(R)- and (S)-4-TIPS-3-butyn-2-ol. Useful Precursors of Chiral Allenylzinc and Indium Reagents

A convenient route to the enantiomers of 4-TIPS-3-butyn-2-ol of >95% enantiomeric purity by reduction of the ynone precursor 4 with the Noyori N-tosyl-1,2-diphenylethylenediamineruthenium cymene catalyst is described. The mesylate derivative of the (S) enantiomer (1c) is converted in situ to an a...

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Bibliographic Details
Published in:Journal of organic chemistry 2006-06, Vol.71 (13), p.4840-4844
Main Authors: Marshall, James A, Eidam, Patrick, Eidam, Hilary Schenck
Format: Article
Language:English
Subjects:
Alkadienes - chemistry
Butanols - chemical synthesis
Butanols - chemistry
Catalysis
Catalysts: preparations and properties
Chemistry
Exact sciences and technology
General and physical chemistry
Indium - chemistry
Molecular Structure
Organic chemistry
Organometallic Compounds - chemistry
Ruthenium - chemistry
Silanes - chemical synthesis
Silanes - chemistry
Stereoisomerism
Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry
Zinc - chemistry
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Summary:A convenient route to the enantiomers of 4-TIPS-3-butyn-2-ol of >95% enantiomeric purity by reduction of the ynone precursor 4 with the Noyori N-tosyl-1,2-diphenylethylenediamineruthenium cymene catalyst is described. The mesylate derivative of the (S) enantiomer (1c) is converted in situ to an allenylzinc or indium reagent in the presence of a catalyst derived from Pd(OAc)2 and Ph3P and either Et2Zn or InI. A second in situ addition of these reagents to aldehydes leads to anti homopropargylic alcohol adducts. The additions proceed in generally high (60−90%) yield with modest to excellent diastereoselectivity and high enantioselectivity. Only slight mismatching (
ISSN:0022-3263
1520-6904
DOI:10.1021/jo060542k