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From kinetics to the synthesis of chiral tetraorganotin compounds

Published on Jun 1, 1973in Accounts of Chemical Research21.661
· DOI :10.1021/ar50066a004
Marcel Gielen38
Estimated H-index: 38
Abstract
  • References (30)
  • Citations (34)
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References30
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#1Stéphane Boué (ULB: Université libre de Bruxelles)H-Index: 8
#2Marcel Gielen (ULB: Université libre de Bruxelles)H-Index: 38
Last. Jacques Nasielski (ULB: Université libre de Bruxelles)H-Index: 10
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The mass spectra of mixed tetraalkyltins are described and analysed. The fragmentation pattern is in agreement with the hypothesis of prefered Sn(IV) and Sn(II) valence states in the tin‐containing fragments. These states are reached by losing an alkyl radical from the next higher unfavourable valence state, or by losing an alkene or alkane molecule from a favourable valence state. The ease of cleavage of a carbon‐tin bond in the molecular ion parallels the stabilization of the leaving alkyl rad...
32 CitationsSource
#1Marcel Gielen (ULB: Université libre de Bruxelles)H-Index: 4
#2J. Topart (ULB: Université libre de Bruxelles)H-Index: 7
The reaction of organotin alcohols ϕR2Sn(CH2)n,CR'R”;OH (n = 1; R= ϕ R', R”; = H, H – n = 2; R = ϕ R', R”; = H, H; H, CH3; CH3, CH3; R = Me, ϕ R', R”; = H, CH3) with CCl4 or CBr4 in the presence of triphenylphosphine yields the corresponding halides, ϕR2Sn(CH2)n,CR'R”;X, which may readily be converted into triorganotin halides R2XSn(CH2).,CR'R”;X, good precursors of stannacyclo‐propanes and ‐butanes. Copyright © 1971 Wiley‐VCH Verlag GmbH & Co. KGaA, Weinheim
11 CitationsSource
#1Marcel Gielen (ULB: Université libre de Bruxelles)H-Index: 4
#2Noel Vanlautem (ULB: Université libre de Bruxelles)H-Index: 1
Permutations may be used to describe the transformations of a given complex MLn into one of the n!/hr, possible isomers. The determination of the n! possible permutations gives all the isomerization paths of this complex occuring by nonbond‐rupture mechanisms. This is applied to the case of four; five‐ and six‐ coordinate structures and might be applied as well to higher coordination numbers. Copyright © 1970 Wiley‐VCH Verlag GmbH & Co. KGaA, Weinheim
35 CitationsSource
#1Stéphane Boué (ULB: Université libre de Bruxelles)H-Index: 8
#2Marcel Gielen (ULB: Université libre de Bruxelles)H-Index: 4
Last. Richard Spielmann (ULB: Université libre de Bruxelles)H-Index: 2
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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
23 CitationsSource
#1Jean Brocas (ULB: Université libre de Bruxelles)H-Index: 9
#2Marcel Gielen (ULB: Université libre de Bruxelles)H-Index: 4
6 CitationsSource
#1Marcel Gielen (ULB: Université libre de Bruxelles)H-Index: 4
#2Jacques Nasielski (ULB: Université libre de Bruxelles)H-Index: 13
Last. J. Topart (ULB: Université libre de Bruxelles)H-Index: 7
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18 CitationsSource
#1Marcel Gielen (Free University of Brussels)H-Index: 38
#2Marie-Rose Barthels (Free University of Brussels)H-Index: 1
Last. Jacques Nasielski (Free University of Brussels)H-Index: 10
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The J(Sn‐CH2) coupling constants in a series of benzyltin derivatives are examined as a function of the substituents. A J vs Σσ* graph shows three equidistant and parallel lines. The mass spectra of these compounds confirm the fragmentation rules described before. Copyright © 1971 Wiley‐VCH Verlag GmbH & Co. KGaA, Weinheim
8 CitationsSource
#1C. Deblandre (ULB: Université libre de Bruxelles)H-Index: 1
#2Marcel Gielen (ULB: Université libre de Bruxelles)H-Index: 38
Last. Jacques Nasielski (ULB: Université libre de Bruxelles)H-Index: 10
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Symmetrical tetraalkyltins react with chromic anhydryde to yield aldehydes and acids. The rates have been measured, and the kinetic results suggest a five-membered transition state for this bimolecular electrophilic substitution on a saturated carbon atom.
8 CitationsSource
#1Marcel Gielen (ULB: Université libre de Bruxelles)H-Index: 38
#2Jacques Nasielski (ULB: Université libre de Bruxelles)H-Index: 10
The mass spectra of a series of aryltrimethyltins are described and analysed. The main features are: a relatively weak molecular ion, a very important ArSnMe2+ ion (base peak), a low intensity ArSnMe+ fragment and a non negligible ArSn+ peak. These findings may be related to the well known stable valence states of tin (IVSn and IISn) and the unfavourable IIISn and ISn states. Whereas a methyl group is easier to cleave from the ArSnMe3+ ion than the phenyl radical, n-butyl seems to be more strong...
