“Syn-Effect” in the Desulfonylation Reaction of α,α-Dialkylated (E)-Allylic Sulfones
- 1 February 1997
- journal article
- Published by Oxford University Press (OUP) in Bulletin of the Chemical Society of Japan
- Vol. 70 (2) , 381-396
- https://doi.org/10.1246/bcsj.70.381
Abstract
It was found that the desulfonylation reaction of α,α-dialkylated (E)-allylic sulfones with a base preferentially affords the sterically unfavorable (Z)-alkadienes. The relative degree of the “syn-effect”, which is herein defined as an effect which stabilizes the syn-conformation, leading to (Z)-products, in the transition state against the steric hindrance, was revealed for various substituents at the δ-position of the (E)-allylic sulfones to be as follows: RO– >> CH3– > RS– > –CH2– > (CH3)2CH– >> (CH3)3C– > C6H5–. This finding is in accord with a previously found tendency in the conversion of (E)-vinylic sulfones to the corresponding allylic sulfones under basic conditionsKeywords
This publication has 13 references indexed in Scilit:
- Reactions of (E)-2-Iodo-1-tosyl-1-alkenes as Useful Synthetic IntermediatesBulletin of the Chemical Society of Japan, 1992
- “Syn-Effect” in the Conversion of (E)-Vinylic Sulfones to the Corresponding Allylic SulfonesBulletin of the Chemical Society of Japan, 1992
- Regio- and Stereoselective Synthesis of Vinyl and Allyl Sulfones-Toward the Elucidation of the Origin of "Syn-effect".Journal of Synthetic Organic Chemistry, Japan, 1992
- Convenient Methods for the Preparation of Vinylic and Allylic Sulfones from Alkenes, Haloalkanes, and Aldehydes. Stereochemistry of the Conversion of Vinylic Sulfones to the Corresponding Allylic SulfonesBulletin of the Chemical Society of Japan, 1987
- Mechanistic aspects and profiles of the double elimination reaction of .beta.-substituted sulfonesThe Journal of Organic Chemistry, 1986
- .alpha.-Haloalkanesulfonyl bromides in organic synthesis. 5. Versatile reagents for the synthesis of conjugated polyenes, enones, and 1,3-oxathiole 1,1-dioxidesJournal of the American Chemical Society, 1986
- The “syn-effect” in sulfines and carbonyl oxides: Conformational preferences of CH3CHSO and CH3CHOOTetrahedron Letters, 1981
- Stabilities of stereoisomeric imine anionsJournal of the American Chemical Society, 1980
- Theoretical determination of molecular structure and conformation. 6. The Criegee intermediate. Evidence for a stabilization of its syn form by alkyl substituentsJournal of the American Chemical Society, 1979
- The importance of .sigma. conjugative interactions in rotational isomerismJournal of the American Chemical Society, 1978