Recent Advances on the Lewis Acid-Catalyzed Cascade Rearrangements of Propargylic Alcohols and Their Derivatives

Abstract

Propargylic alcohols and their derivatives are important classes of organic compounds that can be easily accessible from terminal alkynes and aldehydes or ketones. They are attractive and have been extensively applied as synthetic intermediates in modern organic synthesis. Recent investigations on the chemistry of propargylic alcohols and their derivatives disclosed a variety of highly efficient Lewis acid-catalyzed cascade reactions based on Meyer−Schuster rearrangement of propargylic alcohols and [3,3] rearrangement of propargylic esters and propargyl vinyl ethers. A tremendous number of structurally versatile enones, carbocycles, and heterocycles have been constructed through these methodologies. These advances, including our recent researches in this field, are summarized in this review.

An Energy Investigation into 1D/2D Oriented‐Attachment Assemblies of 1D Ag Nanocrystals

“…We faced such a case when working with propargyl alcohols tethered to β‐keto esters (Scheme ) 3. Under calcium catalysis,4 3‐carbon‐tethered substrates of type A 2 undergo a Meyer–Schuster rearrangement5/aldol condensation cascade6 to give C 2 ‐type compounds with a 3‐vinylcyclohexenone framework. On the other hand, with 2‐carbon‐tethered compounds A 1 , only Meyer–Schuster products B 1 were obtained, unless i PrOH was used as additive.…”

From QCA (Quantum Cellular Automata) to Organocatalytic Reactions with Stabilized Carbenium Ions

“…A possible solution for the direct and practical activation of alcohols is based on the use of Brønsted or Lewis acids. In 2011, we reported a general review20 of the direct nucleophilic substitution of alcohols, in which Brønsted and Lewis acids were used with several nucleophiles in S N 1‐type reactions 21. However, for the success of this new emerging protocol, the formation of relatively stable carbenium ions needs to be considered.…”

Catalyst‐Controlled Dual Reactivity of Sulfonimidamides: Synthesis of Propargylamines and N‐Propargyl Sulfonimidamides

“…We first synthesized propargyl alcohols 9 via the treatment of aldehydes 2 and acetylenes 3 following the reportedp rocedures. [12] The synthesized propargyl alcohols 9 were further treated with SIAs 1 in the presence of strong Lewis acid to obtain propargyl sulfonimidamides 10 via the nucleophilicsubstitutionof-OH group of 9 with imine part of SIAs 1.…”