Propargylamines are a versatile class of compounds which find broad application in many fields of chemistry. This review aims to describe the different strategies developed so far for the synthesis of propargylamines and their derivatives as well as to highlight their reactivity and use as building blocks in the synthesis of chemically relevant organic compounds. In the first part of the review, the different synthetic approaches to synthesize propargylamines, such as A3 couplings and C–H functionalization of alkynes, have been described and organized on the basis of the catalysts employed in the syntheses. Both racemic and enantioselective approaches have been reported. In the second part, an overview of the transformations of propargylamines into heterocyclic compounds such as pyrroles, pyridines, thiazoles, and oxazoles, as well as other relevant organic derivatives, is presented.

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Synthesis and Reactivity of Propargylamines in Organic Chemistry

An intermolecular, three-component reductive dicarbofunctionalization of alkenes is presented here. The combination of Ni catalysis with TDAE as final reductant enables the direct formation of Csp3–Csp3 and Csp3–Csp2 bonds across a variety of π-systems using two different electrophiles that are sequentially activated with exquisite selectivity under mild reaction conditions.

Nickel-Catalyzed Reductive Dicarbofunctionalization of Alkenes.

Carbon dioxide (CO2) has emerged as a sustainable, feasible, abundant one-carbon synthon and displays great potential in the synthesis of heterocycles such as lactones, lactams, and 2-oxazolidinones, which are privileged motifs in pharmaceutical chemistry demonstrating bioactivities. Although the fixation of CO2 is restricted due to its thermodynamic stability and kinetic inertness, multiple breakthroughs have been realized in annulation chemistry. This review concentrates on the advances made in the last five years in CO2-incorporated cyclization triggered by N-, O-, and C-nucleophiles. Three transformation modes of CO2 including carboxylative cyclization, carbonylative cyclization, and reductive cyclization have been summarized. Moreover, typical mechanisms and significant applications of these reactions are also described.

Recent advances in nucleophile-triggered CO2-incorporated cyclization leading to heterocycles.

Catalytic reduction of CO2 into fuels and fine chemicals

Homogeneous gold catalysis has experienced extraordinary development since the dawn of this millennium. Oxidative gold catalysis is a vibrant and fertile subfield and has over the years delivered a diverse array of versatile synthetic methods of exceptional value to synthetic practices. This review aims to cover this topic in a comprehensive manner. The discussions are organized by the mechanistic aspects of the metal oxidation states and further by the types of oxidants or oxidizing functional groups. Synthetic applications of oxidative gold catalysis are also discussed.

Homogeneous Gold-Catalyzed Oxidation Reactions.

Methods to incorporate atmospheric CO2 into organic molecules are on demand. Here we present two Pd-catalyzed multicomponent reactions that provide functionalized oxazolidinones from propargylamines, aryl halides and CO2 as starting materials. These transformations, devoid of high CO2 pressures, represent a streamlined stereocontrolled synthesis of previously inaccessible versions of these useful heterocycles in an atom-economic manner, as up to four new single bonds are formed in a single synthetic operation.

/pdf/palladium-catalyzed-incorporation-of-atmospheric-co2-3tbz8o18zj.pdf

Palladium-catalyzed incorporation of atmospheric CO2: efficient synthesis of functionalized oxazolidinones

Palladium‐Catalyzed Incorporation of Atmospheric CO2: Efficient Synthesis of Functionalized Oxazolidinones.

The reaction of indoles and stabilized cyclopropyl alkynes under gold- and/or gold & Bronsted acid-catalysis provided access to highly substituted tetrahydrocarbazoles. A mechanistic study revealed the complex mechanism underlying these processes and the opportunistic cooperation of Lewis and Bronsted acid-catalysts towards the formation of complex molecular scaffolds.

https://www.zora.uzh.ch/id/eprint/134278/1/ZORA134278.pdf

A Gold‐ and Brønsted Acid Catalytic Interplay Towards the Synthesis of Highly Substituted Tetrahydrocarbazoles

This paper describes an efficient aminoesterification of unactivated alkenes through Au(I)/Au(III) redox catalytic cycles using Selectfluor or hypervalent iodine(III) reagents.

Giulia Rusconi

Papers

Palladium-catalyzed incorporation of atmospheric CO2: efficient synthesis of functionalized oxazolidinones

Palladium‐Catalyzed Incorporation of Atmospheric CO2: Efficient Synthesis of Functionalized Oxazolidinones.

A Gold‐ and Brønsted Acid Catalytic Interplay Towards the Synthesis of Highly Substituted Tetrahydrocarbazoles

Gold-catalyzed oxidative aminoesterification of unactivated alkenes