Copper-Catalyzed Rearrangement of Tertiary Amines through Oxidation of Aliphatic CH Bonds in Air or Oxygen: Direct Synthesis of α-Amino Acetals

2010 ◽  
Vol 122 (45) ◽  
pp. 8595-8598 ◽  
Author(s):  
Jie-Sheng Tian ◽  
Teck-Peng Loh
Keyword(s):  
Direct Synthesis ◽  
Tertiary Amines

Tertiary amine-catalyzed and direct synthesis of α-chloroalkanesulfonylhydrazines from azodicarboxylates and sulfonyl chlorides

2016 ◽  
Vol 14 (21) ◽  
pp. 4918-4926 ◽  
Author(s):  
Bingnan Zhou ◽  
Jiaxi Xu
Keyword(s):  
Tertiary Amine ◽  
Direct Synthesis ◽  
Tertiary Amines ◽  
Sulfonyl Chlorides

α-Chloroalkanesulfonylhydrazines were synthesized directly and efficiently from alkanesulfonyl chlorides and dialkyl azodicarboxylates under the catalysis of tertiary amines.

Pt-Sn/γ-Al2O3-Catalyzed Highly Efficient Direct Synthesis of Secondary and Tertiary Amines and Imines

2011 ◽  
Vol 17 (47) ◽  
pp. 13308-13317 ◽  
Author(s):  
Wei He ◽  
Liandi Wang ◽  
Chenglin Sun ◽  
Kaikai Wu ◽  
Songbo He ◽  
...  
Keyword(s):  
Direct Synthesis ◽  
Tertiary Amines ◽  
Highly Efficient

Copper Catalyzed Direct Synthesis of Unsymmetrically Substituted Oxalamides From Bromodifluoroacetamide and Tertiary Amines

2021 ◽  
Vol 10 (4) ◽  
pp. 780-783
Author(s):  
Hongtai Chen ◽  
Lianxin Wang ◽  
Yujie Liu ◽  
Minjie Guo ◽  
Wentao Zhao ◽  
...  
Keyword(s):  
Direct Synthesis ◽  
Tertiary Amines

ChemInform Abstract: Pt-Sn/γ-Al2O3-Catalyzed Highly Efficient Direct Synthesis of Secondary and Tertiary Amines and Imines.

ChemInform ◽  
2012 ◽  
Vol 43 (14) ◽  
pp. no-no
Author(s):  
Wei He ◽  
Liandi Wang ◽  
Chenglin Sun ◽  
Kaikai Wu ◽  
Songbo He ◽  
...  
Keyword(s):  
Direct Synthesis ◽  
Tertiary Amines ◽  
Highly Efficient

Mechanistic Insights into Fe Catalyzed α-C-H Oxidations of Tertiary Amines

2019 ◽  
Author(s):  
Christopher J. Legacy ◽  
Frederick T. Greenaway ◽  
Marion Emmert
Keyword(s):  
Free Radical ◽  
Catalytic Mechanism ◽  
Catalyst System ◽  
Oxidation Products ◽  
Tertiary Amines ◽  
Catalyst Activation ◽  
Rate Determining Step ◽  
Fe Catalyst ◽  
Ligand Coordination ◽  
Rate Kinetics

We report detailed mechanistic investigations of an iron-based catalyst system, which allows the α-C-H oxidation of a wide variety of amines, including acyclic tertiary aliphatic amines, to afford dealkylated or amide products. In contrast to other catalysts that affect α-C-H oxidations of tertiary amines, the system under investigation employs exclusively peroxy esters as oxidants. More common oxidants (e.g. tBuOOH) previously reported to affect amine oxidations via free radical pathways do not provide amine α-C-H oxidation products in combination with the herein described catalyst system. Motivated by this difference in reactivity to more common free radical systems, the investigations described herein employ initial rate kinetics, kinetic profiling, Eyring studies, kinetic isotope effect studies, Hammett studies, ligand coordination studies, and EPR studies to shed light on the Fe catalyst system. The obtained data suggest that the catalytic mechanism proceeds through C-H abstraction at a coordinated substrate molecule. This rate-determining step occurs either at an Fe(IV) oxo pathway or a 2-electron pathway at a Fe(II) intermediate with bound oxidant. We further show via kinetic profiling and EPR studies that catalyst activation follows a radical pathway, which is initiated by hydrolysis of PhCO3 tBu to tBuOOH in the reaction mixture. Overall, the obtained mechanistic data support a non-classical, Fe catalyzed pathway that requires substrate binding, thus inducing selectivity for α-C-H functionalization.<br>

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