797762-23-3 (3-甲氧基苄基硼酸频哪醇酯,2-(3-Methoxybenzyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane)

反应条件：

1.1 Reagents: Potassium hydroxide Catalysts: Bis(tri-tert-butylphosphine)palladium Solvents: 1,4-Dioxane , Water ; 3 h, 25 °C

参考文献：

Chemoselective Suzuki Coupling of Diborylmethane for Facile Synthesis of Benzylboronates

Endo, Kohei; et al, Organic Letters, 2011, 13(13), 3368-3371

合成路线：1 步

1350513-39-1

166330-03-6

_86%

反应条件：

1.1 Reagents: Tripotassium phosphate Catalysts: Tetrakis(triphenylphosphine)palladium Solvents: 1,2-Dichloroethane , Water ; rt → 60 °C; 24 h, 60 °C

参考文献：

Pd-Catalyzed Organometallic-Free Homologation of Arylboronic Acids Enabled by Chemoselective Transmetalation

Bastick, Kane A. C.; et al, ACS Catalysis, 2023, 13(10), 7013-7018

合成路线：1 步

166330-03-6

10365-98-7

_82%

反应条件：

1.1 Reagents: Tripotassium phosphate Catalysts: Tetrakis(triphenylphosphine)palladium Solvents: 1,2-Dichloroethane , Water ; rt → 60 °C; 24 h, 60 °C

参考文献：

A Pd-catalyzed organometallic-free homologation of arylboronic acids enabled by chemoselective transmetalation

Bastick, Kane A. C.; et al, ChemRxiv, 2023, 1, 1-6

合成路线：1 步

166330-03-6

10365-98-7

反应条件：

1.1 Reagents: Water , Tripotassium phosphate Catalysts: Tetrakis(triphenylphosphine)palladium Solvents: 1,2-Dichloroethane ; rt → 60 °C; 24 h, 60 °C

参考文献：

Pd-Catalyzed Homologation of Arylboronic Acids as a Platform for the Diversity-Oriented Synthesis of Benzylic C-X Bonds

Bastick, Kane A. C.; et al, Synlett, 2023, 34(18), 2097-2102

合成路线：1 步

25015-63-8

874-98-6

_80%

反应条件：

1.1 Reagents: Lithium bis(trifluoromethanesulfonyl)imide Solvents: Tetrahydrofuran ; rt
1.2 Solvents: Water ; rt

参考文献：

Electrosynthesis of benzylboronic acids and esters

Pintaric, C.; et al, Tetrahedron Letters, 2004, 45(43), 8031-8033

合成路线：1 步

19350-71-1

_78%

反应条件：

1.1 Reagents: Methanol , Sodium methoxide Solvents: Toluene ; 3 - 12 h, 90 °C

参考文献：

Transition-Metal-Free Synthesis of Pinacol Alkylboronates from Tosylhydrazones

Li, Huan; et al, Angewandte Chemie, 2012, 51(12), 2943-2946

合成路线：1 步

591-31-1

_77%

反应条件：

1.1 Reagents: Methanol , Sodium tert-butoxide Catalysts: Chloro(1,3-dicyclohexyl-1,3-dihydro-2H-imidazol-2-ylidene)copper Solvents: Hexane ; 5 h, 100 °C
1.2 Reagents: Ethyl acetate

参考文献：

Cu-catalyzed deoxygenative gem-hydroborylation of aromatic aldehydes and ketones to access benzylboronic esters

Wang, Lu; et al, Chinese Journal of Catalysis, 2018, 39(11), 1725-1729

合成路线：1 步

874-98-6

_75%

反应条件：

1.1 Reagents: tert-Butyllithium Solvents: Tetrahydrofuran , Heptane
1.2 Catalysts: Ferrous bromide , Dibromo[1,1′-oxybis[ethane]]magnesium Solvents: Tetrahydrofuran ; 1 h, rt

