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An Activated Germanium Metal-Promoted, Highly Diastereoselective Reformatsky Reaction



An Activated Germanium Metal-Promoted, Highly Diastereoselective Reformatsky Reaction



Journal of Organic Chemistry 63(3): 691-697



Activated germanium metal, prepared by the reduction of germanium(II) iodide with potassium metal, was found to promote the Reformatsky reaction effectively under mild conditions. In the presence of activated germanium metal, the reactions of alpha-bromo ketones 2a and 2b and alpha-bromo imides 2e and 2f with benzaldehyde (1a) proceeded smoothly to give the corresponding beta-hydroxy carbonyl compounds 3a, 3b, 3e and 3f, respectively, in good yields and with good syn diastereoselectivity. The activated germanium metal-promoted, asymmetric Reformatsky reaction of enantiomerically pure-oxazolidinone derivatives 2g-j with various aldehydes 1a-d was also examined; the highest diastereoselectivity was achieved when (1S,2R)-2-amino-1,2-diphenylethanol-derived 2j was used as the Reformatsky donor. The excellent diastereoselectivity could be explained in terms of the formation of a chairlike, six-membered transition state between the aldehyde and enolate as in the Zimmerman-Traxler model. A single recrystallization of the Reformatsky adducts, followed by hydrolysis and subsequent esterification, led to enantiomerically pure methyl 3-hydroxy-2-methylalkanoates 10j-m, with almost quantitative recovery of the enantiomerically pure 2-oxazolidinone 14.

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Accession: 045217868

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PMID: 11672062


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