ALKYL- AND ACYL-SUBSTITUTED VINYLSTANNANES: SYNTHESIS AND REACTIVITY IN ELECTROPHILIC SUBSTITUTION REACTIONS

Six substituted vinylstannanes have been prepared. (E)- and (Z)-2-trimethylstannyl-2-butene, (1) and (2), respectively, 2-methyl-1-(trimethylstannyl) propene, (3), and 3-methyl-2-trimethylstannyl-2-butene, (4), were prepared by coupling the appropriate lithium or Grignard reagent with chlorotrimethy...

Full description

Saved in:
Bibliographic Details
Published inSynthesis and reactivity in inorganic and metal-organic chemistry Vol. 32; no. 5; pp. 885 - 902
Main Authors Cochran, John C., Prindle, Vicki, Young, Heather A., Kumar, Mark H., Tom, Samson, Petraco, Nicholas D. K., Mohoro, Clare, Kelley, Brendan
Format Journal Article
LanguageEnglish
Published NEW YORK Taylor & Francis Group 07.11.2002
Marcel Dekker Inc
Subjects
Chemistry
Chemistry, Inorganic & Nuclear
Physical Sciences
Science & Technology
OXIDATION
PALLADIUM
HYDROSTANNATION
COUPLING REACTIONS
CONSTRUCTION
TIN
ORGANOSTANNANES
DESTANNYLATION
STEREOSELECTIVE SYNTHESIS
ORGANOTIN COMPOUNDS
Online AccessGet full text

Cover

More Information
Summary:Six substituted vinylstannanes have been prepared. (E)- and (Z)-2-trimethylstannyl-2-butene, (1) and (2), respectively, 2-methyl-1-(trimethylstannyl) propene, (3), and 3-methyl-2-trimethylstannyl-2-butene, (4), were prepared by coupling the appropriate lithium or Grignard reagent with chlorotrimethylstannane. 3-Trimethylstannyl-3-butene-2-one, (5), and (Z)-3-trimethylstannyl-3-hexene-2-one, (6), were prepared by palladium(O) catalyzed hydrostannation of the appropriate ynone. This reaction was regiospecific such that the trimethylstannyl and carbonyl groups were bonded at the same vinyl carbon. The reaction was also stereospecific giving syn addition in each case. However, isomerization to a mixture of isomers was observed for the reaction of (5) with Me 3 SnD and complete isomerization of E-(6) to Z-(6). Each compound was characterized by 1 H, 13 C, and 119 Sn NMR. The reactivity to protodestannylation was determined for each compound by spectrophotometric measurement of second order rate constants. The reactivity of the multimethyl-substituted vinylstannanes was consistent with the reactivity determined previously for monomethyl-substituted vinylstannanes. However, two methyl groups at the remote vinyl carbon exhibited a synergistic activating effect on the protodestannylation reactivity. The acyl group was found to be deactivating for protodestannylation. The stereochemistry of the reaction was found to take place with retention of configuration.
ISSN:0094-5714
1532-2440
DOI:10.1081/SIM-120005609