Electrochemical Synthesis of Allylic Amines from Terminal Alkenes and Secondary Amines

2021 ◽  
Author(s):  
Diana J. Wang ◽  
Karina Targos ◽  
Zachary K. Wickens
Keyword(s):  
Electrochemical Synthesis ◽  
Secondary Amines ◽  
Allylic Amines ◽  
Terminal Alkenes

Practical regio- and stereoselective azidation and amination of terminal alkenes

2018 ◽  
Vol 16 (48) ◽  
pp. 9354-9358 ◽  
Author(s):  
Olatunji S. Ojo ◽  
Octavio Miranda ◽  
Kyle C. Baumgardner ◽  
Alejandro Bugarin
Keyword(s):  
Allylic Amines ◽  
Reaction Conditions ◽  
Metal Free ◽  
Terminal Alkenes ◽  
Allylic Azides

A metal-free synthesis of allylic azides and allylic amines was achieved under mild reaction conditions, which represents a milder alternative for azidation and amination reactions.

scholarly journals Rhodium(III)-Catalyzed Three-Component 1,2-Diamination of Unactivated Terminal Alkenes

Synthesis ◽  
2019 ◽  
Vol 52 (08) ◽  
pp. 1247-1252 ◽  
Author(s):  
Sumin Lee ◽  
Young Jin Jang ◽  
Erik J. T. Phipps ◽  
Honghui Lei ◽  
Tomislav Rovis
Keyword(s):  
Good Yield ◽  
Ring Opening ◽  
Secondary Amines ◽  
One Pot ◽  
Rapid Access ◽  
Primary And Secondary Amines ◽  
Terminal Alkenes ◽  
Broad Array ◽  
Vicinal Diamines

We report a three-component diamination of simple unactivated alkenes using an electrophilic nitrene source and amine nucleo­philes. The reaction provides rapid access to 1,2-vicinal diamines from terminal alkenes through a one-pot protocol. The transformation proceeds smoothly with excellent tolerance for a broad array of primary and secondary amines, affording the desired products in good yield and regioselectivity. The mechanism is proposed to proceed through a Rh(III)-catalyzed aziridination of alkenes with subsequent ring opening by primary or secondary amines.

scholarly journals Electrochemical Synthesis of Allylic Amines from Alkenes and Amines

2021 ◽  
Author(s):  
Diana Wang ◽  
Karina Targos ◽  
Zachary Wickens
Keyword(s):  
Aliphatic Amine ◽  
Reactive Intermediates ◽  
Building Blocks ◽  
Electrochemical Process ◽  
Biologically Active ◽  
Secondary Amines ◽  
High Yield ◽  
Mechanistic Studies ◽  
Allylic Amines ◽  
Synthetic Strategy

Allylic amines are valuable synthetic targets en route to diverse biologically active amine products. Current allylic C–H amination strate-gies remain limited with respect to the viable N-substituents. Herein we disclose a new electrochemical process to prepare aliphatic allylic amines by coupling two abundant starting materials: secondary amines and unactivated alkenes. This oxidative transformation proceeds via electrochemical generation of an electrophilic adduct between thianthrene and the alkene substrates. Treatment of these adducts with aliphatic amine nucleophiles and base provides allylic amine products in high yield. This synthetic strategy is also amenable to functionali-zation of feedstock gaseous alkenes at 1 atmosphere. In the case of 1-butene, remarkable Z-selective crotylation is observed. This strategy, however, is not limited to the synthesis of simple building blocks; complex biologically active molecules are suitable as both alkene and amine coupling partners. Preliminary mechanistic studies implicate vinylthianthrenium salts as key reactive intermediates.