20 CitationsSource
#1Marcel Gielen (ULB: Université libre de Bruxelles)H-Index: 38
#2Jacques Nasielski (ULB: Université libre de Bruxelles)H-Index: 10
The rates of the reactions of tetraalkyltins (R4Sn) with bromine in dimethylformamide and acetic acid solutions and with iodine in acetic acid are found to depend on steric effects (kMe> kEt > knPr), caused by the R3Sn leaving group. Trialkyltin bromides (R3SnBr) are cleaved by bromine in acetic acid in a reactivity sequence (kMe knPr) which is best explained by an increasing importance of inductive effects.
13 CitationsSource
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#1Xinghua Ma (CCNY: City College of New York)H-Index: 2
#2Mohamed Diane (CCNY: City College of New York)H-Index: 3
Last. Mark R. Biscoe (CCNY: City College of New York)H-Index: 15
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We report the use of isolable primary and secondary alkylcarbastannatrane nucleophiles in site-specific fluorination reactions. These reactions occur without the need for transition metal catalysis or in situ activation of the nucleophile. In the absence of the carbastannatrane backbone, alkyltin nucleophiles exhibit no activity towards fluorination. When enantioenriched alkylcarbastannatranes are employed, fluorination occurs predominately via a stereoinvertive mechanism to generate highly enan...
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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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#1Marcel Gielen (Vrije Universiteit Brussel)H-Index: 4
#2Stéphane Simon (Vrije Universiteit Brussel)H-Index: 1
Last. Cornelis Hoogzand (Vrije Universiteit Brussel)H-Index: 9
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Methylneophylphenyltin hydride (I), (methylneophylphenylstannyl) cyclopentadienyl molybdenum tricarbonyl(II) and dimethylphenylstannylmethyl-α-naphthyl-phenylgermanium (III) are configurationally stable within the NMR time scale, even in the presence of strong nucleophiles.
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#1Marcel Gielen (Vrije Universiteit Brussel)H-Index: 38
#2Hassan Mokhtar-Jamaï (ULB: Université libre de Bruxelles)H-Index: 4
The optical stability of methylneophyltrityltin halides is greater than that of less sterically hindered triorganotin halides.
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#1Bertha De Poorter (Vrije Universiteit Brussel)H-Index: 7
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The synthesis of a series of mixed and asymmetric benzyltin compounds is described. The nuclear magnetic resonance spectra are discussed.
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#1James A. Marshall (USC: University of South Carolina)H-Index: 16
#2Jill A. Jablonowski (USC: University of South Carolina)
1 Introduction 2 Chiral Organometallics of Type R1R2R3R4M 3 Germacyclopentanes and Cyclohexanes 4 Organometallics of Type R*MR3 5 Propargyl/Allenyl Systems Keywords: chiral organometallics of Type R1R2R3R4M; tin and configurational stability; pentacoordinated triorgano halostannanes; germacyclopentanes and cyclohexanes; organometallics of type R*MR3; chiral acyclic systems; propargyl/allenyl systems; germacyclopentanes and cyclohexanes
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Principal Component Analysis (PCA) was applied to 17 selected properties relating to the properties of solvents and their effect on solute spectra and equilibria and rates of reactions in solution. The analysis showed affinities and contrasts among the parameters. Using the first three principal components (PC's) as unit vectors in the Cartesian directions, the properties were represented as vectors in this space with their directions being represented as points on the unit hemisphere; their mag...
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#1Xueqing Song (UDC: University of the District of Columbia)H-Index: 18
#2Guiyun Zhong (NKU: Nankai University)H-Index: 1
Last. George Eng (UDC: University of the District of Columbia)H-Index: 22
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Abstract The reaction of triphenyltin chloride and mercaptoacetic acid under mild reaction conditions in the presence of an amine resulted in the cleavage of a Sn–Ph bond. This cleavage reaction was not observed when triphenyltin hydroxide or other triorganotin chlorides were employed. A possible pathway was proposed for the Sn–Ph cleavage. This is a first report of a mercaptoacetate ligand cleavaging Sn–Ph bonds under mild reaction conditions. It is also the first report of using 3J(119Sn–1H) (...
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#1Sławomir Jarosz (PAN: Polish Academy of Sciences)H-Index: 20
#2Anna Gawel (PAN: Polish Academy of Sciences)H-Index: 2
General methodology for the preparation of allyltin derivatives is reported, with special attention paid to sugar allyltins. Typical procedures affording such organometallics involve the conversion of partially protected hexoses or pentoses (Sug–CH2OH) into homologated allylic alcohols (Sug–CH=CH–CH2OH), which are further transformed into the primary or secondary sugar allyltin derivatives of the general formula Sug–CH=CH–CH2SnR3, (E)/(Z) ratio ≈ 5:1, or Sug–CH*(SnR3)–CH=CH2 (single isomer with ...
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#1Marcel Gielen (Vrije Universiteit Brussel)H-Index: 38
#2Monique Biesemans (Vrije Universiteit Brussel)H-Index: 35
Last. Rudolph Willem (Vrije Universiteit Brussel)H-Index: 38
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An overview is given of the research performed by the authors at the Universite Libre de Bruxelles and Vrije Universiteit Brussel, including the kinetics, stereochemistry and mechanism of SE2 reactions at a saturated carbon atom, the synthesis of chiral organotin compounds and their configurational and optical stability, the fluxionality of trigonal bipyramidal metal atoms and the stereochemistry of SN2 reactions at tetrahedrally substituted P, Si, Ge, Sn atoms, the cytotoxicity of many series o...
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