Pd/Cu‐Cocatalyzed Aerobic Oxidative Carbonylative Homocoupling of Arylboronic Acids and CO: A Highly Selective Approach to Diaryl Ketones

Ren, Liwei; Jiao, Ning

doi:10.1002/asia.201402326

Cited by 25 publications

(16 citation statements)

References 108 publications

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“…Once the loose, spherical particles further clustered to form the tight, bulky palladium black, it sharply lost the absorption capability, thus losing the alcohol oxidation activity. In the common heterogeneous catalysis with supported palladium catalyst, [24][25][26][27][28][29] the active particles generally had a size less than 10 nm, which is similar to the subunits in these loosely, spherically large nanoparticles in the present study.…”

Section: Resultssupporting

confidence: 68%

Palladium (II)‐catalyzed homogeneous alcohol oxidations: Disclosing the crucial contribution of palladium nanoparticles in catalysis

Zhang

Lou

Xue

et al. 2020

Applied Organom Chemis

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Versatile redox catalysts play the significant roles in alcohol oxidations, in which the mechanisms for homogeneous and heterogeneous alcohol oxidations are generally different. This work introduced a Lewis acid (LA) promoted homogeneous alcohol oxidation with Pd (OAc)2 catalyst by using oxygen balloon as the oxidant source. It was found that adding Lewis acid such as Sc (OTf)3 significantly accelerated Pd (II)‐catalyzed alcohol oxidations; notably, the time courses of oxidations monitored by GC and 1H NMR disclosed that there existed two processes including the initial sluggish oxidation followed by a rapid oxidation. The promotional effect of Lewis acid was attributed to the formation of heterobimetallic Pd (II)/LA species, which improved the oxidizing power of the palladium (II) species, thus accelerating alcohol oxidation in the induction period. Correlating the sizes of in situ generated palladium nanoparticles with the time course of alcohol oxidation further disclosed that the loosely, spherically large nanoparticles, which were composed of many tiny nanoparticles having the size less than 10 nm, were responsible for the rapid oxidation, whereas those highly dispersed, tiny nanoparticles having the size less than 10 nm were not responsible for the rapid oxidation.

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Section: Resultssupporting

confidence: 68%

Palladium (II)‐catalyzed homogeneous alcohol oxidations: Disclosing the crucial contribution of palladium nanoparticles in catalysis

Zhang

Lou

Xue

et al. 2020

Applied Organom Chemis

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“…Physical data are in agreement with those reported in the literature. 39 Bis(2-(thiophen-2-yl)phenyl)methanone (1s). 2,2′-Dibromobenzophenone (600 mg, 1.76 mmol), 2-tributylstannylthiophene (1.4 mL, 4.4 mmol), Pd(PPh 3 ) 4 (100 mg, 5 mol %), and toluene (15 mL) are used; the product is obtained as a pale yellow solid (556 mg, 91%).…”

Section: ■ Materials and Methodsmentioning

confidence: 99%

“…All physical data were in agreement with those reported in the literature. 39 4,4′-Spirobi[indeno [1,2-b]thiophene] (spiro-1s). Bis(2-(thiophen-2-yl)phenyl)methanone (1s) (130 mg, 0.38 mmol), methanesulfonic acid (250 mL), and C = 1.52 mmol•L −1 are stirred at room temperature to obtain the desired compound as a white solid (90 mg, 73%).…”

Section: ■ Materials and Methodsmentioning

confidence: 99%

Prediction of the Synthesis of Spiro Derivatives by Double Intramolecular Aromatic Electrophilic Substitution Using Reactivity Indices

et al. 2019

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The synthesis of heterocyclic spirobifluorene (SBF) analogs generally requires long and complicated synthetic pathways. Despite this synthetic effort, such structural modification allows the (opto)electronic properties of this remarkable three-dimensional node to be tuned especially for molecular electronic applications. For this reason, the development of a simple, robust, and efficient synthetic methodology to introduce various heterocycles in place of classical phenyl rings in the spirofluorene motif is highly and timely desirable. In this context, we describe herein our efforts to develop a straightforward and efficient synthesis leading to replacement of 2 phenyl rings by various heterocycles in spiro compounds from 2,2′-dibromobenzophenone. As the same procedure to form fully heterocyclic compounds failed, an original theoretical approach based mainly on the uncommon Fukui dual function was developed in order to determine clearly the limitation of this strategy and provide an efficient predictive tool. Indeed, such calculation allows prediction of the thermodynamic and kinetic aspects of the synthesis of spiro derivatives using a double aromatic electrophilic substitution. If this procedure reproduces well our experimental results focused on (heterocyclic) SBF compounds, it can be certainly adapted and generalized to other intramolecular substitutions.

