Related Experiment Video
Updated: Jul 7, 2026

A Two-Step Protocol for Umpolung Functionalization of Ketones Via Enolonium Species
Published on: August 16, 2018
SmI2-promoted Reformatsky-type coupling reactions in exceptionally hindered contexts
Brian A Sparling1, Ryan M Moslin, Timothy F Jamison
1Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, USA.
Abstract:
Highly substituted, very hindered enones were synthesized using a two-step procedure that utilizes a diiodosamarium-promoted Reformatsky-type coupling and dehydration using Martin sulfurane. Both alpha-chloro- and alpha-bromoketones were coupled with a variety of carbonyl nucleophiles to form the intermediate beta-hydroxyketones, occurring with excellent diastereoselectivity, favoring the syn isomer (R1=Me). This technique complements other methods and enables the preparation of enones outside of the scope of current olefination methodology.
More Related Videos
Related Concept Videos
Limitations of Friedel–Crafts Reactions
Cycloaddition Reactions: MO Requirements for Thermal Activation
Cycloaddition Reactions: Overview
Phase II Reactions: Miscellaneous Conjugation Reactions
A key example involves the conjugation of cyanide ions, which impair cellular respiration and alter hemoglobin into non-oxygen-carrying cyanmethemoglobin. To neutralize this threat, a sulfur atom from thiosulphate is transferred to the cyanide ion, catalyzed by the enzyme rhodanese, resulting in an inactive compound called thiocyanate. The production of...
Woodward–Hoffmann Selection Rules and Microscopic Reversibility
SN2 Reaction: Stereochemistry
If the substrate is an achiral molecule at the α-carbon, the inversion of configuration is not observed.
![Mizoroki-Heck Cross-coupling Reactions Catalyzed by Dichloro{bis[1,1',1''-(phosphinetriyl)tripiperidine]}palladium Under Mild Reaction Conditions](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F51444.jpg&w=3840&q=50)
