Generation, Reactivity and Uses of Sulfines in Organic Synthesis

Abstract

This review focuses on the synthesis and reactivity of thioketone S‐oxides (sulfines). Sulfines have been long established as being reactive intermediates of high interest and with potential for wide application in organic synthesis. The review will cover many aspects of sulfines: the first section looks at the different routes to the synthesis of these compounds with a detailed look at more recently developed routes; the second section details the scope of reactivity of these types of compounds and how they are useful in synthetic organic chemistry with a particular look at cycloaddition and nucleophilic addition reactions.

Parent Thioketene S‐Oxide H2CCSO: Gas‐Phase Generation, Structure, and Bonding Analysis

“…Among the isolated pyrolysis products at 77 K, a new species exhibiting IR bands at 1700, 1040, and 735 cm −1 was tentatively assigned to H 2 C=C=S=O based on the comparison with the theoretically calculated IR frequencies (1811.8, 1127.7, and 791.2 cm −1 , B3LYP/6‐311+G level). However, as very recently pointed out by Maguire et al., this assignment is questionable since no retro Diels–Alder decomposition but intramolecular rearrangement of the precursor occurs under the pyrolysis conditions.…”

“…8, 1127.7, and 791.2 cm À1 ,B 3LYP/6-311 + Gl evel). However,a sv ery recently pointed out by Maguire et al, [9] this assignment is questionable since no retro Diels-Alder decomposition but intramolecular rearrangemento ft he precursor occurs under the pyrolysis conditions.…”

Aminoacyl sulfonamide assembly in SB-203208 biosynthesis

“…An evolving negative charge on sulfur moves to oxygen, resulting in 7a–3 sulfene structure, which is generated through elimination of HCl from sulfinyl chloride in chemical synthesis 39 . Finally, this intermediate generates a more stable ene-thioaldehyde S-oxide 40 7a .…”

Delivering Enhanced Efficiency in the Synthesis of α-Diazosulfoxides by Exploiting the Process Control Enabled in Flow

“…The utility and synthetic versatility of α-oxo sulfines have been reported and reviewed in the literature [32][33][34][35][36].…”