Stereochemical and spectroscopic studies on the reaction of allylstannanes with aldehydes

Scott E. Denmark; Eric J. Weber; Thomas M. Wilson; Timothy M. Willson

doi:10.1016/0040-4020(89)80016-X

Stereochemical and spectroscopic studies on the reaction of allylstannanes with aldehydes

Scott E. Denmark, Eric J. Weber, Thomas M. Wilson, Timothy M. Willson

Chemistry

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Abstract

The orientational preference for the reacting double bonds in the Lewis acid-induced reaction of allylic stannanes and aldehydes has been examined. Model system 1 shows a strong and Lewis-acid independent preference for the synclinal orientation of double bonds. A possible stereoelectronic basis for this preference is discussed. A ¹³C-NMR spcctroscopic study of the reaction between crotyltrialkylstannanes (9) and acetaldehyde (10), pivaldehyde (11) and 4-t-butylbenzaldehyde (12) in the presence of BF₃·OEt₂ and SnCl₄ is described. The spectroscopic study reveals that with BF₃·OEt₂ only direct addition occurs while with SnCl₄ the pathway (addition vs. metathesis) is stoichiometry and aldehyde dependent. The mechanism of metathesis and chlorostannane isomerization is discussed.

Original language	English (US)
Pages (from-to)	1053-1065
Number of pages	13
Journal	Tetrahedron
Volume	45
Issue number	4
DOIs	https://doi.org/10.1016/0040-4020(89)80016-X
State	Published - 1989

ASJC Scopus subject areas

Biochemistry
Drug Discovery
Organic Chemistry

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abstract = "The orientational preference for the reacting double bonds in the Lewis acid-induced reaction of allylic stannanes and aldehydes has been examined. Model system 1 shows a strong and Lewis-acid independent preference for the synclinal orientation of double bonds. A possible stereoelectronic basis for this preference is discussed. A 13C-NMR spcctroscopic study of the reaction between crotyltrialkylstannanes (9) and acetaldehyde (10), pivaldehyde (11) and 4-t-butylbenzaldehyde (12) in the presence of BF3·OEt2 and SnCl4 is described. The spectroscopic study reveals that with BF3·OEt2 only direct addition occurs while with SnCl4 the pathway (addition vs. metathesis) is stoichiometry and aldehyde dependent. The mechanism of metathesis and chlorostannane isomerization is discussed.",

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T1 - Stereochemical and spectroscopic studies on the reaction of allylstannanes with aldehydes

AU - Denmark, Scott E.

AU - Weber, Eric J.

AU - Wilson, Thomas M.

AU - Willson, Timothy M.

PY - 1989

Y1 - 1989

N2 - The orientational preference for the reacting double bonds in the Lewis acid-induced reaction of allylic stannanes and aldehydes has been examined. Model system 1 shows a strong and Lewis-acid independent preference for the synclinal orientation of double bonds. A possible stereoelectronic basis for this preference is discussed. A 13C-NMR spcctroscopic study of the reaction between crotyltrialkylstannanes (9) and acetaldehyde (10), pivaldehyde (11) and 4-t-butylbenzaldehyde (12) in the presence of BF3·OEt2 and SnCl4 is described. The spectroscopic study reveals that with BF3·OEt2 only direct addition occurs while with SnCl4 the pathway (addition vs. metathesis) is stoichiometry and aldehyde dependent. The mechanism of metathesis and chlorostannane isomerization is discussed.

AB - The orientational preference for the reacting double bonds in the Lewis acid-induced reaction of allylic stannanes and aldehydes has been examined. Model system 1 shows a strong and Lewis-acid independent preference for the synclinal orientation of double bonds. A possible stereoelectronic basis for this preference is discussed. A 13C-NMR spcctroscopic study of the reaction between crotyltrialkylstannanes (9) and acetaldehyde (10), pivaldehyde (11) and 4-t-butylbenzaldehyde (12) in the presence of BF3·OEt2 and SnCl4 is described. The spectroscopic study reveals that with BF3·OEt2 only direct addition occurs while with SnCl4 the pathway (addition vs. metathesis) is stoichiometry and aldehyde dependent. The mechanism of metathesis and chlorostannane isomerization is discussed.

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Stereochemical and spectroscopic studies on the reaction of allylstannanes with aldehydes

Abstract

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