79-55-0 (潘必定,Pempidine)

_99%

反应条件：

1.1 Reagents: Hydrogen Catalysts: Palladium dihydroxide , Carbon nitride (C3N4) Solvents: Methanol ; 6 h, 1.5 MPa, 30 °C

参考文献：

Underlying Mechanisms of Reductive Amination on Pd-Catalysts: The Unique Role of Hydroxyl Group in Generating Sterically Hindered Amine

Hong, Zeng ; Ge, Xin; Zhou, Shaodong, International Journal of Molecular Sciences, 2022, 23(14),

合成路线：1 步

_99%

反应条件：

1.1 Reagents: Phenylsilane Catalysts: 2278261-44-0 Solvents: Dimethylacetamide ; 2 h, 60 °C

参考文献：

UiO-type metal-organic frameworks with NHC or metal-NHC functionalities for N-methylation using CO2 as the carbon source

Zhang, Xu; Jiang, Yilin; Fei, Honghan, Chemical Communications (Cambridge, 2019, 55(79), 11928-11931

合成路线：1 步

_99%

反应条件：

1.1 Reagents: 9-BBN dimer Catalysts: 2,8,9-Trimethyl-2,5,8,9-tetraaza-1-phosphabicyclo[3.3.3]undecane Solvents: THF-d8 ; 1 h, 1 bar, 90 °C

参考文献：

Carbon dioxide reduction to methylamines under metal-free conditions

Blondiaux, Enguerrand; Pouessel, Jacky; Cantat, Thibault, Angewandte Chemie, 2014, 53(45), 12186-12190

合成路线：1 步

_98%

反应条件：

1.1 Reagents: Poly(methylhydrosiloxane) Catalysts: Phosphonium, methyltriphenyl-, methyl carbonate (1:1) Solvents: Tetrahydrofuran ; 16 h, 1 bar, 70 °C

参考文献：

Tuneable reduction of CO2 - organocatalyzed selective formylation and methylation of amines

Ren, Changyue; Terazzi, Constanza; Werner, Thomas, Green Chemistry, 2024, 26(1), 439-447

合成路线：1 步

_97%

反应条件：

1.1 Reagents: 9-Borabicyclo[3.3.1]nonane Catalysts: 2-[[1,3-Bis[2,6-bis(1-methylethyl)phenyl]-1,3-dihydro-2H-imidazol-2-ylidene]meth… Solvents: Toluene , Tetrahydrofuran ; rt; rt → 100 °C; 1.5 h, 100 °C

参考文献：

Expanding the ligand framework diversity of carbodicarbenes and direct detection of boron activation in the methylation of amines with CO2

Chen, Wen-Ching; Shen, Jiun-Shian; Jurca, Titel; Peng, Chun-Jung; Lin, Yen-Hsu; et al, Angewandte Chemie, 2015, 54(50), 15207-15212

合成路线：1 步

_95%

反应条件：

1.1 Reagents: Poly(methylhydrosiloxane) Catalysts: [1-[2,6-Bis(1-methylethyl)phenyl]-3,3-diethyl-5,5-dimethyl-2-pyrrolidinylidene]c… Solvents: Butyl ether ; 18 h, 80 °C; 80 °C → rt
1.2 Solvents: Water ; rt

参考文献：

CuH-Catalyzed Selective N-Methylation of Amines Using Paraformaldehyde as a C1 Source

Wang, Diedie; Lang, Wanglv; Wang, Wan ; Zou, Qizhuang; Yang, Chunliang; et al, ACS Omega, 2023, 8(33), 30640-30645

合成路线：1 步

_95%

反应条件：

1.1 Reagents: Phenylsilane Solvents: Dimethylformamide ; 24 h, 1 atm, 90 °C; 90 °C → rt
1.2 Reagents: Water ; rt

参考文献：

Catalyst-free N-methylation of amines using CO2

Niu, Huiying; Lu, Lijun; Shi, Renyi; Chiang, Chien-Wei; Lei, Aiwen, Chemical Communications (Cambridge, 2017, 53(6), 1148-1151

合成路线：1 步

74-88-4

_91%

反应条件：

1.1 Solvents: Chloroform ; cooled; 96 h, rt
1.2 Reagents: Sodium hydroxide Solvents: Water

参考文献：

Atom-Efficient Synthesis of Alkynylfluoroborates Using BF3-Based Frustrated Lewis Pairs

Iashin, Vladimir; Chernichenko, Konstantin; Papai, Imre; Repo, Timo, Angewandte Chemie, 2016, 55(45), 14146-14150

合成路线：1 步

_89%

反应条件：

1.1 Reagents: Triethylamine Solvents: Toluene ; 16 h, 130 °C

参考文献：

Transition metal-free methylation of amines with formaldehyde as the reductant and methyl source

