Highly Regioselective Palladium‐Catalyzed Carboxylation of Allylic Alcohols with CO<sub>2</sub>

Mita, Tsuyoshi; Higuchi, Yuki; Sato, Yoshihiro

doi:10.1002/chem.201503359

Cited by 94 publications

(33 citation statements)

References 74 publications

(24 reference statements)

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“…48 In all cases analyzed, α-branched carboxylic acids were exclusively obtained regardless of whether linear or α-branched allyl alcohols were utilized. The authors demonstrated the utility of this protocol by promoting a one-pot carboxylation using simple aldehydes as starting precursors.…”

Section: Direct Catalytic Carboxylation Of C–heteroatom Bonds With Co2mentioning

confidence: 95%

Metal-Catalyzed Carboxylation of Organic (Pseudo)halides with CO₂

et al. 2016

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The recent years have witnessed the development of metal-catalyzed reductive carboxylation of organic (pseudo)halides with CO2 as C1 source, representing potential powerful alternatives to existing methodologies for preparing carboxylic acids, privileged motifs in a myriad of pharmaceuticals and molecules displaying significant biological properties. While originally visualized as exotic cross-coupling reactions, a close look into the literature data indicates that these processes have become a fertile ground, allowing for the utilization of a variety of coupling partners, even with particularly challenging substrate combinations. As for other related cross-electrophile scenarios, the vast majority of reductive carboxylation of organic (pseudo)halides are characterized by their simplicity, mild conditions, and a broad functional group compatibility, suggesting that these processes could be implemented in late-stage diversification. This perspective describes the evolution of metal-catalyzed reductive carboxylation of organic (pseudo)halides from its inception in the pioneering stoichiometric work of Osakada to the present. Specific emphasis is devoted to the reactivity of these coupling processes, with substrates ranging from aryl-, vinyl-, benzyl- to unactivated alkyl (pseudo)halides. Despite the impressive advances realized, a comprehensive study detailing the mechanistic intricacies of these processes is still lacking. Some recent empirical evidence reveal an intriguing dichotomy exerted by the substitution pattern on the ligands utilized; still, however, some elementary steps within the catalytic cycle of these reactions remain speculative, in many instances invoking a canonical cross-coupling process. Although tentative, we anticipate that these processes might fall into more than one distinct mechanistic category depending on the substrate utilized, suggesting that investigations aimed at unraveling the mechanistic underpinnings of these processes will likely bring new and innovative research grounds in this vibrant area of expertise.

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Section: Direct Catalytic Carboxylation Of C–heteroatom Bonds With Co2mentioning

confidence: 95%

Metal-Catalyzed Carboxylation of Organic (Pseudo)halides with CO₂

et al. 2016

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“…[4] Tsuji and co-workers applied [NiCl 2 (PPh 3 ) 2 ]f or the carboxylation of more inert aryl and vinyl chlorides under aC O 2 pressure of 1atm at room temperature. [5] Later,avariety of surrogates,i ncluding sulfonates, [6] ester derivatives, [7] allylic alcohols, [8] and ammonium salts [9] were devised to complement the reaction scope. Notably,a ll of these systems require stoichiometric metal reagents based on Et 2 Zn, Mn, or Zn powder as reducing agents (Scheme 1a).…”

mentioning

confidence: 99%

Carboxylation of Aromatic and Aliphatic Bromides and Triflates with CO₂ by Dual Visible‐Light–Nickel Catalysis

2017

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We report the efficient carboxylation of bromides and triflates with K 2 CO 3 as the source of CO 2 in the presence of an organic photocatalyst in combination with anickel complex under visible light irradiation at room temperature.T he reaction is compatible with av ariety of functional groups and has been successfully applied to the synthesis and derivatization of biologically active molecules.I np articular, the carboxylation of unactivated cyclic alkyl bromides proceeded well with our protocol, thus extending the scope of this transformation. Spectroscopic and spectroelectrochemical investigations indicated the generation of aN i 0 species as ac atalytic reactive intermediate. Scheme 1. Carboxylation of bromides.

