scholarly journals Practical N-Alkylation via Homogeneous Iridium-Catalyzed Direct Reductive Amination

2021 ◽  
Author(s):  
Jing Wang ◽  
Xiongyu Yang ◽  
Jingwen Liu ◽  
Guorui Gao ◽  
Haizhou Huang ◽  
...  
Keyword(s):  
Late Stage ◽  
Reductive Amination ◽  
Secondary Amines ◽  
Reaction Conditions ◽  
Iridium Catalysis ◽  
Primary And Secondary Amines ◽  
Aldehydes And Ketones ◽  
Synthetic Routes ◽  
Functionally Diverse ◽  
Selection Of

Abstract Direct reductive amination (DRA) is one of the most efficient methods for amine synthesis. Herein we report a practical homogeneous DRA procedure utilizing iridium catalysis. Applying simple, readily available and inexpensive PPh3 and alike ligands at as low as 0.003 mol%, aldehydes and ketones reductively coupled with primary and secondary amines to efficiently form structurally and functionally diverse amine products, including a set of drugs and their late-stage manipulation. The reaction conditions were exceptionally mild and additive-free, and they tolerated oxygen, moisture, polar protic groups and multiple other functional groups. For targeted products, this methodology is versatile and could offer multiple synthetic routes in regard to the selection of starting materials. The 10 gram-scale synthesis further demonstrated the potential and promise of this procedure in practical amine synthesis.

scholarly journals Synthesis of Highly Enantioenriched Sulfonimidoyl Fluorides and Sulfonimidamides by Stereospecific SuFEx Reaction

2020 ◽  
Author(s):  
Stephanie Greed ◽  
Edward L. Briggs ◽  
Fahima Idiris ◽  
Andrew J. P. White ◽  
Ulrich Lücking ◽  
...  
Keyword(s):  
Late Stage ◽  
Stereoselective Synthesis ◽  
Building Blocks ◽  
Enantioselective Synthesis ◽  
Secondary Amines ◽  
Fluoride Ions ◽  
Primary And Secondary Amines ◽  
Stereospecific Reaction ◽  
Selection Of

Sulfonimidamides present exciting opportunities as chiral isosteres of sulfonamides, with potential for additional directional interactions. Here we present the first modular enantioselective synthesis of sulfonimidamides, including the first stereoselective synthesis of enantioenriched sulfonimidoyl fluorides, and studies on their reactivity. A new route to sulfonimidoyl fluorides is presented from solid bench-stable, NBoc-sulfinamide salt building blocks. Enantioenriched arylsulfonimidoyl fluorides are shown to be readily racemized by fluoride ions. Conditions are developed which trap fluoride, and enable the stereospecific reaction of sulfonimidoyl fluorides with primary and secondary amines (100% es) generating sulfonimidamides with up to 99% ee. Aryl and alkyl sulfonimidoyl fluoride reagents are suitable for mild late stage functionalization reactions, exemplified by coupling with a selection of complex amines in marketed drugs.

Synthesis of Highly Enantioenriched Sulfonimidoyl Fluorides and Sulfonimidamides by Stereospecific SuFEx Reaction

2020 ◽  
Author(s):  
Stephanie Greed ◽  
Edward L. Briggs ◽  
Fahima Idiris ◽  
Andrew J. P. White ◽  
Ulrich Lücking ◽  
...  
Keyword(s):  
Late Stage ◽  
Stereoselective Synthesis ◽  
Building Blocks ◽  
Enantioselective Synthesis ◽  
Secondary Amines ◽  
Fluoride Ions ◽  
Primary And Secondary Amines ◽  
Stereospecific Reaction ◽  
Selection Of

Sulfonimidamides present exciting opportunities as chiral isosteres of sulfonamides, with potential for additional directional interactions. Here we present the first modular enantioselective synthesis of sulfonimidamides, including the first stereoselective synthesis of enantioenriched sulfonimidoyl fluorides, and studies on their reactivity. A new route to sulfonimidoyl fluorides is presented from solid bench-stable, NBoc-sulfinamide salt building blocks. Enantioenriched arylsulfonimidoyl fluorides are shown to be readily racemized by fluoride ions. Conditions are developed which trap fluoride, and enable the stereospecific reaction of sulfonimidoyl fluorides with primary and secondary amines (100% es) generating sulfonimidamides with up to 99% ee. Aryl and alkyl sulfonimidoyl fluoride reagents are suitable for mild late stage functionalization reactions, exemplified by coupling with a selection of complex amines in marketed drugs.

scholarly journals Cross-Linked Cyclodextrins Bimetallic Nanocatalysts: Applications in Microwave-Assisted Reductive Aminations

Molecules ◽  
2020 ◽  
Vol 25 (2) ◽  
pp. 410
Author(s):  
Emanuela Calcio Gaudino ◽  
Elisa Acciardo ◽  
Silvia Tabasso ◽  
Maela Manzoli ◽  
Giancarlo Cravotto ◽  
...  
Keyword(s):  
Reductive Amination ◽  
Nitro Compounds ◽  
Secondary Amines ◽  
Cross Linking ◽  
Reaction Conditions ◽  
One Pot ◽  
Microwave Assisted ◽  
Aldehydes And Ketones ◽  
Bimetallic Nanocatalysts ◽  
High Yields