Man, Nikki Y. T.; Li, Wanfang; Stewart, Scott G.; Wu, Xiao-Feng, Chimia, 2015, 69(6), 345-347

合成路线：1 步

_84%

反应条件：

1.1 Reagents: Diphenylsilane Catalysts: 2254080-71-0 Solvents: Acetonitrile ; 24 h, 2.7 atm, 120 °C

参考文献：

Diverse catalytic reactivity of a dearomatized PN3P*-nickel hydride pincer complex towards CO2 reduction

Li, Huaifeng; Goncalves, Theo P.; Zhao, Qianyi; Gong, Dirong; Lai, Zhiping; et al, Chemical Communications (Cambridge, 2018, 54(81), 11395-11398

合成路线：1 步

_82%

反应条件：

1.1 Reagents: Poly(methylhydrosiloxane) Catalysts: Tripotassium phosphate , 18-Crown-6 Solvents: Acetonitrile ; 72 h, 1 atm, 80 °C

参考文献：

Scalable direct N-methylation of drug-like amines using 12CO2/13CO2 by simple inorganic base catalysis

Lu, Chunlei; Qiu, Zetian; Zhu, Yiling; Lin, Bo-Lin, Science Bulletin, 2019, 64(11), 723-729

合成路线：1 步

771436-36-3

_75%

反应条件：

1.1 Reagents: Dimethylthiocarbamoyl chloride Solvents: Dichloromethane ; 3 h, rt
1.2 Solvents: Acetonitrile ; reflux

参考文献：

New deoxygenation method for amine N-oxides using dimethylthiocarbamoyl chloride

Caliskan, Hafize; Zaim, Omer, Synthetic Communications, 2010, 40(20), 3078-3083

合成路线：1 步

_69%

反应条件：

1.1 Reagents: Hydrogen Catalysts: Copper nitrate trihydrate , Zirconium oxychloride octahydrate , Tetrachloropalladic acid Solvents: Octane ; 48 h, 160 °C

参考文献：

N-Methylation of amine and nitro compounds with CO2/H2 catalyzed by Pd/CuZrOx under mild reaction conditions

Cui, Xinjiang; Zhang, Yan; Deng, Youquan; Shi, Feng, Chemical Communications (Cambridge, 2014, 50(88), 13521-13524

合成路线：1 步

_65%

反应条件：

1.1 Reagents: Diphenylsilane Catalysts: 1,3-Bis(1,1-dimethylethyl)-2,3-dihydro-1H-1,3,2-diazaphosphole Solvents: Acetonitrile-d3 ; -196 °C; 12 h, 50 °C

参考文献：

Formylation or methylation: what determines the chemoselectivity of the reaction of amine, CO2, and hydrosilane catalyzed by 1,3,2-diazaphospholene?

Lu, Yu; Gao, Zhong-Hua; Chen, Xiang-Yu; Guo, Jiandong; Liu, Zheyuan; et al, Chemical Science, 2017, 8(11), 7637-7650

合成路线：1 步

_53%

反应条件：

1.1 Reagents: Diphenylsilane Catalysts: 1,3-Bis(1,1-dimethylethyl)-2,3-dihydro-1H-1,3,2-diazaphosphole Solvents: Acetonitrile-d3 ; -196 °C; 7 h, rt

参考文献：

Hydrophosphination of CO2 and Subsequent Formate Transfer in the 1,3,2-Diazaphospholene-Catalyzed N-Formylation of Amines

Chong, Che Chang; Kinjo, Rei, Angewandte Chemie, 2015, 54(41), 12116-12120

合成路线：1 步

_45%

反应条件：

1.1 Reagents: Trimethylamineborane Catalysts: 2-Amino-6-methylpyridine Solvents: 1,2-Dichloroethane ; 6 h, 1 atm, 100 °C; 100 °C → rt
1.2 Reagents: Ammonium chloride Solvents: Water

参考文献：

Borane-Trimethylamine Complex as a Reducing Agent for Selective Methylation and Formylation of Amines with CO2

Zhang, Yanmeng; Zhang, He; Gao, Ke, Organic Letters, 2021, 23(21), 8282-8286

合成路线：1 步

_41%

反应条件：

1.1 Reagents: Sodium borohydride Solvents: 1,4-Dioxane ; 10 bar, rt; rt → 100 °C; 24 h, 100 °C; 100 °C → rt
1.2 Solvents: Water ; rt

参考文献：

Catalyst-free selective N-formylation and N-methylation of amines using CO2 as a sustainable C1 source

Zou, Qizhuang; Long, Guangcai; Zhao, Tianxiang; Hu, Xingbang, Green Chemistry, 2020, 22(4), 1134-1138

合成路线：1 步

_32%