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“…[7] Oxidative addition of the allylic C (sp 3 )À H bond to I affords η 3 -allylcobalt(III) intermediate II, which is tautomerized to η 1 -allylcobalt(III) intermediate III with the assistance of the oxygen atom in the Xantphos ligand. The cobalt atom should be located at the terminal position to avoid steric repulsion between the bulky Xantphos ligand and an alkyl substituent (similar to nucleophilic η 1 -allylpalladium species [13,14] ). Subsequently, reductive elimination of methane from III leads to a low-valent allylcobalt(I) species IV, and CÀ C bond formation with the ketone moiety occurs to produce cobalt(I) alkoxide V. In this step, the nucleophilic addition takes place from IV rather than IV' to avoid steric repulsion between the bulky Xantphos ligand and the phenyl substituent, affording syn-oriented intermediate V. Transmetallation of V with AlMe 3 furnishes the branched aluminum alkoxide VI and regenerates I. Alkoxide VI is converted into product 2 a upon workup.…”

Section: Communications Ascwiley-vchdementioning

confidence: 99%

Catalytic Intramolecular Coupling of Ketoalkenes by Allylic C(sp³)−H Bond Cleavage: Synthesis of Five‐ and Six‐Membered Carbocyclic Compounds

2020

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In the presence of a catalytic amount of cobalt(II) acetylacetonate/Xantphos in combination with trimethylaluminum, various ketoalkenes underwent an intramolecular cyclization reaction triggered by cleavage of the allylic C(sp3)−H bond, affording carbocyclic compounds with high regio‐ and diastereoselectivity. Mono‐, bi‐, and tricarbocyclic compounds were produced in good yields. One of the products thus obtained was derivatized into tramadol in four simple steps. Notably, these intramolecular cyclizations took place in the absence of a gem‐disubstituent on the tethered carbon chain (without the Thorpe‐Ingold effect).

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Highly Regioselective Palladium‐Catalyzed Carboxylation of Allylic Alcohols with CO₂

Cited by 94 publications

References 74 publications

Metal-Catalyzed Carboxylation of Organic (Pseudo)halides with CO₂

Metal-Catalyzed Carboxylation of Organic (Pseudo)halides with CO₂

Carboxylation of Aromatic and Aliphatic Bromides and Triflates with CO₂ by Dual Visible‐Light–Nickel Catalysis

Catalytic Intramolecular Coupling of Ketoalkenes by Allylic C(sp³)−H Bond Cleavage: Synthesis of Five‐ and Six‐Membered Carbocyclic Compounds

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Highly Regioselective Palladium‐Catalyzed Carboxylation of Allylic Alcohols with CO2

Cited by 94 publications

References 74 publications

Metal-Catalyzed Carboxylation of Organic (Pseudo)halides with CO2

Metal-Catalyzed Carboxylation of Organic (Pseudo)halides with CO2

Carboxylation of Aromatic and Aliphatic Bromides and Triflates with CO2 by Dual Visible‐Light–Nickel Catalysis

Catalytic Intramolecular Coupling of Ketoalkenes by Allylic C(sp3)−H Bond Cleavage: Synthesis of Five‐ and Six‐Membered Carbocyclic Compounds

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Highly Regioselective Palladium‐Catalyzed Carboxylation of Allylic Alcohols with CO₂

Metal-Catalyzed Carboxylation of Organic (Pseudo)halides with CO₂

Metal-Catalyzed Carboxylation of Organic (Pseudo)halides with CO₂

Carboxylation of Aromatic and Aliphatic Bromides and Triflates with CO₂ by Dual Visible‐Light–Nickel Catalysis

Catalytic Intramolecular Coupling of Ketoalkenes by Allylic C(sp³)−H Bond Cleavage: Synthesis of Five‐ and Six‐Membered Carbocyclic Compounds