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Synthesis of chiral organotins suitable for the preparation of asymmetric heterogeneous catalysts

Published on Apr 1, 2005in Applied Organometallic Chemistry3.259
· DOI :10.1002/aoc.794
M. Belén Faraoni4
Estimated H-index: 4
(UNS: Universidad Nacional del Sur),
A. D. Ayala7
Estimated H-index: 7
(UNS: Universidad Nacional del Sur)
+ 3 AuthorsJulio C. Podestá13
Estimated H-index: 13
(UNS: Universidad Nacional del Sur)
Abstract
A key step in the preparation of asymmetric heterogeneous catalysts based on silica-supported rhodium and platinum chemically modified with chiral organotins, is the synthesis of optically pure tin derivatives. We report on the synthetic pathways leading to the synthesis of (−)-menthyltin derivatives without the formation of epimerization by-products. The physical properties (including full 1H, 13C and 119Sn NMR spectra) of the new compounds, containing between one and three (−)-menthyl ligands attached to the tin atom, are reported. The preparation of two catalysts based on silica-supported rhodium and platinum chemically modified with (−)-menthyldiphenylmethyltin, as well as some studies on the catalytic hydrogenation of ethyl pyruvate, are also described. These studies show that the reductions lead to (R)- and (S)-ethyl lactates as the only products, that the (S) enantiomer was the isomer formed preferentially, and that the degree of conversion observed using both catalytic systems was almost quantitative (97–100%). The enantiomeric excesses observed were in the range 7–8%. One important advantage of these catalytic systems is their stability. Recycling of the used catalysts is possible, without any loss in the degree of conversion or enantiomeric excess. Copyright © 2005 John Wiley & Sons, Ltd.
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References27
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#1Marcel Gielen (ULB: Université libre de Bruxelles)H-Index: 4
#2Hassan Mokhtar-Jamaï (ULB: Université libre de Bruxelles)H-Index: 4
The synthesis of optically active p‐anisyl‐(3‐hydroxy‐3‐methylbutyl)methyl‐α‐naphthyl tin (IV) is described. The spectroscopic properties of this compound and of the products used as synthesis intermediates are given. The two diastereoisomers of (‐)‐menthyl‐β‐(methylnaphthyl‐phenylstannyl)‐propionate (V) could not be separated. Copyright © 1975 Wiley‐VCH Verlag GmbH & Co. KGaA, Weinheim
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#1Stéphane Boué (ULB: Université libre de Bruxelles)H-Index: 8
#2Marcel Gielen (ULB: Université libre de Bruxelles)H-Index: 4
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Nine new racemic organotin derivatives: MePriPrSnR (R = Br, Et, Bu, iBu, sBu, tBu) and MeiPrcycloHexSnR′ (R′ = Br, Et, anisyl) have been synthesized in high yields. Their mass spectra and those of some intermediates are given and discussed on the basis of previous results. Copyright © 1969 Wiley‐VCH Verlag GmbH & Co. KGaA, Weinheim
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#1Marcel Gielen (Vrije Universiteit Brussel)H-Index: 38
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The optical stability of methylneophyltrityltin halides is greater than that of less sterically hindered triorganotin halides.
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#1Virginia Vetere (CONICET: National Scientific and Technical Research Council)H-Index: 4
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The catalytic behaviour of some compounds containing CO and/or CC bonds has been studied over silica-supported platinum-based catalysts, modified with tin. Tin was introduced by means of surface organometallic chemistry on metals (SOMC/M) techniques. The effect of the obtention conditions upon the catalytic performance was evidenced through the study of three systems having the same Sn/Pt atomic ratio (0.4), but prepared and activated at different temperature. In the hydrogenation of butyralde...
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The importance of the preparation procedure and the understanding of the mechanisms that control this stage on the final properties of the catalyst are evidenced for PtSn systems obtained via surface organometallic chemistry on metals (SOMC/M) techniques. The temperature of preparation reaction also plays a fundamental role as regards the nature of the active phase finally obtained, giving rise to catalytic phases having different levels of selectivity to unsaturated alcohols (UOL) in the croton...
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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-...
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Chiral tin(IV) derivatives with two or three chiral centers adjacent to the metal (−)-Ment2SnMe2, (−)-Ment2SnPh2, (−)-Ment3 SnCl, (−)-Ment3SnH; (−)-Ment  (1R, 2S, 5R)-1-chloro-5-methyl-2-isopropylcyclohexane, R2Sn[CH(Me)(n-Hex)]2 (R  Bu or Ph) have been prepared either by the coupling of methylmagnesium chloride with tin halides or by the reaction of lithium stannates with optically active (2-octyl)tosylate. The stereospecificity of both processes was remarkably high, leading to new optically ...
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The synthesis of chiral molecules or complexes containing tin(IV) and tin(II) is reported considering the type of chirality and the nature of the bonding to tin. The tin-centered chirality is first examined considering different types of functionalization and focusing on the configurational stability at the tin center, which provides useful information for organometallic chemists. Chiral ligands C -linked, O -linked, or N -linked to tin have been subsequently considered focusing first on the syn...
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