936618-92-7 (3-氟苯硼酸频那醇酯,3-Fluorophenylboronic acid pinacol ester)

1121-86-4

_100%

反应条件：

1.1 Reagents: Sodium tert-butoxide Catalysts: Diethylzinc Solvents: Tetrahydrofuran , Hexane ; 0 °C; 30 min, rt
1.2 rt → 75 °C; 24 h, 75 °C
1.3 Reagents: Ammonium chloride Solvents: Water

参考文献：

Design, Generation, and Synthetic Application of Borylzincate: Borylation of Aryl Halides and Borylzincation of Benzynes/Terminal Alkyne

Nagashima, Yuki; Takita, Ryo; Yoshida, Kengo; Hirano, Keiichi; Uchiyama, Masanobu, Journal of the American Chemical Society, 2013, 135(50), 18730-18733

合成路线：1 步

_99%

反应条件：

1.1 Reagents: Cesium carbonate Catalysts: Phenothiazine Solvents: Acetonitrile ; 48 h

参考文献：

Visible Light-Induced Borylation of C-O, C-N, and C-X Bonds

Jin, Shengfei; Dang, Hang. T.; Haug, Graham C.; He, Ru; Nguyen, Viet D.; et al, Journal of the American Chemical Society, 2020, 142(3), 1603-1613

合成路线：1 步

625-98-9

_90%

反应条件：

1.1 Reagents: Sodium oxalate , Tripotassium phosphate Catalysts: 4-Cyanopyridine , 2,4,5-Tri-9H-carbazol-9-yl-6-(ethylphenylamino)-1,3-benzenedicarbonitrile Solvents: Acetonitrile ; 24 h, rt
1.2 Reagents: Ammonium chloride Solvents: Ethyl acetate , Water ; rt

参考文献：

Unveiling Extreme Photoreduction Potentials of Donor-Acceptor Cyanoarenes to Access Aryl Radicals from Aryl Chlorides

Xu, Jinhui ; Cao, Jilei; Wu, Xiangyang; Wang, Han; Yang, Xiaona; et al, Journal of the American Chemical Society, 2021, 143(33), 13266-13273

合成路线：1 步

625-98-9

_90%

反应条件：

1.1 Reagents: Sodium oxalate , 4-Cyanopyridine , Tripotassium phosphate Catalysts: 2,4,5-Tri-9H-carbazol-9-yl-6-(ethylphenylamino)-1,3-benzenedicarbonitrile Solvents: Acetonitrile ; 24 h, rt
1.2 Reagents: Ammonium chloride Solvents: Ethyl acetate , Water

参考文献：

Unveiling extreme photoreduction potentials of donor-acceptor cyanoarenes to access aryl radicals from aryl chlorides

Xu, Jinhui; Cao, Jilei; Wu, Xiangyang; Wang, Han; Yang, Xiaona; et al, ChemRxiv, 2021, 1, 1-7

合成路线：1 步

1121-86-4

_78%

反应条件：

1.1 Reagents: Pyridine , Cesium fluoride Solvents: Dimethyl sulfoxide ; rt → 105 °C; 2 h, 105 °C

参考文献：

Radical Metal-Free Borylation of Aryl Iodides

Pinet, Sandra; Liautard, Virginie; Debiais, Megane; Pucheault, Mathieu, Synthesis, 2017, 49(21), 4759-4768

合成路线：1 步

557087-01-1

_76%

反应条件：

1.1 Reagents: Magnesium Catalysts: Iodine Solvents: Tetrahydrofuran ; rt → 45 °C
1.2 Solvents: Tetrahydrofuran ; 45 °C; 5 h, 45 °C
1.3 Solvents: Tetrahydrofuran ; 0 - 5 °C; 1 h, 0 - 5 °C; 5 °C → rt; 2 h, rt
1.4 Reagents: Sodium chloride Solvents: Water

参考文献：

Novel boronizing reagent pinacolyl dimethylamino-borate, and the preparation method and application thereof

, China, , ,

合成路线：1 步

_70%

反应条件：

1.1 Reagents: N,N-Bis(1-methylethyl)boranamine Catalysts: Ferrocene Solvents: Acetonitrile ; 2.5 h, rt
1.2 Reagents: Methanol ; 0 °C; 1 h, rt
1.3 Solvents: Diethyl ether ; 4 h, rt

参考文献：

New process for preparing arylboranes, arylboronates and MIDA-borates by arylation of organoboron compounds with aryldiazonium salts

, World Intellectual Property Organization, , ,

合成路线：1 步

_70%

反应条件：

1.1 Reagents: N,N-Bis(1-methylethyl)boranamine Catalysts: Ferrocene Solvents: Acetonitrile ; 2.5 h, rt
1.2 Reagents: Methanol ; 0 °C; 1 h, rt
1.3 Solvents: Diethyl ether ; 4 h, rt

参考文献：

New process for preparing arylboranes by arylation of organoboron compounds

, European Patent Organization, , ,

合成路线：1 步

_70%

反应条件：

1.1 Reagents: N,N-Bis(1-methylethyl)boranamine Catalysts: Ferrocene Solvents: Acetonitrile ; 2.5 h, rt
1.2 Reagents: Methanol ; 0 °C; 1 h, rt
1.3 Solvents: Diethyl ether ; 4 h, rt

参考文献：

Iron-Catalyzed Borylation of Arenediazonium Salts to Give Access to Arylboron Derivatives via Aryl(amino)boranes at Room Temperature

Marciasini, Ludovic D.; Richy, Nicolas; Vaultier, Michel; Pucheault, Mathieu, Advanced Synthesis & Catalysis, 2013, 355(6), 1083-1088

