Match!

Synthesis of an Optically Active Triorganostannyl Ketone

Published on Sep 1, 2010in Bulletin des Sociétés Chimiques Belges
· DOI :10.1002/bscb.19770860107
Marcel Gielen38
Estimated H-index: 38
(Vrije Universiteit Brussel),
Stéphane Simon8
Estimated H-index: 8
(ULB: Université libre de Bruxelles)
Abstract
Racemic p-(cyclohexylmethyl-l-naphthylstannyl) acetophenone (I) is transformed into its menthydrazone which is, after four recrystallizations, reconverted to optically active (I), [α]20°436 +0.25° ± 0.05°. Several methods have been used to determine the optical purity of optically active (I) without success.
  • References (9)
  • Citations (7)
📖 Papers frequently viewed together
1 Citations
1979
78% of Scinapse members use related papers. After signing in, all features are FREE.
References9
Newest
#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
25 CitationsSource
Reactions of cyanoalkyl- and methoxycarbonylalkyl-tin compounds with lithium aluminium hydride and Grignard reagents have been studied. Several new organo-tin compounds containing hydroxyalkyl, aminoalkyl and ketoalkyl groups are described.
12 CitationsSource
#1M. LequanH-Index: 7
#2F. MeganemH-Index: 4
Last. Y. BesaceH-Index: 6
view all 3 authors...
Abstract Synthesis and properties of chiral stannic amines are investigated. Tentative resolution has been carried out with tartaric acid and its derivatives
7 CitationsSource
#1S.Z. Abbas (Queen Elizabeth College, Mauritius)H-Index: 1
#2R.C. Poller (Queen Elizabeth College, Mauritius)H-Index: 12
Abstract The structures of the oximes formed from (4-oxopentyl)triphenyltin and (4-oxopentyl)diphenyltin chloride have been determined using IR, PMR and Mossbauer spectroscopy. Beckmann rearrangement of (4-oximinopentyl)diphenyltin chloride with phosphorus pentachloride gave the amide resulting from exchange of syn groups. Treatment of the second oxime with phosphorus pentachloride caused other reactions but the O -tosyl derivative was rearranged under mild conditions to give a mixture of amides...
12 CitationsSource
#1M. Lequan (ENSCP: Chimie ParisTech)H-Index: 7
#2F. Meganem (ENSCP: Chimie ParisTech)H-Index: 4
Resume p -(Phenylmethylisopropylstannyl)benzoic acid was prepared and resolved by fractional crystallisation of its (−)-brucine salt from methanol. The least soluble diastereoisomer yields the (−)-acid [α] 22 D = −0.50° in CHCl 3 and from the mother liquor repeated fractionations gave the other impure diastereoisomer leading to the (+)-acid [α] 22 D = +0.34° in CHCl 3 . Diazomethane in ethereal solution reacted with both acids to give the corresponding methyl esters.
10 CitationsSource
Protection of the carbonyl group in 1-chloropentan-4-one by dioxolan formation has enabled preparation of a series of 4-oxopentyltin compounds via the Grignard reagent. I.r., n.m.r., and Mogssbauer spectroscopy have been used to aid structure assignments: in many of the-compounds the carbonyl group is intramolecularly co-ordinated to tin. Stereochemical assignments have been made for (4-oxopentyl)diphenyltin chloride and di(4-oxopentyl)tin dibromide.
6 CitationsSource
Chemical shift non-equivalence of diastereotopic groups has been studied for a series of organotin monohalides with organic groups of different sizes to test the stereochemical stability of the asymmetric tin centre. The mutually related effects of halogen intermolecular exchange, nature of tin–halogen bond, intrinsic asymmetry of the molecules, and the steric requirements of the organotin groups are discussed in the light of the experimental findings. The effect of the bulk of the organic group...
20 CitationsSource
Methyl- bzw. Isopropylferrocen-carbonamide und-aldehyde wurden durch geeignete Substitution (NH2COCl/AlCl3 bzw.Vilsmeier-Formylierung) der entsprechenden Alkylferrocene dargestellt und in die Stellungsisomeren aufgetrennt. Nach Reduktion des homoannularen α-Carbamyl-methylferrocens zum entsprechenden Amin wurde dieses mit Benzoyl-(R)-weinsaure bzw. (S)-Apfelsaure in die Antipoden gespalten. Racematspaltung von 1,1′-Diisopropyl-β-formyl-ferrocen mittels (−)-Menthydrazid fuhrte zum (+)-Aldehyd.
33 CitationsSource
30 CitationsSource
43 CitationsSource
Cited By7
Newest
#1Marcel Gielen (Vrije Universiteit Brussel)H-Index: 38
#2Stéphane Simon (ULB: Université libre de Bruxelles)H-Index: 8
(Dimethylphenylstannyl)methyl‐1‐naphthyl‐phenylgermanium (I) and methylneophylphenyl (triphenylgermyl)tin (II) are configurationally stable even in the presence of strong nucleophiles. Optically active isopropylmethylphenyl (triphenylgermyl)tin (III) has been synthesized by asymmetric induction and shows that hexaorganodimetal compounds with a tin‐germanium bond are optically stable. The synthesis of functionally substituted organometallic compounds with a Sn‐Ge bond, like 5‐[(phenyldimethylstan...
8 CitationsSource
Source
#1Marcel Gielen (Vrije Universiteit Brussel)H-Index: 4
#2Serge Simon (Vrije Universiteit Brussel)H-Index: 1
Last. Michel van de Steen (Vrije Universiteit Brussel)H-Index: 1
view all 3 authors...
13 CitationsSource
#1Marcel Gielen (Vrije Universiteit Brussel)H-Index: 38
Many organotin compounds are optically stable for long periods so that all the reactions transforming one of them into another can be studied from the stereochemical point of view. Several stereoselective reactions at tin have already been found. However the stereochemistries and even the stereoselectivities have not yet been determined (if the H—D exchange is not taken into account) because the optical purities (and a fortiori the absolute configurations) of the starting materials and of the re...
15 CitationsSource
#1M. Lequan (ENSCP: Chimie ParisTech)H-Index: 7
#2S. Queroix (ENSCP: Chimie ParisTech)H-Index: 1
Resume p -(Methylphenylisopropylstannyl)benzaldehyde has been prepared and resolved by menthyl carbazate in ethanol ([α] 20 D –34.6°). Functional exchange with acetone of the less soluble diastereomer catalysed by traces of p -toluenesulfonic acid yields the optically active aldehyde with [α] 20 436 +0.35°.
7 CitationsSource
#1Marcel Gielen (Vrije Universiteit Brussel)H-Index: 4
#2Ivan Vanden Eynde (Vrije Universiteit Brussel)H-Index: 6
The configurational stability of triorganostannyl–iron, –manganese and –cobalt complexes has been determined by studying the coalescence of the NMR signals of diastereotopic groups and by looking at the epimerization of diastereomeric mixtures of these compounds. Possible substitution reactions, transforming the studied derivatives into one another, have been checked.
13 CitationsSource
#1Marcel Gielen (Vrije Universiteit Brussel)H-Index: 38
#2H. ZimmerH-Index: 1
1 CitationsSource