Related Experiment Video
Updated: Jun 4, 2025

Constructing Thioether/Vinyl Sulfide-tethered Helical Peptides Via Photo-induced Thiol-ene/yne Hydrothiolation
Published on: August 1, 2018
A Formal 1,2-Stevens Rearrangement of Thioester Ylides as a Single-Atom Molecular Editing Tool
Ivan Borkovic1, Zorana Ferjancic1, Filip Bihelovic1
1University of Belgrade, Faculty of Chemistry, Studentski trg 16, P.O. Box 51, 11158 Belgrade 118, Serbia.
Abstract:
A rhodium-catalyzed reaction of thioesters with diazo reagents was recognized as a powerful and unprecedented tool for single-atom molecular editing by the insertion of a single carbon atom into the C(O)─S thioester bond, thereby leading to various α-thioketones possessing a quaternary carbon atom. A selective and precise defunctionalization of the polyfunctionalized products further demonstrated the synthetic utility of the reaction for the synthesis of more common structural classes of compounds.
Related Concept Videos
Aldehydes and Ketones to Alkenes: Wittig Reaction Overview
[3,3] Sigmatropic Rearrangement of Allyl Vinyl Ethers: Claisen Rearrangement
Aldehydes and Ketones to Alkenes: Wittig Reaction Mechanism
The reaction begins with the nucleophilic addition between a phosphorus ylide and the carbonyl compound. Due to its carbanionic character, phosphorus ylide acts as a strong nucleophile and attacks the electrophilic carbonyl group. This generates a charge-separated dipolar intermediate called betaine. The negatively charged oxygen atom and...
Preparation and Reactions of Thiols
Preparation of 1° Amines: Hofmann and Curtius Rearrangement Mechanism
Esters to β-Ketoesters: Claisen Condensation Mechanism

