Silver(i)-catalyzed carboxylation of arylboronic esters with CO2

Zhang, Xiǎo; Zhang, Wenzhen; Shi, Ling‐Long; Guo, Cheng; Zhang, Lingling; Lu, Xiao‐Bing

doi:10.1039/c2cc32045b

Cited by 83 publications

(24 citation statements)

References 60 publications

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“…5. 58 catalysts has been developed. These coupling reagents exhibit milder nucleophilicity, better stability to air and moisture as well as higher compatibility with sensitive functional groups.…”

Section: Box 1 | Coordination Modes Of Co 2 With Transition Metalsmentioning

confidence: 99%

Using carbon dioxide as a building block in organic synthesis

et al. 2015

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Carbon dioxide exits in the atmosphere and is produced by the combustion of fossil fuels, the fermentation of sugars and the respiration of all living organisms. An active goal in organic synthesis is to take this carbon-trapped in a waste product-and re-use it to build useful chemicals. Recent advances in organometallic chemistry and catalysis provide effective means for the chemical transformation of CO 2 and its incorporation into synthetic organic molecules under mild conditions. Such a use of carbon dioxide as a renewable one-carbon (C1) building block in organic synthesis could contribute to a more sustainable use of resources.A more sensible resource management is the prerequisite for the sustainable development of future generations. However, when dealing with the feedstock of the chemical industry, the level of sustainability is still far from satisfactory. Until now, the vast majority of carbon resources are based on crude oil, natural gas and coal. In addition to biomass, CO 2 offers the possibility to create a renewable carbon economy. Since pre-industrial times, the amount of CO 2 has steadily increased and nowadays CO 2 is a component of greenhouse gases, which are primarily responsible for the rise in atmospheric temperature and probably abnormal changes in the global climate. This increase in CO 2 concentration is largely due to the combustion of fossil fuels, which are required to meet the world's energy demand 1 . Obviously, there is an urgent need to control CO 2 emissions and develop efficient carbon capture systems. Although the extensive use of carbon dioxide for chemical production cannot solve this problem alone, CO 2 is a useful one-carbon (C1) building block in organic synthesis due to its abundance, availability, nontoxicity and recyclability. As a result, valorization of CO 2 is currently receiving considerable and ever increasing attention by the scientific community 2-4 . However, activation and utilization of CO 2 is still problematic due to the fact that it is the most oxidized form of carbon, which is also thermodynamically stable and/or kinetically inert in certain desired transformations. Consequently, most of the known studies used highly reactive substrates and/or severe reaction conditions to activate CO 2 , limiting the application of such methods. In particular, the catalytic coupling of CO 2 with energy-rich substrates, such as epoxides and aziridines, to generate polycarbonates/polycarbamates and/or cyclic carbonates/carbamates has drawn significant attention over the past decades. To create C-C bonds with CO 2 , the use of carbon nucleophiles is specifically limited to strong nucleophilic organolithiums and Grignard reagents, as well as phenolates.

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Section: Box 1 | Coordination Modes Of Co 2 With Transition Metalsmentioning

confidence: 99%

Using carbon dioxide as a building block in organic synthesis

et al. 2015

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“…To date, two types of catalytic transformations using CO 2 with CC bond formation have been investigated intensively: a) the substitution of Ar–Y with CO 2 (Scheme ) and b) the hydrocarboxylation of C–C unsaturates (Scheme ). The former reactions involve the carboxylations of organozinc3a,b and organoborane3c–f compounds, CH bonds,3g‐j and bromoarenes3k (Scheme ). Recently, we reported the Ni‐catalyzed carboxylation of chloroarenes with CO 2 in the presence of Mn powder under ambient conditions 4a.…”

Section: Methodsmentioning

confidence: 99%

“…Some control experiments were carried out (Scheme ) to provide an insight into the silacarboxylation mechanism. There is some possibility that the reaction could proceed stepwise through two sequential known reactions, that is, the silaboration of an alkyne15 followed by the carboxylation of the resulting vinylboronic ester 3c–f. Thus, we first prepared a possible intermediate 4 i 15a through the silaboration of 1 i with Me 2 PhSi‐B(pin).…”

Section: Methodsmentioning

confidence: 99%

Copper‐Catalyzed Silacarboxylation of Internal Alkynes by Employing Carbon Dioxide and Silylboranes

et al. 2012

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“…More recently, Iwasawa reported the first carboxylation of organoboronates in the presence of a rhodium catalyst . Copper‐ and silver‐based catalytic systems for this reaction have been developed subsequently, and Nolan recently reported a nickel catalyst for this reaction (see Scheme ) . These findings triggered the attention of the synthetic community, leading to intense studies in the field…”

Section: Introductionmentioning

confidence: 99%

Mechanism of the Catalytic Carboxylation of Alkylboronates with CO₂ Using Ni−NHC Complexes: A DFT Study

Delarmelina

Marelli

Carneiro

et al. 2017

Chemistry A European J

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A new mechanism is proposed for the Ni-catalyzed carboxylation of organoboronates with CO . DFT investigations at the PBE0-D3 level have shown that direct CO addition to the catalysts [Ni(NHC)(Allyl)Cl] (1 , NHC=IMe, IPr, SIPr and IPr*) is kinetically disfavored and formation of the Aresta-type intermediate is unlikely to occur. According to the mechanism proposed here, the carboxylation process starts with addition of the borate species to 1 , followed by transmetalation, CO cycloaddition and carboxylation. The rate-determining step was identified as being the transmetalation process, with computed relative free energy barriers of 34.8, 36.8, and 33.5 kcal mol for 1 , 1 and 1 , respectively.

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Silver(i)-catalyzed carboxylation of arylboronic esters with CO2

Abstract: A variety of arylboronic esters were efficiently carboxylated with CO(2) using a simple AgOAc/PPh(3) catalyst, affording the corresponding carboxylic acids in good yield. This simple and efficient silver(i) catalytic system showed wide functional group compatibility.

Cited by 83 publications

References 60 publications

Using carbon dioxide as a building block in organic synthesis

Using carbon dioxide as a building block in organic synthesis

Copper‐Catalyzed Silacarboxylation of Internal Alkynes by Employing Carbon Dioxide and Silylboranes

Mechanism of the Catalytic Carboxylation of Alkylboronates with CO₂ Using Ni−NHC Complexes: A DFT Study

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Silver(i)-catalyzed carboxylation of arylboronic esters with CO2

Abstract: A variety of arylboronic esters were efficiently carboxylated with CO(2) using a simple AgOAc/PPh(3) catalyst, affording the corresponding carboxylic acids in good yield. This simple and efficient silver(i) catalytic system showed wide functional group compatibility.

Cited by 83 publications

References 60 publications

Using carbon dioxide as a building block in organic synthesis

Using carbon dioxide as a building block in organic synthesis

Copper‐Catalyzed Silacarboxylation of Internal Alkynes by Employing Carbon Dioxide and Silylboranes

Mechanism of the Catalytic Carboxylation of Alkylboronates with CO2 Using Ni−NHC Complexes: A DFT Study

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Mechanism of the Catalytic Carboxylation of Alkylboronates with CO₂ Using Ni−NHC Complexes: A DFT Study