main Navigation
. 2022 May 26;58(43):6308-6311.
doi: 10.1039/d2cc00666a.

Silyl formates as hydrosilane surrogates for the transfer hydrosilylation of ketones

R Martin Romero  1 , Neethu Thyagarajan  1 , Nora Hellou  1 , Clément Chauvier  1 , Timothé Godou  1 , Lucile Anthore-Dalion  1 , Thibault Cantat  1
Affiliations

Silyl formates as hydrosilane surrogates for the transfer hydrosilylation of ketones

R Martin Romero et al. Chem Commun (Camb). .

Abstract

A transfer hydrosilylation of ketones employing silyl formates as hydrosilane surrogates under mild conditions is presented. A total of 24 examples of ketones have been successfully converted to their corresponding silyl ethers with 61-99% yields in the presence of a PNHP-based ruthenium catalyst and silyl formate reagent. The crucial role of the ligand for the transformation is demonstrated.

PubMed Disclaimer

Conflict of interest statement

There are no conflicts to declare.

Figures

Scheme 1
Scheme 1. (A) Hydrosilane surrogates. (B) Applications of silyl formates as hydrosilane surrogates. (C) Ruthenium-catalyzed transfer hydrosilylation of ketones (this work).
Scheme 2
Scheme 2. Silyl formate scope for the hydrosilylation of acetophenone. 0.1 mmol scale. Yields are determined by 1H NMR with mesitylene as an internal standard. See ESI for more details.
Scheme 3
Scheme 3. Substrate scope for the transfer hydrosilylation of ketones (0.1 mmol scale). Yields were determined by 1H NMR with mesitylene as an internal standard. Scaled-up reactions (0.5 mmol scale) were performed with toluene as the solvent. Yields of isolated products from scaled-up reactions are given within parentheses. [a] 2 equivalents of 5a were used. [b] Reaction performed in anisole as the solvent. [c] Reaction performed at 60 °C.
Scheme 4
Scheme 4. Yields were determined by 1H NMR with mesitylene as an internal standard. (A) Selectivity of the PNHP-based ruthenium catalyst 2 for the transfer hydrosilylation of carbonyl groups (0.1 mmol scale). (B) Deuterosilylation of ketones (0.1 mmol scale).
Scheme 5
Scheme 5. Putative mechanism for the transfer hydrosilylation of ketones with silyl formates.
See this image and copyright information in PMC

References

    1. Marciniec B., in Hydrosilylation: A Comprehensive Review on Recent Advances, ed. B. Marciniec, Springer Netherlands, Dordrecht, 2009, pp. 3–51
    2. Lipke M. C. Liberman-Martin A. L. Tilley T. D. Angew. Chem., Int. Ed. 2017;56:2260–2294. doi: 10.1002/anie.201605198. - DOI - PubMed
    1. Oestreich M. Angew. Chem., Int. Ed. 2016;55:494. doi: 10.1002/anie.201508879. - DOI - PubMed
    1. Amrein S. Studer A. Helv. Chim. Acta. 2002;85:3559. doi: 10.1002/1522-2675(200210)85:10<3559::AID-HLCA3559>3.0.CO;2-6. - DOI
    2. Amrein S. Timmermann A. Studer A. Org. Lett. 2001;3:2357. doi: 10.1021/ol016160c. - DOI - PubMed
    3. Studer A. Amrein S. 39 . Angew. Chem., Int. Ed. 2000:3080. doi: 10.1002/1521-3773(20000901)39:17<3080::AID-ANIE3080>3.0.CO;2-E. - DOI - PubMed
    1. Simonneau A. Oestreich M. Angew. Chem., Int. Ed. 2013;52:11905. doi: 10.1002/anie.201305584. - DOI - PubMed
    2. Keess S. Simonneau A. Oestreich M. Organometallics. 2015;34:790. doi: 10.1021/om501284a. - DOI
    1. Chauvier C. Thuéry P. Cantat T. Angew. Chem., Int. Ed. 2016;55:14096. doi: 10.1002/anie.201607201. - DOI - PubMed