合成路线：1 步

1121-86-4

_66%

反应条件：

1.1 Catalysts: Bis(dimethylamino)methane Solvents: Acetone , Acetonitrile , Water ; 15 min, -5 °C

参考文献：

Efficient metal-free photochemical borylation of aryl halides under batch and continuous-flow conditions

Chen, Kai; Zhang, Shuai; He, Pei; Li, Pengfei, Chemical Science, 2016, 7(6), 3676-3680

合成路线：1 步

_66%

反应条件：

1.1 Reagents: N,N-Bis(1-methylethyl)boranamine Catalysts: Titanocene dichloride Solvents: Acetonitrile ; 2 h, rt
1.2 Solvents: Methanol ; 0 °C; 1 h, rt
1.3 Solvents: Diethyl ether ; 4 h, rt

参考文献：

Borylation using group IV metallocene under mild conditions

Marciasini, Ludovic D.; Vaultier, Michel; Pucheault, Mathieu, Tetrahedron Letters, 2014, 55(10), 1702-1705

合成路线：1 步

_65%

反应条件：

1.1 Reagents: Pyridine Solvents: Acetone , Water ; 12 h, rt

参考文献：

Redox-Neutral Borylation of Aryl Sulfonium Salts via C-S Activation Enabled by Light

Huang, Chen; Feng, Jie ; Ma, Rui; Fang, Shuaishuai; Lu, Tao; et al, Organic Letters, 2019, 21(23), 9688-9692

合成路线：1 步

_63%

反应条件：

1.1 Reagents: Potassium tert-butoxide Catalysts: Chloro[rel-(3aR,9aS)-1,3,3a,4,9,9a-hexahydro-1,3-bis(1-methylethyl)-4,9[1′,2′]-b… Solvents: tert-Butyl methyl ether ; 25 °C; 4 h, 25 °C
1.2 Reagents: Ammonium chloride Solvents: Water ; 0 °C

参考文献：

A Bicyclic N-Heterocyclic Carbene as a Bulky but Accessible Ligand: Application to the Copper-Catalyzed Borylations of Aryl Halides

Ando, Shin; Matsunaga, Hirofumi; Ishizuka, Tadao, Journal of Organic Chemistry, 2015, 80(19), 9671-9681

合成路线：1 步

372-20-3

_59%

反应条件：

1.1 Reagents: Tripotassium phosphate , Methanaminium, N-[(dimethylamino)fluoromethylene]-N-methyl-, hexafluorophosphate… Catalysts: Bis(1,5-cyclooctadiene)nickel , Tricyclohexylphosphine Solvents: 1,4-Dioxane ; 24 h, 60 °C

参考文献：

Ni-Catalyzed Deoxygenative Borylation of Phenols Via O-Phenyl-uronium Activation

Liu, Xiaojie; Xu, Biping; Su, Weiping, ACS Catalysis, 2022, 12(15), 8904-8910

合成路线：1 步

_57%

反应条件：

1.1 Reagents: Potassium acetate Catalysts: Tetrakis(triphenylphosphine)palladium Solvents: 1,4-Dioxane ; 17 h, 100 °C

参考文献：

Effect of conjugated small molecular electrolytes based on carbazole with N and F atoms for the automatic formation of electron transport layer in polymer solar cell

Kim, Juae; Kim, Yong Ryun; Kim, Minji; Yoon, Chang Jae; Piao, Junying; et al, Synthetic Metals, 2021, 275,

合成路线：1 步

372-18-9

_50%

反应条件：

1.1 Catalysts: Tetramethylammonium fluoride , Bis[1,3-dihydro-1,3-bis(2,4,6-trimethylphenyl)-2H-imidazol-2-ylidene]nickel Solvents: Methylcyclopentane ; 15 h, 80 °C

参考文献：

Preparing (Multi)Fluoroarenes as Building Blocks for Synthesis: Nickel-Catalyzed Borylation of Polyfluoroarenes via C-F Bond Cleavage

Zhou, Jing; Kuntze-Fechner, Maximilian W.; Bertermann, Rudiger; Paul, Ursula S. D.; Berthel, Johannes H. J.; et al, Journal of the American Chemical Society, 2016, 138(16), 5250-5253

合成路线：1 步

372-19-0

_47%

反应条件：

1.1 Reagents: tert-Butyl nitrite Solvents: Acetonitrile

参考文献：

Direct synthesis of arylboronic pinacol esters from arylamines

Qiu, Di; Zhang, Yan; Wang, Jianbo, Organic Chemistry Frontiers, 2014, 1(4), 422-425

合成路线：1 步

372-19-0

_47%

反应条件：

1.1 Reagents: tert-Butyl nitrite Solvents: Acetonitrile ; 2 h, 80 °C

参考文献：

Synthesis of Pinacol Arylboronates from Aromatic Amines: A Metal-Free Transformation

Qiu, Di; Jin, Liang; Zheng, Zhitong; Meng, He; Mo, Fanyang; et al, Journal of Organic Chemistry, 2013, 78(5), 1923-1933

合成路线：1 步

_31%

反应条件：

1.1 Reagents: Potassium acetate Catalysts: [1,1′-Bis(diphenylphosphino)ferrocene]dichloropalladium Solvents: Dimethyl sulfoxide ; 48 h, 80 °C

参考文献：

Group 4 Post-Metallocenes Supported by [OCH2N,C(σ-aryl)] Auxiliaries Bearing a Seven-Membered Metallacycle: Synthesis, Characterization, and Catalysts for Olefin Polymerization

Liu, Cham-Chuen; Liu, Qian; Yiu, Shek-Man; Chan, Michael C. W., Organometallics, 2019, 38(15), 2963-2971

合成路线：1 步

935447-39-5

_30%