The optimization of sustainable protocols for reductive amination has been a lingering challenge in green synthesis. In this context, a comparative study of different metal-loaded cross-linked cyclodextrins (CDs) were examined for the microwave (MW)-assisted reductive amination of aldehydes and ketones using either H2 or formic acid as a hydrogen source. The Pd/Cu heterogeneous nanocatalyst based on Pd (II) and Cu (I) salts embedded in a β-CD network was the most efficient in terms of yield and selectivity attained. In addition, the polymeric cross-linking avoided metal leaching, thus enhancing the process sustainability; good yields were realized using benzylamine under H2. These interesting findings were then applied to the MW-assisted one-pot synthesis of secondary amines via a tandem reductive amination of benzaldehyde with nitroaromatics under H2 pressure. The formation of a CuxPdy alloy under reaction conditions was discerned, and a synergic effect due to the cooperation between Cu and Pd has been hypothesized. During the reaction, the system worked as a bifunctional nanocatalyst wherein the Pd sites facilitate the reduction of nitro compounds, while the Cu species promote the subsequent imine hydrogenation affording structurally diverse secondary amines with high yields.

Nonmetal-catalyzed hydroamination of ynamides with amines

2021 ◽  
Author(s):  
Yanru Wang ◽  
Zhen Zhao ◽  
Songkui Lv ◽  
Lixia Ding ◽  
Xiao-Na Wang ◽  
...  
Keyword(s):  
Secondary Amines ◽  
Efficient Synthesis ◽  
Reaction Conditions ◽  
Primary And Secondary Amines

A TfOH-catalyzed hydroamination of ynamides with primary and secondary amines under mild reaction conditions is described for the efficient synthesis of N-arylimines and ethene-1,1-diamines.

Selective synthesis of secondary amines by Pt nanowire catalyzed reductive amination of aldehydes and ketones with ammonia

2012 ◽  
Vol 48 (77) ◽  
pp. 9631 ◽  
Author(s):  
Fenqiang Qi ◽  
Lei Hu ◽  
Shuanglong Lu ◽  
Xueqin Cao ◽  
Hongwei Gu
Keyword(s):  
Reductive Amination ◽  
Secondary Amines ◽  
Selective Synthesis ◽  
Aldehydes And Ketones

scholarly journals A CO2-Catalyzed Transamidation Reaction

2020 ◽  
Author(s):  
Yang Yang ◽  
Jian Liu ◽  
JIWOONG LEE
Keyword(s):  
Transition State ◽  
Bond Formation ◽  
Metal Catalysts ◽  
Amide Bond ◽  
Secondary Amines ◽  
Coupling Reagents ◽  
Reaction Conditions ◽  
Amide Bond Formation ◽  
Primary And Secondary Amines ◽  
Bond Formation Reactions

<div> <div> <div> <p>Amide bond formation reactions are often mediated by reactive substrates in the presence of over-stoichiometric activating reagents and/or catalysts. Here we report a CO2-promoted transamidation reaction without additive metal catalysts or coupling reagents. The reaction forms byproducts, ammonia, primary and secondary amines, which can form adducts with CO2, thereby shifting the equilibrium in the desired direction. A comparison of Hammett studies under CO2 and N2 atmospheres suggests that the reaction transition state can be stabilized by electrophilic CO2. Selective modification of peptides was demonstrated, showing that CO2 can be utilized to control the nature of the electrophilicity and nucleophilicity of reaction partners under practical reaction conditions. </p> </div> </div> </div>

scholarly journals A CO2-Catalyzed Transamidation Reaction

2020 ◽  
Author(s):  
Yang Yang ◽  
Jian Liu ◽  
JIWOONG LEE
Keyword(s):  
Transition State ◽  
Bond Formation ◽  
Metal Catalysts ◽  
Amide Bond ◽  
Secondary Amines ◽  
Coupling Reagents ◽  
Reaction Conditions ◽  
Amide Bond Formation ◽  
Primary And Secondary Amines ◽  
Bond Formation Reactions

<div> <div> <div> <p>Amide bond formation reactions are often mediated by reactive substrates in the presence of over-stoichiometric activating reagents and/or catalysts. Here we report a CO2-promoted transamidation reaction without additive metal catalysts or coupling reagents. The reaction forms byproducts, ammonia, primary and secondary amines, which can form adducts with CO2, thereby shifting the equilibrium in the desired direction. A comparison of Hammett studies under CO2 and N2 atmospheres suggests that the reaction transition state can be stabilized by electrophilic CO2. Selective modification of peptides was demonstrated, showing that CO2 can be utilized to control the nature of the electrophilicity and nucleophilicity of reaction partners under practical reaction conditions. </p> </div> </div> </div>

scholarly journals Reductive amination of fusidane triterpenoid ketones

2018 ◽  
Vol 7 (3) ◽  
pp. 198-203 ◽  
Author(s):  
Elena Salimova ◽  
Andrey Mamaev ◽  
Elena Tretyakova ◽  
Olga Kukovinets ◽  
Lyudmila Parfenova
Keyword(s):  
Methyl Ester ◽  
Fusidic Acid ◽  
Reductive Amination ◽  
Secondary Amines ◽  
Primary And Secondary Amines ◽  
Reaction Proceeds ◽  
Derivatives Of

New nitrogen-containing analogues of fusidane triterpenoids were synthesized via the reductive amination of 3,11-dioxo derivatives of fusidic acid and its methyl ester by primary and secondary amines (BunNH2, Pyrrolidine, NH2CH2CH2NH2) in the presence of sodium borohydrides. The reaction proceeds with high chemo- and stereoselectivity and gives 3β-amino substituted products with yields of 75-88%.

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