Electrochemical Synthesis of Hindered Primary and Secondary Amines via Proton-Coupled Electron Transfer

2019 ◽  
Vol 142 (1) ◽  
pp. 468-478 ◽  
Author(s):  
Dan Lehnherr ◽  
Yu-hong Lam ◽  
Michael C. Nicastri ◽  
Jinchu Liu ◽  
Justin A. Newman ◽  
...  
Keyword(s):  
Electron Transfer ◽  
Electrochemical Synthesis ◽  
Secondary Amines ◽  
Proton Coupled Electron Transfer ◽  
Primary And Secondary Amines

Ruthenium-catalyzed regioselective allylic amination of 2,3,3-trifluoroallylic carbonates

2017 ◽  
Vol 15 (14) ◽  
pp. 2938-2946 ◽  
Author(s):  
Shin-ichi Isobe ◽  
Shou Terasaki ◽  
Taisyun Hanakawa ◽  
Shota Mizuno ◽  
Motoi Kawatsura
Keyword(s):  
Allylic Amines ◽  
Allylic Amination ◽  
Terminal Alkenes

Synthesis of trifluorinated terminal alkenes possessing allylic amines by ruthenium-catalyzed branch selective allylic amination.

Electrochemical Synthesis of Cyanoformamides from Trichloroacetonitrile and Secondary Amines Mediated by the B12 Derivative

2021 ◽  
Author(s):  
Mohammad Moniruzzaman ◽  
Yoshio Yano ◽  
Toshikazu Ono ◽  
Kenji Imamura ◽  
Yoshihito Shiota ◽  
...  
Keyword(s):  
Electrochemical Synthesis ◽  
Secondary Amines

ANIPE-Cu Catalyst Enables Highly Enantioselective Markovnikov Hydroboration of α-Olefins

Synlett ◽  
2020 ◽  
Author(s):  
Shi-Liang Shi ◽  
Yuan Cai
Keyword(s):  
Petrochemical Industry ◽  
Future Directions ◽  
Asymmetric Hydroboration ◽  
Terminal Alkenes ◽  
Cu Catalyst

AbstractAsymmetric hydroboration of simple and unactivated terminal alkenes (α-olefins), feedstock chemicals derived from the petrochemical industry, has not been efficiently realized for past decades. Using a bulky ANIPE ligand, we achieved a rare example of highly enantioselective copper-catalyzed Markovnikov hydroboration of α-olefins. The chiral secondary alkylboronic ester products were obtained in moderate to good yields and regioselectivities with excellent enantioselectivities.1 Introduction2 Conditions Optimization3 Substrate Scope4 Application5 Mechanistic Discussion6 Conclusions and Future Directions

Acceptorless amine dehydrogenation and transamination using Pd-doped layered double hydroxides

2018 ◽  
Author(s):  
Diana Ainembabazi ◽  
Nan An ◽  
Jinesh Manayil ◽  
Kare Wilson ◽  
Adam Lee ◽  
...  
Keyword(s):  
Layered Double Hydroxides ◽  
Oxidation States ◽  
Secondary Amines ◽  
Primary Amines ◽  
Acid Dissolution ◽  
Oxidative Amination ◽  
Strong Function ◽  
Excellent Activity ◽  
High Yields ◽  
Double Hydroxides

<div> <p>The synthesis, characterization, and activity of Pd-doped layered double hydroxides (Pd-LDHs) for for acceptorless amine dehydrogenation is reported. These multifunctional catalysts comprise Brønsted basic and Lewis acidic surface sites that stabilize Pd species in 0, 2+, and 4+ oxidation states. Pd speciation and corresponding cataytic performance is a strong function of metal loading. Excellent activity is observed for the oxidative transamination of primary amines and acceptorless dehydrogenation of secondary amines to secondary imines using a low Pd loading (0.5 mol%), without the need for oxidants. N-heterocycles, such as indoline, 1,2,3,4-tetrahydroquinoline, and piperidine, are dehydrogenated to the corresponding aromatics with high yields. The relative yields of secondary imines are proportional to the calculated free energy of reaction, while yields for oxidative amination correlate with the electrophilicity of primary imine intermediates. Reversible amine dehydrogenation and imine hydrogenation determine the relative imine:amine selectivity. Poisoning tests evidence that Pd-LDHs operate heterogeneously, with negligible metal leaching; catalysts can be regenerated by acid dissolution and re-precipitation.</p> </div> <br>

Sign in / Sign up

Export Citation Format

Share Document