59528-27-7Relevant articles and documents
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.
Catalytic Staudinger Reduction at Room Temperature
Lenstra, Danny C.,Wolf, Joris J.,Mecinovi?, Jasmin
, p. 6536 - 6545 (2019/05/24)
We report an efficient catalytic Staudinger reduction at room temperature that enables the preparation of a structurally diverse set of amines from azides in excellent yields. The reaction is based on the use of catalytic amounts of triphenylphosphine as a phosphine source and diphenyldisiloxane as a reducing agent. Our catalytic Staudinger reduction exhibits a high chemoselectivity, as exemplified by reduction of azides over other common functionalities, including nitriles, alkenes, alkynes, esters, and ketones.
Boron-Catalyzed Silylative Reduction of Nitriles in Accessing Primary Amines and Imines
Gandhamsetty, Narasimhulu,Jeong, Jinseong,Park, Juhyeon,Park, Sehoon,Chang, Sukbok
, p. 7281 - 7287 (2015/07/28)
Silylative reduction of nitriles was studied under transition metal-free conditions by using B(C6F5)3 as a catalyst with hydrosilanes as a reductant. Alkyl and (hetero)aryl nitriles were efficiently converted to primary amines or imines under mild conditions. The choice of silanes was found to determine the selectivity: while a full reduction of nitriles was highly facile, the use of sterically bulky silanes allowed for the partial reduction leading to N-silylimines.
