No Making Without Breaking: Nitrogen-Centered Carbonylation Reactions

Abstract

Carbonylation, an efficient and straightforward approach for installing a carbonyl group into their parent compounds, is an important area in modern organic synthesis. This Review outlines the recent advances in the development of nitrogen-centered carbonylation reactions, which consists of two parts: nitrogen-center-directed carbonylation reactions and carbonylative C−N bonds activation. According to the reaction mechanisms, two-electron-and single-electron-mediated carbonylation reactions were systematically classified and discussed in detail. Different inert bonds such as C(sp 2 )−H, C(sp 3 )−H, C−C, C(sp 3 )−N, and C(sp 2 )−N bonds can be activated and ready for a carbonylative transformation toward the synthesis of the corresponding carbonyl-containing compounds.

Ligand‐Controlled Copper‐Catalyzed Regiodivergent Carbonylative Synthesis of α‐Amino Ketones and α‐Boryl Amides from Imines and Alkyl Iodides

“…Over the past few decades, carbonylation reactions have experienced significant progresses with CO as an attractive C1 source for the preparation of various carbonyl-containing compounds and extending the carbon chain at the same time. [1] Among the numerous transformations, transition metal catalyzed borocarbonylation represents a novel strategy for converting CO/boron(ester) into complexed carbonylboryl compounds. Some borocarbonylation reactions of alkynes and alkene have been achieved by using Cu [2] or Cu/Pd [3] catalyst systems.…”

A Stereoselective, Multicomponent Catalytic Carbonylative Approach to a New Class of α,β-Unsaturated γ-Lactam Derivatives

“…Based on the existing knowledge on carbonylations [1][2][3][4][5] and on our expertise in PdI 2 /KI-catalyzed carbonylation reactions [7,8], we can propose the mechanistic pathway shown in Scheme 2 for the formation of (Z)-2-(2-oxopyrrolidin-3-ylidene)acetates 2. Palladation of the nitrogen of 1 initially leads to alkynylaminopalladium intermediate I, stabilized by the intramolecular triple bond coordination (anionic iodide ligands are omitted for clarity).…”

“…Carbonylation reactions represent an excellent approach for the direct synthesis of carbonyl compounds using the simplest and readily available C-1 source, that is, carbon monoxide [1][2][3][4][5]. CO is produced industrially starting from petroleum hydrocarbons, natural gas, and coal, and, in the future, a growing amount of carbon monoxide is also expected to be available from renewable feedstocks, such as biowastes and CO 2 [6].…”

Catalytic challenges and strategies for the carbonylation of σ-bonds

“…Although the catalytic carbonylation of several C-N bonds are known when the amines are activated, only few methods have been described starting from tertiary non-activated amines. 81 This observation can be rationalized by the fact that the carbonylation of a tertiary amine requires the breaking of a C-N bond to insert CO. However, the C-N bonds in allylic and benzylic molecules are more reactive than in simple alkylamines, this is explained by comparing their respective BDEs: while the BDE of the benzyl-N(CH3)2 linkage is about 255 kJ.mol -1 , it reaches 272 kJ.mol -1 for CH3-N(CH3)Ph.…”