A Convenient Palladium‐Catalyzed Reductive Carbonylation of Aryl Iodides with Dual Role of Formic Acid

Abstract

Palladium-catalyzed reductive carbonylation of aryl halides represents a straightforward pathway for the synthesis of aromatic aldehydes. The known reductive carbonylation procedures either require CO gas or complexed compounds as CO sources. In this communication, we developed a palladium-catalyzed reductive carbonylation of aryl iodides with formic acid as the formyl source. As a convenient, practical, and environmental friendly methodology, no additional silane or H2 was required. A variety of aromatic aldehydes were isolated in moderate to excellent yields under mild reaction conditions. Notably, this is the first procedure on using formic acid as the formyl source.

Synthesis of Amido Esters and Amido Phosphonates through Carbonylation of Diazo Compounds Followed by Nucleophilic Addition Reaction

“…By applying the developed protocol, we synthesized a number of amido esters and amido phosphonates. [31][32][33] Although there are difficulties in the handling of CO, few alternate methods have been developed for the carbonylation of alkyl or aryl halides by using nongaseous carbon monoxide sources. thermal conditions.…”

Recent developments in carbonylation chemistry using [13C]CO, [11C]CO, and [14C]CO

“…The decarbonylation of formic acid is achieved by forming an unstable mixed anhydride by reaction with acetic anhydride. Wu and coworkers have demonstrated this concept by synthesizing 13 C‐labeled aldehydes ( 107 ; Scheme 28A) and formates ( 108 ; Scheme 28B) using palladium catalysis. Fu et al recently used a similar procedure for liberating [ 13 C ]CO in situ from [ 13 C ]HCOOH for accessing 13 C‐labeled carboxylic acids from allylic alcohols ( 109 ; Scheme 28C).…”

Transition‐Metal‐Free Acceptorless Decarbonylation of Formic Acid Enabled by a Liquid Chemical‐Looping Strategy

“…[9] In situ decomposition of formic acid to promote for example formal carbonylation or hydroxycarbonylation, for example,has been reported. [10] Only afew methods have been developed to promote the acceptorless decarbonylation of FA,w hich relied on the use of stoichiometric amounts of sulfuric or phosphoric acids [11] or on thermolytic conditions. [12] Catalytic strategies are scarce.T hese involve zeolite-based catalysts able to decompose FA at high temperatures (> 150 8 8C), to remove water, and exhibit modest activity with turnover frequencies up to 39 h À1 .…”