Palladium-catalyzed carbonylative coupling reactions between Ar-X and carbon nucleophiles.

Imai K.

Nakamura A., Munakata K., Ito S., Kochi T., Chung L.W., Morokuma K., Nozaki K.

Full details are provided for the alternating copolymerization of acrylic esters with carbon monoxide (CO) catalyzed by palladium species bearing a phosphine-sulfonate bidentate ligand. The copolymer of methyl acrylate (MA) and CO had complete regioregularity with stereocenters that slowly epimerize in the presence of methanol. In the presence of ethylene, terpolymers of MA/ethylene/CO were also prepared. The glass transition temperatures of the co- and terpolymers were higher than that of the ethylene/CO copolymer. Both experimental and theoretical investigations were performed to clarify the superior nature of the palladium phosphine-sulfonate system compared to an unsuccessful conventional palladium diphosphine system: (i) The reversible insertion of CO was directly observed with the isolated alkylpalladium complexes, [{o-((o-MeOC(6)H(4))(2)P)C(6)H(4)SO(3)}PdCH(CO(2)Me)CH(2)COMe], whereas it was not observed with the corresponding complex bearing 1,2-bis(diphenylphosphino)ethane (DPPE). (ii) The transition state of the subsequent MA insertion, the rate-determining step of the catalytic cycle, was lower in energy in the phosphine-sulfonate system than in the DPPE system. This stabilization could be attributed to the less hindered sulfonate moiety as well as the stronger back-donation from palladium to the electron-deficient olefin, which is located trans to the sulfonate.

Wu X., Neumann H., Beller M.

A general palladium-catalyzed carbonylative cross-coupling reaction of benzyl chlorides with potassium aryltrifluoroborates in water has been developed. Applying this improved methodology 16 different 1,2-diarylethanones have been synthesized in 40–89% yield.

Wu X., Jiao H., Neumann H., Beller M.

cHeck you out! A general and efficient palladium-catalyzed carbonylative Heck coupling reaction of aryl bromides with styrenes is described. In the presence of [{(cinnamyl)PdCl}2]/PPh3, 22 different chalcones have been synthesized in high yield.

Wu X., Sundararaju B., Neumann H., Dixneuf P.H., Beller M.

Trifling with triflates: A new protocol for the carbonylative Sonogashira reactions of aryl triflates (see scheme) that provides a significant extension of this interesting methodology is described.

Sävmarker J., Lindh J., Nilsson P.

Stille-type carbonylative cross-couplings, employing palladium catalysis and Mo(CO)6 as the carbon monoxide carrier, were used for the preparation of deoxybenzoins. Straightforward transformations ...

Wu X., Neumann H., Beller M.

A novel chemoselective protocol for the carbonylative Suzuki coupling of benzyl chlorides with aryl boronic acids at low pressure of carbon monoxide has been developed. Applying a commercially available palladium acetate/PCy3 catalyst system in the presence of potassium phosphate as the base and water as the solvent the coupling reactions proceeded smoothly. To demonstrate the general applicability 12 different α-arylated acetophenones have been synthesized in moderate to good yields (41–78%) under mild conditions.

Wu X., Anbarasan P., Neumann H., Beller M.

Konrad T.M., Fuentes J.A., Slawin A.M., Clarke M.L.

Wu X., Neumann H., Spannenberg A., Schulz T., Jiao H., Beller M.

The first general palladium-catalyzed carbonylative vinylation of aryl halides with olefins in the presence of CO has been developed. Applying a catalyst system consisting of [(cinnamyl)PdCl](2) and bulky imidazolyl-phosphine ligand L1 allows for the efficient and selective synthesis of α,β-unsaturated ketones under mild reaction conditions. Starting from easily available aryl halides and olefins, versatile building blocks can be prepared in a straightforward manner. The generality and functional group tolerance of this novel protocol is demonstrated.

Wu X., Neumann H., Beller M.

Bloome K.S., Alexanian E.J.

A palladium-catalyzed carbonylative Heck-type cyclization of alkyl halides is described. Treatment of a range of primary and secondary alkyl iodides with catalytic palladium(0) under CO pressure forms a variety of synthetically versatile enone products. The reactivity described represents a rare example of a palladium-catalyzed Heck-type cyclization involving unactivated alkyl halides with β-hydrogens. Alkene substitution is well tolerated, and mono- and bicyclic carbocycles may be easily accessed.

Wu X., Anbarasan P., Neumann H., Beller M.

Custar D.W., Le H., Morken J.P.

The Pd-catalyzed addition of organozinc reagents to unsaturated carbonyls in the presence of carbon monoxide provides 1,4-diketones in good yield. The reaction was studied with a number of substituted cyclic and acyclic ketones as well as α,β-unsaturated aldehydes.

Szuroczki P., Jenei L.B., Sándor V., Bényei A., Kollár L.

Xu C., Bao Z., Wang L., Wu X.

A mild cobalt-catalyzed direct aminocarbonylation and alkoxycarbonylation of chloroacetonitrile promoted by an N,N,N-tridentate ligand was established.

Li J., Yang Q., Qi Y., Jiang H.

Wang L., Wu X.