参考文献：

Iron-Catalyzed Borylation of Alkyl, Allyl, and Aryl Halides: Isolation of an Iron(I) Boryl Complex

Bedford, Robin B.; et al, Organometallics, 2014, 33(21), 5940-5943

合成路线：1 步

_74%

反应条件：

1.1 Solvents: Hexane , 1,4-Dioxane ; 4 h, 50 °C
1.2 Reagents: Tetrabutylammonium fluoride Solvents: Tetrahydrofuran , Hexane , Water ; 4 h, 50 °C

参考文献：

One-carbon homologation of arylboronic acids: a convenient approach to the synthesis of pinacol benzylboronates

Wu, Chaoqiang; et al, Organic Chemistry Frontiers, 2016, 3(7), 817-822

合成路线：1 步

78782-17-9

66107-33-3

_66%

反应条件：

1.1 Reagents: Tetrabutylammonium hydroxide Catalysts: Triphenylphosphine , Palladium diacetate Solvents: 1,4-Dioxane , Water ; 1 min, rt
1.2 3 - 6 h, rt

参考文献：

Pd-catalyzed cross-coupling of 1,1-diborylalkanes with aryl triflates

Cui, Long-Can; et al, RSC Advances, 2016, 6(57), 51932-51935

合成路线：1 步

6971-51-3

_55%

反应条件：

1.1 Catalysts: Copper(2+), tetrakis(acetonitrile)-, tetrafluoroborate(1-) (1:2) , 1,1′-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis[1,1-diphenylphosphine] Solvents: tert-Butyl methyl ether ; 5 min, rt
1.2 Reagents: Titanium isopropoxide Solvents: tert-Butyl methyl ether ; 30 h, 100 °C

参考文献：

Synthesis of Benzyl-, Allyl-, and Allenyl-boronates via Copper-Catalyzed Borylation of Alcohols

Mao, Lujia; et al, Organic Letters, 2017, 19(5), 1204-1207

合成路线：1 步

153974-48-2

_50%

反应条件：

1.1 Reagents: Lithium tert-butoxide Catalysts: Bis(acetylacetonato)nickel , 1H-Imidazolium, 1,3-bis[2,6-bis(1-methylethyl)phenyl]-4,5-dimethyl-, chloride (1… Solvents: Cyclopentyl methyl ether ; 16 h, 100 °C

参考文献：

Nickel-Catalyzed Ipso-Borylation of Silyloxyarenes via C-O Bond Activation

Pein, Wesley L. ; et al, Organic Letters, 2021, 23(12), 4588-4592

合成路线：1 步

153974-48-2

_50%

反应条件：

参考文献：

Nickel-catalyzed ipso-borylation of silyloxyarenes via C-O bond activation

Pein, Wesley L.; et al, ChemRxiv, 2021, 1, 1-6

合成路线：1 步

1632411-83-6

874-98-6

反应条件：

1.1 Catalysts: Ferrous bromide , Dibromo[1,1′-oxybis[ethane]]magnesium Solvents: Tetrahydrofuran ; 1 h, rt

参考文献：

Iron-Catalyzed Borylation of Alkyl, Allyl, and Aryl Halides: Isolation of an Iron(I) Boryl Complex

Bedford, Robin B.; et al, Organometallics, 2014, 33(21), 5940-5943

合成路线：2 步

358-23-6

150-19-6

反应条件：

1.1 Reagents: Pyridine Solvents: Dichloromethane ; 0 °C; 1.5 h, rt
1.2 Reagents: Hydrochloric acid Solvents: Diethyl ether , Water ; rt
2.1 Reagents: Tetrabutylammonium hydroxide Catalysts: Triphenylphosphine , Palladium diacetate Solvents: 1,4-Dioxane , Water ; 1 min, rt
2.2 3 - 6 h, rt