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“…Considering that arylboronic acids are readily available and air/moisture-stable reagents, we disclosed a highly selective Pd/Cu cocatalyzed aerobic oxidative carbonylative homocoupling of arylboronic acids (Scheme 30a). [50] The use of simple catalysts under 1 atm atmosphere of CO/O 2 and the tolerance of various functional groups make this transformation applicable for the synthesis of symmetric diaryl ketones.…”

Section: Methodologies Through Other Oxidative Couplingmentioning

confidence: 99%

Reoxidation of Transition‐metal Catalysts with O₂

Jiao

2017

Chin. J. Chem.

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Transition‐metal catalyzed oxidation reactions are central components of organic chemistry. On behalf of green and sustainable chemistry, molecular oxygen (O2) has been considered as an ideal oxidant due to its natural, inexpensive, and environmentally friendly characters, and therefore offers attractive academic and industrial prospects. In recent years, some powerful organic oxidation methods have been continuously developed. Among them, the use of molecular oxygen (O2) as a green and sustainable oxidant has attracted considerable attentions. However, the development of new transition metal‐catalyzed protocols using O2 as an ideal oxidant is highly desirable but very challenging because of the low standard electrode potential of O2 to reoxidize the transition‐metal catalysts. In this Account, we highlight some of our progress toward the use of transition‐metal catalyzed aerobic oxidation reactions. Through the careful selection of ligand and the acidic additives, we have successfully realized the reoxidation of Cu, Pd, Mn, Fe, Ru, Rh, and bimetallic catalysts under O2 or air atmosphere (1 atm) for the oxidative coupling, oxygenation reactions, oxidative C‐H/C‐C bond cleavage, oxidative annulation, and olefins difunctionalization reactions. Most of the reactions can tolerate a range of functional groups. These methods provide new strategies for the green synthesis of alkynes, (α‐keto)amides/esters, ketones/diones, O/N‐heterocycles, β‐azido alcohols, and nitriles. The high efficiency, low cost, and simple operation under air make these methodologies very attractive and practical. We will also discuss the mechanisms of these reactions which might be useful to promote the new type of aerobic oxidative reaction design.

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Pd/Cu‐Cocatalyzed Aerobic Oxidative Carbonylative Homocoupling of Arylboronic Acids and CO: A Highly Selective Approach to Diaryl Ketones

Cited by 25 publications

References 108 publications

Palladium (II)‐catalyzed homogeneous alcohol oxidations: Disclosing the crucial contribution of palladium nanoparticles in catalysis

Palladium (II)‐catalyzed homogeneous alcohol oxidations: Disclosing the crucial contribution of palladium nanoparticles in catalysis

Prediction of the Synthesis of Spiro Derivatives by Double Intramolecular Aromatic Electrophilic Substitution Using Reactivity Indices

Reoxidation of Transition‐metal Catalysts with O₂

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Pd/Cu‐Cocatalyzed Aerobic Oxidative Carbonylative Homocoupling of Arylboronic Acids and CO: A Highly Selective Approach to Diaryl Ketones

Cited by 25 publications

References 108 publications

Palladium (II)‐catalyzed homogeneous alcohol oxidations: Disclosing the crucial contribution of palladium nanoparticles in catalysis

Palladium (II)‐catalyzed homogeneous alcohol oxidations: Disclosing the crucial contribution of palladium nanoparticles in catalysis

Prediction of the Synthesis of Spiro Derivatives by Double Intramolecular Aromatic Electrophilic Substitution Using Reactivity Indices

Reoxidation of Transition‐metal Catalysts with O2

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Reoxidation of Transition‐metal Catalysts with O₂