Highly chemoselective addition of Schwartz’s reagent to widely available azlactones is described. This method allows the preparation of challenged functionalized α-amino aldehydes, in good to high isolated yields at room temperature, after only 2 min reaction. The presence of sensitive functionalities or electronic factors does not compromise the potential of the method. The use of an excess of the reducing reagent gave a very functionalized allylic alcohol derivative in 86% yield.

Chemoselective Reduction of Azlactones Using Schwartz's Reagent.

An operationally simple, efficient, and metal-/peroxide-free three-component reaction of alkynes, iodine, and sodium sulfinates has been developed for the construction of highly functionalized tetrasubstituted alkenes. Iodo- and sulfonyl-containing tetrasubstituted alkenes, such as vinyl ketones, allylic alcohols, and conjugated enynes, could be obtained regio- and stereoselectively in up to 96% yield.

Metal-Free Synthesis of Functionalized Tetrasubstituted Alkenes by Three-Component Reaction of Alkynes, Iodine, and Sodium Sulfinates.

Facile and modular access to stereodefined disubstituted aldehyde-derived silyl enol ethers allowed their successful application in a stereoselective aldol reaction affording the products with excellent yields and diastereomeric ratios. The counter-intuitive stereochemical behavior of this Mukaiyama-aldol reaction is accounted for by a non-classical open transition state.

Stereoselective Sc(OTf)3‐Catalyzed Aldol Reactions of disubstituted Silyl Enol Ethers of Aldehydes with Acetals

Copper‐Catalyzed β‐Iodovinylation of Carbamates: Expedient Access to Highly Functionalized Vinyl‐Carbamates

Alcohol as a Reagent in Homogeneous Catalysis

A new method to synthesize γ,δ-unsaturated α-nitrogenated aldehydes in very good yields is described herein. This method involves a copper-coupling reaction between β-iodoenamide derivatives and allylic alcohols to generate β-allyloxyenamide derivatives. The latter, when heated, undergo a Claisen rearrangement and form γ,δ-unsaturated α-nitrogenated aldehydes.

Neel Rahem

Papers

Synthesis of γ,δ-Unsaturated α-Aminoaldehydes Using a Copper-Catalyzed Vinylation Reaction Followed by a Claisen Rearrangement

Synthesis of γ,δ-Unsaturated α-Aminoaldehydes Using a Copper-Catalyzed Vinylation Reaction Followed by a Claisen Rearrangement.