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Antimony(v) cations for the selective catalytic transformation of aldehydes into symmetric ethers, α,β-unsaturated aldehydes, and 1,3,5-trioxanes
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Arias Ugarte, Renzo, Devarajan, Deepa, Mushinski, Ryan and Hudnall, Todd W. (2016) Antimony(v) cations for the selective catalytic transformation of aldehydes into symmetric ethers, α,β-unsaturated aldehydes, and 1,3,5-trioxanes. Dalton Transactions, 45 (27). pp. 11150-11161. doi:10.1039/c6dt02121b ISSN 1477-9226.
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Official URL: http://dx.doi.org/10.1039/c6dt02121b
Abstract
1-Diphenylphosphinonaphthyl-8-triphenylstibonium triflate ([2][OTf]) was prepared in excellent yield by treating 1-lithio-8-diphenylphosphinonaphthalene with dibromotriphenylstiborane followed by halide abstraction with AgOTf. This antimony(V) cation was found to be stable toward oxygen and water, and exhibited exceptional Lewis acidity. The Lewis acidity of [2][OTf] was exploited in the catalytic reductive coupling of a variety of aldehydes into symmetric ethers of type L in good to excellent yields under mild conditions using Et3SiH as the reductant. Additionally, [2][OTf] was found to selectively catalyze the Aldol condensation reaction to afford α-β unsaturated aldehydes (M) when aldehydes with 2 α-hydrogen atoms were used. Finally, [2][OTf] catalyzed the cyclotrimerization of aliphatic and aromatic aldehydes to afford the industrially-useful 1,3,5 trioxanes (N) in good yields, and with great selectivity. This phosphine–stibonium motif represents one of the first catalytic systems of its kind that is able to catalyze these reactions with aldehydes in a controlled, efficient manner. The mechanism of these processes has been explored both experimentally and theoretically. In all cases the Lewis acidic nature of the antimony(V) cation was found to promote these reactions.
Item Type: | Journal Article | ||||||||
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Divisions: | Faculty of Science, Engineering and Medicine > Science > Life Sciences (2010- ) | ||||||||
Journal or Publication Title: | Dalton Transactions | ||||||||
Publisher: | Royal Society of Chemistry | ||||||||
ISSN: | 1477-9226 | ||||||||
Official Date: | 21 July 2016 | ||||||||
Dates: |
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Volume: | 45 | ||||||||
Number: | 27 | ||||||||
Page Range: | pp. 11150-11161 | ||||||||
DOI: | 10.1039/c6dt02121b | ||||||||
Status: | Peer Reviewed | ||||||||
Publication Status: | Published | ||||||||
Access rights to Published version: | Restricted or Subscription Access |
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