Tandem Reactions Based on the Cyclization of Carbon Dioxide and Propargylic Alcohols: Derivative Applications of α-Alkylidene Carbonates

As a well-known greenhouse gas, carbon dioxide (CO2) has attracted increasing levels of attention in areas of energy, environment, climate, etc. Notably, CO2 is an abundant, nonflammable, and renewable C1 feedstock in view of chemistry. Therefore, the transformation of CO2 into organic compounds is an extremely attractive research topic in modern green and sustainable chemistry. Among the numerous CO2 utilization methods, carboxylative cycloaddition of CO2 into propargylic alcohols is an ideal route due to the corresponding products, α-alkylidene cyclic carbonates, which are a series of highly functionalized compounds that supply numerous potential methods for the construction of various synthetically and biologically valuable agents. This cyclization reaction has been intensively studied and systematically summarized, in the past years. Therefore, attention has been gradually transferred to produce more derivative compounds. Herein, the tandem reactions of this cyclization with hydration, amination, alcoholysis, and isomerization to synthesize α-hydroxyl ketones, oxazolidinones, carbamates, unsymmetrical carbonates, tetronic acids, ethylene carbonates, etc. were systematically reviewed.

Nickel-Catalyzed Dimerization/(4+2) Cycloaddition Tandem of Terminal Alkynes with Four-Membered Ring Ketones

Controlling the behaviour of terminal alkynes in metal-catalysed intermolecular tandem reactions is a formidable challenge despite the potential advantage offered by these strategies in modern synthesis. Herein, we describe that a nickel catalyst enables a tandem consisting in the rapid dimerization of terminal alkynes into 1,3-enynes and the cycloaddition of these intermediates with an azetidinone, an oxetanone and benzocyclobutenones. Significantly, the slow or sequential additions of reagents and catalysts is not required to orchestrate their reactivity. These results are in stark contrast with previous cycloadditions of terminal alkynes with those strained four-membered ring substrates, which previously led to oligomerization or cyclotrimerization, except in the case of tert-butylacetylene.

α-Ketol and α-iminol rearrangements in synthetic organic and biosynthetic reactions

In the presence of a suitable acid or base, α-hydroxyaldehydes, ketones, and imines can undergo isomerization that features the 1,2-shift of an alkyl or aryl group. In the process, the hydroxy group is converted to a carbonyl and the aldehyde/ketone or imine is converted to an alcohol or amine. Such α-ketol/α-iminol rearrangements are used in a wide variety of synthetic applications including asymmetric synthesis, tandem reactions, and the total synthesis and biosynthesis of natural products. This review explores the use of α-ketol rearrangements in these contexts over the past two decades.

Organocatalytic total synthesis of bioactive compounds based on one-pot methodologies

The combination of one-pot methodologies to asymmetric organocatalysis allow a green and direct access to many types of complex highly functionalized chiral products, including important key intermediates in total syntheses of important bioactive compounds. A series of chiral organocatalysts have already been successfully applied to such syntheses. This report collects major developments in the total synthesis of biologically active products based on the use of enantioselective organocatalytic domino/tandem reactions as key steps. It is divided into two parts dealing successively with reactions based on the use of proline-derived catalysts and other organocatalysts.