Mechanistic Insight into the Nickel‐Catalyzed Cross‐Coupling of Aryl Phosphates with Arylboronic Acids: Potassium Phosphate is Not a Spectator Base but is Involved in the Transmetalation Step in the Suzuki–Miyaura Reaction

Liu, Liu; Zhang, Shuangyan; Chen, Hu; Lv, Ye; Zhu, Jun; Zhao, Yufen

doi:10.1002/asia.201300688

Cited by 36 publications

(20 citation statements)

References 72 publications

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“…At first, Na 2 CO 3 reacts with the oxidative addition intermediate C with almost no energy barrier, and leads to the formation of the unprecedented Ni-[NaCO 3 NaOPh] cluster complex D ( Fig. 2b ) 24 25 35 36 37 . Overall reaction, C +Na 2 CO 3 → D , is found to be exergonic by 22.2 kcal mol −1 .…”

Section: Resultsmentioning

confidence: 99%

Decarbonylative organoboron cross-coupling of esters by nickel catalysis

et al. 2015

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The Suzuki–Miyaura cross-coupling is a metal-catalysed reaction in which boron-based nucleophiles and halide-based electrophiles are reacted to form a single molecule. This is one of the most reliable tools in synthetic chemistry, and is extensively used in the synthesis of pharmaceuticals, agrochemicals and organic materials. Herein, we report a significant advance in the choice of electrophilic coupling partner in this reaction. With a user-friendly and inexpensive nickel catalyst, a range of phenyl esters of aromatic, heteroaromatic and aliphatic carboxylic acids react with boronic acids in a decarbonylative manner. Overall, phenyl ester moieties function as leaving groups. Theoretical calculations uncovered key mechanistic features of this unusual decarbonylative coupling. Since extraordinary numbers of ester-containing molecules are available both commercially and synthetically, this new ‘ester' cross-coupling should find significant use in synthetic chemistry as an alternative to the standard halide-based Suzuki–Miyaura coupling.

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Section: Resultsmentioning

confidence: 99%

Decarbonylative organoboron cross-coupling of esters by nickel catalysis

et al. 2015

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“…We noticed that water could promote the conversion of chlorobenzene to 62% which might be due to the better solubility of the base in toluene/H 2 O (2.5:1) mixed solvents ( Table 3 , entry 1). Bases have been proven to play an important role in Suzuki coupling reactions [ 74 ]. Then, in mixed solvents, various bases were examined ( Table 3 , entries 1–10).…”

Section: Resultsmentioning

confidence: 99%

Highly bulky and stable geometry-constrained iminopyridines: Synthesis, structure and application in Pd-catalyzed Suzuki coupling of aryl chlorides

Lai¹,

Zong²,

Tang³

et al. 2017

Beilstein J. Org. Chem.

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A series of bulky geometry-constrained iminopyridylpalladium chlorides were developed. The steric environment adjacent to the nitrogen atom in the pyridine rings and diimine parts enhanced the thermal stability of the palladium species. Bulkier groups at the imino group stabilized the palladium species and the corresponding palladium chlorides showed high activities in the coupling reaction of aryl chlorides.

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“…Phosphate anion is able to coordinate to arylboronic acids, the former and the latter act as Lewis's base and acid respectively. This complex improves the leaving character of the boronic group . Within the scope of this study, a new modification was developed by the addition of K 3 PO 4 in the reaction.…”

Section: Resultsmentioning

confidence: 99%

A Green Alternative for the Conversion of Arylboronic Acids/Esters into Phenols Promoted by a Reducing Agent, Sodium Sulfite

2019

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Hydroxylation of arylboronic acids and arylboronic esters using sodium sulfite and oxygen as the source of ultimate oxidant proceeds rapidly in water under transition metal‐free conditions. This remarkable mild and environmentally benign protocol represents a green alternative to synthesize phenols using inexpensive starting materials in a simple methodology. This new application for sodium sulfite shows a wide tolerance of functional groups, and it is compatible with oxidizable functionalities.

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Mechanistic Insight into the Nickel‐Catalyzed Cross‐Coupling of Aryl Phosphates with Arylboronic Acids: Potassium Phosphate is Not a Spectator Base but is Involved in the Transmetalation Step in the Suzuki–Miyaura Reaction

Cited by 36 publications

References 72 publications

Decarbonylative organoboron cross-coupling of esters by nickel catalysis

Decarbonylative organoboron cross-coupling of esters by nickel catalysis

Highly bulky and stable geometry-constrained iminopyridines: Synthesis, structure and application in Pd-catalyzed Suzuki coupling of aryl chlorides

A Green Alternative for the Conversion of Arylboronic Acids/Esters into Phenols Promoted by a Reducing Agent, Sodium Sulfite

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