Stereoselective Synthesis of Z-α,β-Unsaturated Sulfones Using Peterson Reagents

Abstract

New Peterson reagents were prepared by introducing alkyloxy groups on the silicon atom in order to fix the conformation of the sulfone anion. The reagents 1d and 1e reacted with a variety of aldehydes after the treatment with Li-base to give Z-α,β-unsaturated sulfones with up to >99:1 selectivity in good to excellent yields. For the reaction with aliphatic aldehydes, CPME (cyclopentyl methyl ether) is the choice of solvent, while DME (1,2-dimethoxyethane) gave higher selectivity for the reaction with aromatic aldehydes.

Aminooxylation Horner–Wadsworth–Emmons Sequence for the Synthesis of Enantioenriched γ-Functionalized Vinyl Sulfones

“…A traditional sodium hydride-based HWE reaction gave E- 9 in 42% yield (entry 5) . We also attempted a Z -selective Ando HWE olefination using phosphonate 10 and literature conditions deviating slightly from our optimal procedure (entry 6). However, in this instance only moderate yields and poor Z -selectivity were observed.…”

Styrylsulfonates and ‐Sulfonamides through Pd‐Catalysed Matsuda–Heck Reactions of Vinylsulfonic Acid Derivatives and Arenediazonium Salts

“…Most syntheses rely on phosphonate‐based olefination reactions, an approach that can also be used for sulfonic acid esters and amides , , , . A stereoselective synthesis of Z ‐vinylsulfones by Peterson olefination has recently been reported . Another group of syntheses proceeds through transition‐metal‐catalysed allylic substitution–isomerization sequences, or cross‐coupling reactions, using sodium aryl sulfinates or sulfinate surrogates as nucleophiles.…”

“…[30,31,43,44] A stereoselective synthesis of Z-vinylsulfones by Peterson olefination has recently been reported. [45] Another group of syntheses proceeds through transition-metal-catalysed allylic substitutionisomerization sequences [46,47] or cross-coupling reactions [48,49] using sodium aryl sulfinates or sulfinate surrogates as nucleophiles. In a third class of syntheses, the C-C double bond of the vinylsulfonyl derivatives is formed by elimination of water or hydrogen halide after introduction of the sulfone.…”

Iron-catalyzed regioselective synthesis of (E)-vinyl sulfones mediated by unprotected hydroxylamines

“…On the other hand, common sulfonylation reagents such as sulfonyl chlorides, sulfonyl hydrazides, sodium sulfinates, sulfinic acids and thiols have been used to prepare vinyl sulfones. 8–12 Despite the great achievements having been made, some limitations still remain in terms of expensive and toxic catalysts, complicated operation, poor regioselectivity and low atom economy.…”