Recent Advances in Nickel Catalyzed Carbonylative Reactionsviathe Insertion of Carbon Monoxide^†

Abstract

Comprehensive SummaryCarbonyl compounds have attracted considerable attention due to their extensive applications in drug discovery. Furthermore, they are important synthetic intermediates for the construction of carbon‐carbon and carbon‐heteroatom bonds. Transition‐metal‐catalyzed carbonylation via the insertion of CO is one of the most efficient and straightforward strategies to access carbonyl compounds. However, most of the transition‐metal‐catalyzed carbonylative reactions require expensive and toxic noble‐metal catalysts. Therefore, there is a growing demand for the exploration of nickel‐catalyzed carbonylative reactions via the insertion of CO due to the earth abundance and low cost of nickel. Compared with the well‐established palladium‐catalyzed carbonylative reactions, nickel‐catalyzed analogous transformations have been relatively underdeveloped. This is primarily because CO strongly binds to nickel, often resulting in catalyst poisoning. In recent years, some research groups have focused on using CO surrogates or NN2 pincer nickel catalyst to circumvent the formation of Ni(CO)4. Nickel‐catalyzed carbonylation has been applied in the construction of carbonyl‐containing compounds, such as ketones, carboxylic acids, thioesters, acyl chloride and carboxamides.

Nickel-Catalyzed Carbonylative Negishi Cross-Coupling of Unactivated Secondary Alkyl Electrophiles with 1 atm CO Gas

“…Ligand-accelerated nickel-catalyzed carbonylative cross-coupling has emerged as a rapid development in the field of carbonylation chemistry, wherein the supportive ligand plays a crucial role in overriding the strong affinity of excess of CO with the nickel center, thus preventing the deactivation of the nickel catalyst center . In addition to the utilization of abundant and inexpensive CO gas, − several CO surrogates including CO-gen, chloroformate, and metal carbonyl complex through the slow release of CO gas have proven successful in the nickel-catalyzed carbonylations. − We recently realized the carbonylation of allylic alcohol with organoalanes under 1 atm of CO gas to regioselectively access the β,γ-unsaturated ketones, wherein the nickel serves as the sole catalyst, enabling the direct use of alcohol as organoelectrophiles .…”

Nickel-Catalyzed Four-Component Carbonylation of 1,3-Butadiene To Access β,γ-Unsaturated Ketones

“…In the catalytic carbonylation field, the palladium catalytic system has been well-established, while nickel-catalyzed carbonylation is underdeveloped. The reason for this is that the strong binding affinity between CO and nickel prevents nickel from interacting with the substrates . We sought to develop a convenient synthetic method toward β,γ-unsaturated ketones through cross-coupling to construct three C–C bonds directly.…”

“…The reason for this is that the strong binding affinity between CO and nickel prevents nickel from interacting with the substrates. 8 We sought to develop a convenient synthetic method toward β,γ-unsaturated ketones through cross-coupling to construct three C–C bonds directly. To validate the conceptual framework mentioned above, we achieved a Ni-catalyzed highly regionally selective four-component carbonylation of 1,3-butadiene, arylboronic acids, alkyl bromides, and 1 bar of CO ( Figure 1 c).…”

Nickel/Photoredox-Catalyzed Carbonylative Cross-Electrophile Coupling of Organohalides and Carboxylic Acid Esters with Phenyl Formate

“…In recent years, reductive cross-electrophile coupling utilizing earth abundant transition metals (e.g., Ni, Co) has achieved increasing attention to mitigate the aforementioned issues . To avoid the deactivation of metal carbonyl complexes in the presence of a high concentration level of CO, pioneering studies of Gosmini and Hu have disclosed ethyl chloroformate is an effective CO surrogate and realized the reductive carbonylation of organohalides in the presence of a zinc reductant . Building upon this foundation, an array of elegant reductive carbonylative couplings have been well-established (Scheme a, right) .…”