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Synfacts 2022; 18(04): 0383
DOI: 10.1055/s-0041-1737972
Metals in Synthesis

Cyclopropanation of Alkenes via a Siloxycarbene–Palladium Complex

Contributor(s):
Mark Lautens
,
Alexa Torelli
Sakurai S, Inagaki T, Kodama T, Yamanaka M, *, Tobisu M. * Rikkyo University, Tokyo and Osaka University, Japan
Palladium-Catalyzed Siloxycyclopropanation of Alkenes Using Acylsilanes.

J. Am. Chem. Soc. 2022;
144: 1099-1105
DOI: 10.1021/jacs.1c11497.
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Key words

palladium catalysis - homoenolates - carbenes

Significance

The authors reveal that, under palladium catalysis, an acylsilane can serve as a source of an electron-rich carbene to undergo cyclopropanation with an alkene. The corresponding siloxy cyclopropanes serve as valuable homonenolates, as demonstrated through various derivatizations.


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Comment

Both electron-neutral and electron-rich alkenes were compatible substrates in the ­cyclopropanation; however, electron-rich alkenes were more reactive, suggesting an electrophilic metal carbene species is involved in the catalytic pathway. DFT studies indicate that the mechanism of the cyclopropanation proceeds through a [2+2] cycloaddition to form a palladocyclobutane intermediate.


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Publication History

Article published online:
18 March 2022

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