参考文献：

Pd-catalyzed cross-coupling of 1,1-diborylalkanes with aryl triflates

Cui, Long-Can; et al, RSC Advances, 2016, 6(57), 51932-51935

合成路线：2 步

18162-48-6

6971-51-3

反应条件：

1.1 Reagents: Imidazole Solvents: Dimethylformamide ; rt
2.1 Reagents: Lithium tert-butoxide Catalysts: Bis(acetylacetonato)nickel , 1H-Imidazolium, 1,3-bis[2,6-bis(1-methylethyl)phenyl]-4,5-dimethyl-, chloride (1… Solvents: Cyclopentyl methyl ether ; 16 h, 100 °C

参考文献：

Nickel-Catalyzed Ipso-Borylation of Silyloxyarenes via C-O Bond Activation

Pein, Wesley L. ; et al, Organic Letters, 2021, 23(12), 4588-4592

合成路线：2 步

18162-48-6

6971-51-3

反应条件：

参考文献：

Nickel-catalyzed ipso-borylation of silyloxyarenes via C-O bond activation

Pein, Wesley L.; et al, ChemRxiv, 2021, 1, 1-6

合成路线：2 步

594-19-4

反应条件：

1.1 Solvents: Tetrahydrofuran , Heptane ; 0 °C
2.1 Catalysts: Ferrous bromide , Dibromo[1,1′-oxybis[ethane]]magnesium Solvents: Tetrahydrofuran ; 1 h, rt

参考文献：

Iron-Catalyzed Borylation of Alkyl, Allyl, and Aryl Halides: Isolation of an Iron(I) Boryl Complex

Bedford, Robin B.; et al, Organometallics, 2014, 33(21), 5940-5943

合成路线：2 步

反应条件：

1.1 Solvents: Dimethylformamide ; 24 h, 40 °C
2.1 Reagents: Tetrabutylammonium hydroxide Catalysts: Triphenylphosphine , Palladium diacetate Solvents: 1,4-Dioxane , Water ; 1 min, rt
2.2 3 - 6 h, rt

参考文献：

Pd-catalyzed cross-coupling of 1,1-diborylalkanes with aryl triflates

Cui, Long-Can; et al, RSC Advances, 2016, 6(57), 51932-51935

合成路线：2 步

76-09-5

反应条件：

1.1 Reagents: Butyllithium , Triisopropyl borate Solvents: Tetrahydrofuran , Hexane ; 2 h, < -80 °C; 1 h, -80 °C; -80 °C → rt; 2 h, rt; rt → 0 °C
1.2 Reagents: Methanesulfonic acid ; 10 min, 0 °C; 0 °C → rt; 1 h, rt
1.3 overnight, rt
2.1 Reagents: Water , Tripotassium phosphate Catalysts: Tetrakis(triphenylphosphine)palladium Solvents: 1,2-Dichloroethane ; rt → 60 °C; 24 h, 60 °C

参考文献：

Pd-Catalyzed Homologation of Arylboronic Acids as a Platform for the Diversity-Oriented Synthesis of Benzylic C-X Bonds

Bastick, Kane A. C.; et al, Synlett, 2023, 34(18), 2097-2102

合成路线：2 步

76-09-5

反应条件：

1.1 Reagents: Butyllithium , Triisopropyl borate Solvents: Tetrahydrofuran , Hexane ; < -80 °C; 2 h, < -80 °C; 1 h, -80 °C; 30 min, -80 °C → rt; 2 min, rt; rt → 0 °C
1.2 Reagents: Methanesulfonic acid ; 10 min, 0 °C; 0 °C → rt; 1 min, rt
1.3 overnight, rt
2.1 Reagents: Tripotassium phosphate Catalysts: Tetrakis(triphenylphosphine)palladium Solvents: 1,2-Dichloroethane , Water ; rt → 60 °C; 24 h, 60 °C

参考文献：

Pd-Catalyzed Organometallic-Free Homologation of Arylboronic Acids Enabled by Chemoselective Transmetalation

Bastick, Kane A. C.; et al, ACS Catalysis, 2023, 13(10), 7013-7018

合成路线：2 步

76-09-5