Issue 5, 2004

On the use of mixtures of organotin species for catalytic enantioselective ketone allylation—a detective story

Abstract

In the presence of enantiopure MTBH2 (monothiobinaphthol, 2-hydroxy-2′mercapto-1,1′-binaphthyl; 0.2 eq.) quantitative allylation of ArC([double bond, length as m-dash]O)Me takes place with impure Sn(CH2CH[double bond, length as m-dash]CH2)4 (prepared from allyl chloride, air-oxidised magnesium and SnCl4) to yield tert-homoallylic alcohols in 85–92% ee. In the same process highly purified, or commercial, Sn(CH2CH[double bond, length as m-dash]CH2)4 yields material of only 35–50% ee. The origin of these effects is the presence of small amounts of the compounds, EtSn(CH2CH[double bond, length as m-dash]CH2)3, ClSn(CH2CH[double bond, length as m-dash]CH2)3 ClSnEt(CH2CH[double bond, length as m-dash]CH2)2 in the tetraallyltin sample and the presence of traces of water (which inhibits achiral background reactions). All the triallyl and diallyl species enhance the stereoselectivity in the catalytic allylation reaction, the chlorides more so than the ethyl compound. Hydrolysis of ClSnEt(CH2CH[double bond, length as m-dash]CH2)2 affords crystallographically characterised Sn43-O)(μ2-Cl)2Cl2Et4(CH2CH[double bond, length as m-dash]CH2)4. Reaction of this latter compound with MTBH2 leads to the most potent catalyst.

Graphical abstract: On the use of mixtures of organotin species for catalytic enantioselective ketone allylation—a detective story

Supplementary files

Article information

Article type
Paper
Submitted
27 Oct 2003
Accepted
05 Jan 2004
First published
05 Feb 2004

Org. Biomol. Chem., 2004,2, 741-748

On the use of mixtures of organotin species for catalytic enantioselective ketone allylation—a detective story

A. Cunningham, V. Mokal-Parekh, C. Wilson and S. Woodward, Org. Biomol. Chem., 2004, 2, 741 DOI: 10.1039/B313384B

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