Organostannanes derived from (−)-Menthol: Controlling stereochemistry during the preparation of (1R,2S,5R)-Menthyldiphenyltin Hydride and Bis((1R,2S,5R)-menthyl)phenyltin Hydride

D. Dakternieks; K. Dunn; D.J. Henry; C.H. Schiesser; E.R.T. Tiekink

doi:10.1021/om990088t

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Organostannanes derived from (−)-Menthol: Controlling stereochemistry during the preparation of (1R,2S,5R)-Menthyldiphenyltin Hydride and Bis((1R,2S,5R)-menthyl)phenyltin Hydride

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Organostannanes derived from (−)-Menthol: Controlling stereochemistry during the preparation of (1R,2S,5R)-Menthyldiphenyltin Hydride and Bis((1R,2S,5R)-menthyl)phenyltin Hydride

D. Dakternieks, K. Dunn, D.J. Henry, C.H. Schiesser and E.R.T. Tiekink

Organometallics, Vol.18(17), pp.3342-3347

1999

DOI: https://doi.org/10.1021/om990088t

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Abstract

Reaction of (1R,2S,5R)-menthylmagnesium chloride (MenMgCl) with triphenyltin chloride in THF proceeds with epimerization of the C-1 carbon of the menthyl group and results in a mixture of (1R,2S,5R)-menthyltriphenyltin (1) and (1S,2S,5R)-menthyltriphenyltin (2). Addition of Lewis bases such as triphenylphosphine to the THF solution of triphenyltin chloride prior to addition of the Grignard reagent suppresses epimerization and enables isolation of pure 1. An epimerization mechanism involving one-electron-transfer reactions is postulated. Compound 1 is the precursor for reactions that lead to the formation of a series of compounds, namely, (1S,2S,5R)-menthyldiphenyltin iodide (4), (1S,2S,5R)-menthyldiphenyltin fluoride (5), (1S,2S,5R)-menthyldiphenyltin hydride (6), (1S,2S,5R)-menthylphenyltin dibromide (7), and (1S,2S,5R)-menthylphenyltin dichloride (8). The synthesis of the dimenthyl derivatives bis((1S,2S,5R)-menthyl)diphenyltin (9), bis((1S,2S,5R)-menthyl)phenyltin iodide (10), bis((1S,2S,5R)-menthyl)phenyltin hydride (11), and bis((1S,2S,5R)-menthyl)tin di(chloroacetate) (12) is described. Crystal structure determinations of 7, 8, and 12 confirm the absolute configuration of the menthyl groups.

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Title: Organostannanes derived from (−)-Menthol: Controlling stereochemistry during the preparation of (1R,2S,5R)-Menthyldiphenyltin Hydride and Bis((1R,2S,5R)-menthyl)phenyltin Hydride
Authors/Creators: D. Dakternieks (Author/Creator)
K. Dunn (Author/Creator)
D.J. Henry (Author/Creator)
C.H. Schiesser (Author/Creator)
E.R.T. Tiekink (Author/Creator)
Publication Details: Organometallics, Vol.18(17), pp.3342-3347
Publisher: American Chemical Society
Identifiers: 991005543954007891
Murdoch Affiliation: Murdoch University
Language: English
Resource Type: Journal article

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Collaboration types: Domestic collaboration
Citation topics: 2 Chemistry; 2.1 Synthesis; 2.1.1299 Radical Cyclization
Web Of Science research areas: Chemistry, Inorganic & Nuclear; Chemistry, Organic
ESI research areas: Chemistry