¹³C NMR Analysis as a Useful Tool for Structural Assignment of Vinyl- and Dienyltin Derivatives

Jean-François Betzer; Patrick Le Ménez; Joëlle Prunet; Jean-Daniel Brion; Janick Ardisson; Ange Pancrazi

doi:10.1055/s-2002-19316

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Synlett 2002(1): 0001-0015
DOI: 10.1055/s-2002-19316

ACCOUNT

^¹³C NMR Analysis as a Useful Tool for Structural Assignment of Vinyl- and Dienyltin Derivatives

Jean-François Betzer^a, Patrick Le Ménez^b, Joëlle Prunet^c, Jean-Daniel Brion^b, Janick Ardisson*^a, Ange Pancrazi*^a
^a Laboratoire de Synthèse Organique Sélective et Chimie Organométallique, CNRS-UCP-ESCOM, FRE 2126, 13 Bd de l"Hautil,95092 Cergy-Pontoise Cedex, France
Fax: +33(1)30756015; e-Mail: j.ardisson@escom.fr; e-Mail: a.pancrazi@escom.fr;
^b Laboratoire de Chimie des Substances Naturelles associé au CNRS, BIOCIS, Centre d"Etudes Pharmaceutiques, 92290 Châtenay-Malabry, France
^c Ecole Polytechnique, Laboratoire de Synthèse Organique, DCSO, 91128 Palaiseau, France

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Publication History

Received 11 June 2001
Publication Date:
01 February 2007 (online)

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Abstract

During the last decade, vinyl- and dienyltin derivatives have been extensively developed and used in organic synthesis. ¹H NMR analysis of these compounds was the first analytical tool employed, together with ¹¹⁹Sn NMR, for the assignment of the E or Z stereochemistry of vinylstannyl derivatives. In this paper we want to show that ¹³C NMR is a powerful tool for structural analysis of vinyl- and dienyltin compounds. Chemical shifts and ¹³C-^119-117Sn coupling constants are reported for several examples. In all cases described, the ^³ J ¹³C_- ^119-117Sn values give the most definitive argument for structural assignment. ^¹ J, ^² J and ^³ J ¹³C-^119-117Sn coupling constants are also reported, along with the α, β, γ, and δ effects of the stannyl group. When the vinyltin function is functionalized with a heteroatomic substituant, some important changes occur in the chemical shifts and coupling constants. Some examples are given in the α-oxygen, -sulfur, -halogen, -silyl, and -tin substituted vinyltin series.

Key words

vinyltin - dienyltin - chemical shifs - coupling constants - heterosubstituted vinyltin

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7

Practical information: in general the central ¹H signal is associated with two satellites corresponding to both ¹¹⁹Sn and ¹¹⁷Sn isotopes (for J ¹H-^119,117Sn > 70.0-100.0 Hz) but when J ¹H ^119,117Sn < 70.0-100.0 Hz, the two pairs of satellites are unresolved and only one coupling constant can be measured.

29

Le Menez, P.; Brion, J.-D.; Pancrazi, A.; Ardisson, J. unpublished results.