The Chemistry of CO: Carbonylation

Abstract

Carbon monoxide is one of the most important C1 molecules in organic chemistry. Many novel procedures for its conversion have been developed, and some have even been industrialized. In this review, we discuss and categorize CO chemistry into four classes: (1) transition-metal-mediated carbonylation, (2) strong-acid-initiated cationic carbonylation, (3) anionic carbonylation, and (4) free-radical carbonylation. Relevant achievements are selected and discussed in detail.

Synergetic Catalysis for One‐pot Bis‐alkoxycarbonylation of Terminal Alkynes over Pd/Xantphos−Al(OTf)3 Bi‐functional Catalytic System

“…Typically, succinates (derivatives) are obtained by oxidative alkoxycarbonylation of olefins, but suffering from the disadvantages like high loading of the palladium catalyst, excessive side reactions, and the risky use of dangerous oxidants . In comparison, the strategy based on bis‐alkoxycarbonylation of alkynes has attracted great attention due to 100 % atomic economy and simplified one‐pot operation, which allows for the preparation of succinates from alkynes and alcohol (nucleophile) via two successive alkoxycarbonylation (Scheme ) …”

“…[3] In comparison, the strategy based on bis-alkoxycarbonylation of alkynes has attracted great attention due to 100 % atomic economy and simplified one-pot operation, which allows for the preparation of succinates from alkynes and alcohol (nucleophile) via two successive alkoxycarbonylation (Scheme 1). [4] In 2018, Beller's group achieved the one-pot bi-alkoxycarbonylation of various aromatic and aliphatic alkynes over the catalytic system containing Pd(acac) 2 , an pyridinyl-tailed ligand and the Bronsted acid of PTSA · H 2 O, which exhibited the good activity as well as the high chemical/regional selectivity. [5] More recently, our group developed a bi-functional ligand containing both tert-phosphino-fragment and Bronsted acid group (À SO 3 H), which was applied successfully for Pd-catalyzed bisalkoxycarbonylation of alkynes towards 2-substituted succinates (diesters) in one-pot process.…”

Nickel‐catalyzed aminocarbonylation of aryl halides with carbamoylsilanes: efficient synthesis of secondary (primary) aromatic amides

“…So numerous alternate protocols have been explored. Among reported methods, palladium–catalyzed aminocarbonylation is a powerful method for the synthesis of aryl amides starting from aryl halides, amines and carbon monoxide, and is most frequently use reaction in organic synthesis . Although this method offers the advantage of functional group tolerance, it suffers from the troublesome handling of hazardous carbon monoxide gas, and the reaction setup requiring high–pressure reactors and harsh reaction conditions .…”

Quinolin-8-yl Formate: A New Option for Small-Scale Carbonylation Reactions in Microwave Reactors

“…Many mild methods now exist that permit reliable alkoxycarbonylations, aminocarbonylations, reductive carbonylations, and even carbonylative variants of C-C cross-couplings to be conducted with a range of aryl or hetaryl halides or pseudohalides. 4,5 The challenges associated with handling a highly toxic, odorless gas have, however, driven many groups to explore alternatives to the use of high-pressure CO sources, especially in small-scale settings. 6 We were particularly interested in the nearly simultaneous reports by the groups of Manabe and Tsuji of the use of phenyl formate (1) and its derivatives in palladium-catalyzed carbonylations.…”