70720-38-6Relevant academic research and scientific papers
Copper-catalyzed direct amination of benzylic hydrocarbons and inactive aliphatic alkanes with arylamines
Jin, Shengzhou,Lin, Sen,Xie, Bo,Yan, Zhaohua,Yao, Hua,Zhong, Xiaoyang
supporting information, p. 3263 - 3268 (2020/05/14)
A new synthetic method toward direct C-N bond formation through saturated C-H amination of benzylic hydrocarbons and inactive aliphatic alkanes with primary aromatic amines under an inexpensive catalyst/oxidant (Cu/DTBP) system has been developed. Both aminopyridines and anilines could react smoothly with primary and secondary benzylic C-H substrates or cyclohexane to form the corresponding aromatic secondary amines in moderate to good yields. This protocol has the advantages of wide functional group tolerance and use of readily available raw materials.
Reductions of Imines Using Zirconocene Chloride Hydride
Vargová, Denisa,Mudráková, Brigita,Némethová, Ivana,?ebesta, Radovan
, p. 7606 - 7612 (2019/12/03)
Herein, we describe the fast, chemoselective, and clean reduction of imines with zirconocene chloride hydride. The reaction works well on aromatic and enolizable aliphatic aldimines, as well as ketimines. A range of N-protecting groups and various functio
Toluene and its Derivatives as Atom-Efficient Benzylating Agents for Secondary Amines
Sch?nbauer, David,Lukas, Florian,Schnürch, Michael
supporting information, p. 94 - 98 (2019/01/04)
Toluene as a replacement for common N -benzylating agents, such as benzyl bromide, can be an atom-efficient alternative reagent. Under nickel catalysis and mildly oxidative conditions, it is possible to activate toluene efficiently and use it directly for the benzylation of different 2-aminopyridines. The transformation is not restricted to simple toluene, but also substituted derivatives give the desired product in good yields. Effective cleavage of the pyridine moiety is presented.
Investigations of the generality of quaternary ammonium salts as alkylating agents in direct C-H alkylation reactions: Solid alternatives for gaseous olefins
Sch?nbauer, David,Spettel, Manuel,Pollice, Robert,Pittenauer, Ernst,Schnürch, Michael
supporting information, p. 4024 - 4030 (2019/04/29)
C-H alkylation reactions using short chain olefins as alkylating agents could be operationally simplified on the lab scale by using quaternary ammonium salts as precursors for these gaseous reagents: Hofmann elimination delivers in situ the desired alkenes with the advantage that the alkene concentration in the liquid phase is high. In case a catalytic system did not tolerate the conditions for Hofmann elimination, a very simple spatial separation of both reactions, Hofmann elimination and direct alkylation, was achieved to circumvent possible side reactions or catalyst deactivation. Additionally, the truly catalytically active species of a rhodium(i) mediated alkylation reaction could be identified by using this approach.
Rhodium-catalyzed direct alkylation of benzylic amines using alkyl bromides
Anschuber, Martin,Pollice, Robert,Schnürch, Michael
, p. 127 - 138 (2018/11/23)
Within this contribution, the development and substrate scope evaluation of a direct alkylation protocol of the C(sp3)–H bond of benzylic amines using alkyl bromides is reported. This pyridine-directed method is initiated by elimination of the alkyl bromide to a terminal olefin, which is then the true alkylating agent. Graphical abstract: [Figure not available: see fulltext.].
A borrowing hydrogen methodology: Palladium-catalyzed dehydrative: N -benzylation of 2-aminopyridines in water
Hikawa, Hidemasa,Imamura, Hirokazu,Kikkawa, Shoko,Azumaya, Isao
supporting information, p. 3044 - 3049 (2018/07/13)
We demonstrate a greener borrowing hydrogen methodology using the π-benzylpalladium system, which offers an efficient and environmentally friendly dehydrative N-monobenzylation of 2-aminopyridines with benzylic alcohols in the absence of base. The crossover experiment using benzyl-α,α-d2 alcohol and 3-methylbenzyl alcohol afforded H/D scrambled products, suggesting that the dehydrative N-benzylation in our catalytic system involves a borrowing hydrogen pathway. KIE experiments show that C-H bond cleavage at the benzylic position of benzyl alcohol is involved in the rate-determining step (KIE = 2.9). This simple base-free protocol can be achieved under mild conditions in an atom-economic process, affording the desired products in moderate to excellent yields.
Hemilabile N-heterocyclic carbene (NHC)-nitrogen-phosphine mediated Ru (II)-catalyzed N-alkylation of aromatic amine with alcohol efficiently
Yu, Xiao-Jun,He, Hai-Yu,Yang, Lei,Fu, Hai-Yan,Zheng, Xue-Li,Chen, Hua,Li, Rui-Xiang
, p. 54 - 57 (2017/03/22)
Based on the hemilability, a novel N-heterocyclic carbene (NHC)-nitrogen-phosphine ligand (1) was synthesized, and the combination of it with [Ru(COD)Cl2]n showed the high activity and selectivity with a low Ru loading of 0.1% for the N-alkylation of amine with alcohol. Especially, for these substrates with pyridine backbone, even if the catalyst loading was as low as 0.01%, good yields (81–95%) of the desired products were achieved.
Quaternary Ammonium Salts as Alkylating Reagents in C-H Activation Chemistry
Spettel, Manuel,Pollice, Robert,Schnürch, Michael
supporting information, p. 4287 - 4290 (2017/08/23)
A rhodium(I)-catalyzed alkylation reaction of benzylic amines via C(sp3)-H activation using quaternary ammonium salts as alkyl source is described. The reaction proceeds via in situ formation of an olefin via Hofmann elimination, which is the actual alkylating reagent. This represents an operationally simple method for substituting gaseous and liquid olefins with solid quaternary ammonium salts as alkylating reagents, which is transferable to other C-H activation protocols as well.
Selective Monoarylation of Primary Amines Using the Pd-PEPPSI-IPentCl Precatalyst
Sharif, Sepideh,Rucker, Richard P.,Chandrasoma, Nalin,Mitchell, David,Rodriguez, Michael J.,Froese, Robert D. J.,Organ, Michael G.
supporting information, p. 9507 - 9511 (2015/08/11)
A single set of reaction conditions for the palladium-catalyzed amination of a wide variety of (hetero)aryl halides using primary alkyl amines has been developed. By combining the exceptionally high reactivity of the Pd-PEPPSI-IPentCl catalyst (PEPPSI=pyridine enhanced precatalyst preparation, stabilization, and initiation) with the soluble and nonaggressive sodium salt of BHT (BHT=2,6-di-tert-butyl-hydroxytoluene), both six- and five-membered (hetero)aryl halides undergo efficient and selective amination.
Iridium- and rhodium-catalyzed dehydrogenative silylations of C(sp 3) - H bonds adjacent to a nitrogen atom using hydrosilanes
Mita, Tsuyoshi,Michigami, Kenichi,Sato, Yoshihiro
supporting information, p. 2970 - 2973 (2014/01/06)
Now that is just silylated: In the presence of iridium or rhodium catalysts, C(sp3) - H bonds adjacent to a nitrogen atom were silylated by the aid of a pyridine-directing group. In iridium catalysis, a hydrogen-trapping reagent such as norbornene or tert-butylethylene, which is usually required in late transition-metal-catalyzed dehydrogenative coupling reactions, was not required. In rhodium catalysis, however, 1 equivalent of COD (1,5-cyclooctadiene) was necessary to induce higher conversion. Copyright
