3167-07-5Relevant academic research and scientific papers
Phosphine-Free Manganese Catalyst Enables Selective Transfer Hydrogenation of Nitriles to Primary and Secondary Amines Using Ammonia-Borane
Sarkar, Koushik,Das, Kuhali,Kundu, Abhishek,Adhikari, Debashis,Maji, Biplab
, p. 2786 - 2794 (2021/03/03)
Herein we report the synthesis of primary and secondary amines by nitrile hydrogenation, employing a borrowing hydrogenation strategy. A class of phosphine-free manganese(I) complexes bearing sulfur side arms catalyzed the reaction under mild reaction conditions, where ammonia-borane is used as the source of hydrogen. The synthetic protocol is chemodivergent, as the final product is either primary or secondary amine, which can be controlled by changing the catalyst structure and the polarity of the reaction medium. The significant advantage of this method is that the protocol operates without externally added base or other additives as well as obviates the use of high-pressure dihydrogen gas required for other nitrile hydrogenation reactions. Utilizing this method, a wide variety of primary and symmetric and asymmetric secondary amines were synthesized in high yields. A mechanistic study involving kinetic experiments and high-level DFT computations revealed that both outer-sphere dehydrogenation and inner-sphere hydrogenation were predominantly operative in the catalytic cycle.
Regio- and stereoselective hydroamination of alkynes using an ammonia surrogate: Synthesis of N -Silylenamines as reactive synthons
Lui, Erica K. J.,Brandt, Jason W.,Schafer, Laurel L.
supporting information, p. 4973 - 4976 (2018/04/24)
An anti-Markovnikov selective hydroamination of alkynes with N-silylamines to afford N-silylenamines is reported. The reaction is catalyzed by a bis(amidate)bis(amido)Ti(IV) catalyst and is compatible with a variety of terminal and internal alkynes. Stoichiometric mechanistic studies were also performed. This method easily affords interesting N-silylenamine synthons in good to excellent yields and the easily removable silyl protecting group enables the catalytic synthesis of primary amines.
Phenethylamines via Heck Arylation of a New Vinylamine Equivalent
Busacca, Carl A.,Johnson, Robert E.,Swestock, John
, p. 3299 - 3303 (2007/10/02)
A new vinylamine equivalent, N-vinyloxazolone 3, has been prepared in three steps and shown to undergo Heck arylation with a variety of substrates.The Heck adducts thus obtained are then converted in one step and high yield to phenethylamine hydrochlorides.As a general synthetic method for preparation of substituted phenethylamines, use of this new reagent is shown to be superior to N-vinylphthalimide in number of steps, regiospecificity, and chemical yield.
