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. 2019 Jun 21;84(12):7564-7574.
doi: 10.1021/acs.joc.9b00642. Epub 2019 May 30.

Cobalt-Catalyzed Intramolecular Silylperoxidation of Unsaturated Diisopropylsilyl Ethers

Jonathan P Oswald  1 , K A Woerpel  1
Affiliations

Cobalt-Catalyzed Intramolecular Silylperoxidation of Unsaturated Diisopropylsilyl Ethers

Jonathan P Oswald et al. J Org Chem. .

Abstract

A cobalt-catalyzed intramolecular silylperoxidation reaction was developed that allows for the conversion of unsaturated diisopropylsilyl ethers to 3-sila-1,2,4-trioxepanes. Reduction of the peroxide unit of the 3-sila-1,2,4-trioxepane yields six-membered ring diisopropylsilylene acetals.

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Conflict of interest statement

The authors declare no competing financial interests.

Figures

Scheme 1.
Scheme 1.. Co-Catalyzed Endoperoxide Formation
Scheme 2.
Scheme 2.. Products of Co-Catalyzed Intramolecular Silylperoxidation of Unsaturated Diisopropylsilyl Ethers
Scheme 3.
Scheme 3.. Formation of Diisopropylsilylene Acetal 3 from 3-Sila-1,2,4-Trioxepane 2
Scheme 4.
Scheme 4.. Exchange of Silanes Not Observed
Scheme 5.
Scheme 5.. Co-Catalyzed Silylperoxidation Using Diisopropylsilane 8
Scheme 6.
Scheme 6.. Proposed Mechanism for the Co-Catalyzed Intramolecular Silylperoxidation of Unsaturated Diisopropylsilyl Ethers
Scheme 7.
Scheme 7.. Synthesis of Unsaturated Diisopropylsilyl Ethers
Scheme 8.
Scheme 8.. Deprotection of Diisopropylsilylene Acetals
Scheme 9.
Scheme 9.. Ring Size Screen for the Co-Catalyzed Intramolecular Silylperoxidation of Unsaturated Diisopropylsilyl Ethers
See this image and copyright information in PMC

References

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