Oxidative functionalization of the .beta.-carbon in .alpha.,.beta.-unsaturated systems. Preparation of 3-phenylthio enones, acrylates, and other vinyl derivatives

Abstract

The /3-carbon of ,/3-unsaturated ketones, esters, lactones, and nitriles can be oxidatively functionalized in a regiospecific manner in a simple sequence of reactions. Michael addition of thiophenol followed by oxidation with jV-chlorosuccinimide gives chloro sulfides that readily lose HC1 to give 3-phenylthio enones, acrylates, and other vinyl derivatives.

Addition of nucleophiles to (E)-3-phenylsulfonylprop-2-enenitrile: a route to β-substituted α,β-unsaturated nitriles and to acetals of cyanoacetaldehyde

“…When exposed to one equivalent each of thiophenol and triethylamine in chloroform solution (E)-β-thiophenylacrylonitrile 19 was obtained in 76% yield. This compound has been synthesised previously by several authors, [7][8][9] but each of the routes that have been described are multi-step, and most give mixtures of (E)-and (Z)-products. We did not detect measurable amounts of (Z)-isomers in this or any of the other addition -elimination reaction products described in this paper.…”

The synthesis and screening of the antimicrobial activity of some novel 3-(furan-2-yl)-1-(aryl)-3-(phenylthio) propan-1-one derivatives

“…The thio-Michael addition reaction has emerged as one of the most powerful tools for C-S bond formation (Fujita and Nagao, 1977). Thio-Michael addition provides a widespread synthetic utility in organic chemistry (i) for chemo-selective protection of olefinic double band in unsaturated carbonyl compounds, (Trost and Keeley, 1975), (ii) for the generation of acyl vinyl cation equivalents (Bakuzia and Bakuzis, 1981), and (iii) for the synthesis of medicinally important compounds (Kumar et al, 1991). Thiol nucleophilic reagents are also known to show chemical reactivity toward chalcones, chalcon epoxides, chalcone dibromides, and their corresponding propynones.…”

Pronounced Catalytic Effect of a Micellar Solution of Sodium Dodecyl Sulfate (SDS) on the Efficient C‐S Bond Formationviaan Odorless Thia‐Michael Addition Reaction through thein situGeneration ofS‐Alkylisothiouronium Salts

“…Regeneration of the olefinic double bond is easily achieved by oxidative elimination [2] or induced by Cu + . [3] In addition, these compounds are starting materials for the generation of b-acylvinyl cations [4] and homoenolate anion equivalents. [5] For these and other reasons, the thia-Michael addition is an important reaction in organic synthesis and plays a crucial role in biosynthesis and the synthesis of bioactive compounds.…”