720712-00-5Relevant academic research and scientific papers
Iron-Catalyzed Intramolecular Aminations of C(sp3)?H Bonds in Alkylaryl Azides
Alt, Isabel T.,Guttroff, Claudia,Plietker, Bernd
supporting information, p. 10582 - 10586 (2017/08/22)
The nucleophilic iron complex Bu4N[Fe(CO)3(NO)] (TBA[Fe]) catalyzes the direct intramolecular amination of unactivated C(sp3)?H bonds in alkylaryl azides, which results in the formation of substituted indoline and tetrahydroquinoline derivatives.
Catalytic C(sp3)?H Arylation of Free Primary Amines with an exo Directing Group Generated In Situ
Xu, Yan,Young, Michael C.,Wang, Chengpeng,Magness, David M.,Dong, Guangbin
, p. 9084 - 9087 (2016/07/26)
Herein, we report the palladium-catalyzed direct arylation of unactivated aliphatic C?H bonds in free primary amines. This method takes advantage of an exo-imine-type directing group (DG) that can be generated and removed in situ. A range of unprotected aliphatic amines are suitable substrates, undergoing site-selective arylation at the γ-position. Methyl as well as cyclic and acyclic methylene groups can be activated. Furthermore, when aniline-derived substrates were used, preliminary success with δ-C?H arylation was achieved. The feasibility of using the DG component in a catalytic fashion was also demonstrated.
Metal-Free Visible Light-Mediated Photocatalysis: Controlling Intramolecular [2 + 2] Photocycloaddition of Enones through Axial Chirality
Clay, Anthony,Vallavoju, Nandini,Krishnan, Retheesh,Ugrinov, Angel,Sivaguru, Jayaraman
, p. 7191 - 7200 (2016/08/30)
Atropisomeric enone-imides and enone-amides featuring N-CAryl bond rotation were evaluated for intramolecular [2 + 2] photocycloaddition. Straight addition product was observed over cross-addition product with good control over reactivity. The atropselectivity was found to be dependent on the substituent on the aryl ring. Substitution-dependent atropselectivity was rationalized on the basis of a divergent mechanistic pathway.
Rh2(II)-catalyzed intramolecular aliphatic C-H bond amination reactions using aryl azides as the N-atom source
Nguyen, Quyen,Sun, Ke,Driver, Tom G.
, p. 7262 - 7265 (2012/06/16)
Rhodium(II) dicarboxylate complexes were discovered to catalyze the intramolecular amination of unactivated primary, secondary, or tertiary aliphatic C-H bonds using aryl azides as the N-atom precursor. While a strong electron-withdrawing group on the nitrogen atom is typically required to achieve this reaction, we found that both electron-rich and electron-poor aryl azides are efficient sources for the metal nitrene reactive intermediate.
Stereoselectivity in reactions of atropisomeric lactams and imides
Bennett, D. Jonathan,Blake, Alexander J.,Cooke, Paul A.,Godfrey, Christopher R.A.,Pickering, Paula L.,Simpkins, Nigel S.,Walker, Matthew D.,Wilson, Claire
, p. 4491 - 4511 (2007/10/03)
A range of reactions of cyclic lactam systems is described in which an atropisomeric C-N axis controls the stereochemical outcome of ring substitution or addition. In the case of enantiopure menthol adducts, substitution via N-acyliminium intermediates occurred with essentially complete control. However, the range of nucleophiles that participate in the reaction is very limited and at present the removal of the N-aryl substituent is problematic. A six-membered enamide is of moderate configurational stability and the axis exerts synthetically useful levels of control over enolate alkylations of the system. A novel Lewis acid mediated enamide arylation process was identified.
Synthesis of functionalized carbamates through a palladium-catalyzed reductive carbonylation of substituted nitrobenzenes
Wchman, Petra,Borst, Leo,Kamer, Paul C. J.,Van Leeuwen, Piet W. N. M.
, p. 13 - 21 (2007/10/03)
The palladium-catalyzed reductive carbonylation of ortho and para-substituted nitrobenzenes has proven to be an attractive route for the synthesis of functionalized carbamates. For the Pd(1,10-phenanthroline)2(triilate}2 catalyst system, the scope of the reaction has been studied. Substrates with electron-donating substituents at the para position were found to decrease the catalytic activity, most probably as a result of their relatively low oxidizing capacity. The selectivity towards the desired carbamate, however, was increased for these substrates. Under the influence of electron-withdrawing substituents the azoxybenzene and azobenzene derivatives became important side products. Introduction of large steric hindrance at the ortho position of the nitro substrates gave rise to an interesting side reaction, viz. methoxylation of the aromatic ring. The methoxylation reaction appeared to occur on an intermediate species in the catalytic cycle. Several functionalities have shown to be resistant to the reaction conditions required for the conversion of the nitro group. Especially with 4-nitrobenzoic acid, an extremely high activity and selectivity was found, thus yielding a very convenient synthesis for N-protected amines containing carboxylic acid functions. VCH Verlagsgesellschaft mbH.