Tao S., Yang Y., Chen L., Xu J., Fu H., Chen H., Jiang W., Li R., Xue W., Zheng X.

Chakraborty P., Mandal R., Sundararaju B.

Abstract Carbonylative transformations for the incorporation of a “C1 unit” in an organic molecule using readily available carbon monoxide gas or other surrogates has witnessed decades of progress under transition metal catalysis. With the necessity for energy‐efficient, economic and environmentally friendly techniques, the scientific research community has been working towards achieving this goal in varied chemical transformations. First‐row transition‐metal‐catalyzed carbonylation not only does serve the purpose but also opens gateway to new reactivity due to its ability to participate in both one‐ and two‐electron transfer reactions. In this chapter, we discuss and summarize the development of cobalt‐catalyzed carbonylative transformations providing an insight into the diverse applications that has been achieved in this field so far.

Mai Q., Dedieu P., Lescot C.

Wang L., Cai Y., Huang Y.

AbstractKetone synthesis via radical coupling mechanisms has recently gained significant attention. Traditionally, these methods have relied on N‐heterocyclic carbenes (NHCs) to generate the key ketyl radical intermediate, either through single‐electron reduction of acyl azolium or single‐electron oxidation involving the Breslow intermediate. In this report, we introduce a novel photoredox protocol that directly generates ketyl radicals from stable acyl imidazoles without the need for NHCs. This approach not only simplifies the process, but also demonstrates broad tolerance for various alkyl radical substrates. Additionally, it can be extended to facilitate relay‐radical coupling reactions.

Liu Z., Yang H., Bao Z., Zhang J., Wu X.

AbstractCarbonylative transformation is already been accepted as a powerful toolbox in synthetic chemistry. However, the manipulation of toxic and smell‐less carbon monoxide gas lagged it from wide range applications. Hence the developing of new and efficient CO surrogates become an attractive topic. Herein, we developed a novel mannitol‐based carbon monoxide surrogate with an enhanced carbon monoxide loading capacity compared to known organic carbon monoxide surrogates. We successfully used it in the palladium‐catalyzed alkoxycarbonylation of aryl bromides with phenols only 0.5 equivalent of it required. This newly designed carbon monoxide surrogate offers additional possibility for further development in CO chemistry.

Tang W., Wu L., Zhou Q., Wan J.

The synthesis of ynones has been realized via visible light-induced alkynylation of carboxylic acids with alkynyl sulfones as the alkynyl source, providing a mild and green new protocol for the synthesis of useful ynones.

Yang M., Liu Y., Yang P., Zhao Y., Wu X.

A photochemically induced carbon monoxide-inclusive four-component carbonylation reaction has been delineated, facilitating the diacylation of styrenes with acyl azolium salts to synthesize valuable 1,4-diketone compounds with moderate to good yields. This process proceeds by generating acyl radicals from the Hantzsch esters and carbon monoxide, which subsequently add to the terminal position of styrenes. Then, under light irradiation, the newly generated carbon radical can further react with activated acyl azolium salts to finish the desired 1,4-diketone products.

Guo M., Yang H., Wang J., Jian Y., Zhang W., Gao Z.

AbstractPalladium‐catalyzed carbonylative C─C coupling reactions provide an efficient route to synthesize natural products and pharmaceuticals through three‐component condensation processes. However, the use of gaseous carbon monoxide (CO) – a colorless, odorless, and toxic gas – has hindered its broad adoption as a C1 source. Addressing this, the development of versatile CO‐releasing molecules (CORMs) and user‐friendly, nongaseous palladium‐catalyzed carbonylation techniques have emerged as a crucial research area. This review outlines recent advancements in the application of CORMs to palladium‐catalyzed carbonylative C─C coupling reactions, with a focus on CO generation mechanisms and carbonyl utilization efficiency. CORMs are classified into three categories: single carbon monoxide releasing molecules (s‐CORMs), multiple carbon monoxide releasing molecules (m‐CORMs), and binary metal carbonyl compounds (BMCCs). By offering a comprehensive overview of the current research landscape and providing practical guidelines for CORM selection, this review aims to assist researchers in developing effective carbonylative strategies.

Yan F., Zhang X., Li D., Zhu N., Bao H.

ABSTRACTMetal‐catalyzed cross‐coupling reactions are essential tools for constructing C–C bonds in organic synthesis. Among these prominent approaches, the Sonogashira reaction stands out as a key player and is widely utilized in medicinal chemistry. This versatile method enables the creation of complex C (sp2)–C (sp) bonds by linking aryl or vinyl halides with terminal alkynes, facilitating the efficient construction of molecular structures crucial for drug development. A notable application of the Sonogashira reaction is its ability to incorporate aromatic and alkynyl functionalities into pharmaceutical compounds. Depending on the impactful catalytic system evolved gradually, the Sonogashira reaction can involve either double‐metal catalysis or single‐metal catalysis. This review sheds light on the diverse applications of the Sonogashira coupling approach in drug synthesis and the generation of their derivatives.

Khan H., Rajesh V.M., Ravva M.K., Sen S.

Zhang S., Mou Q., Cao B., Han T., Liu M.