32366-28-2Relevant articles and documents
An Enantioselective Bidentate Auxiliary Directed Palladium-Catalyzed Benzylic C?H Arylation of Amines Using a BINOL Phosphate Ligand
Wang, Hao,Tong, Hua-Rong,He, Gang,Chen, Gong
, p. 15387 - 15391 (2016)
A new enantioselective palladium(II)-catalyzed benzylic C?H arylation reaction of amines is enabled by the bidentate picolinamide (PA) directing group. This reaction provides the first example of enantioselective benzylic γ-C?H arylations of alkyl amines,
Mangana(iii/iv)electro-catalyzed C(sp3)-H azidation
Meyer, Tjark H.,Samanta, Ramesh C.,Del Vecchio, Antonio,Ackermann, Lutz
, p. 2890 - 2897 (2021/03/14)
Manganaelectro-catalyzed azidation of otherwise inert C(sp3)-H bonds was accomplished using most user-friendly sodium azide as the nitrogen-source. The operationally simple, resource-economic C-H azidation strategy was characterized by mild reaction conditions, no directing group, traceless electrons as the sole redox-reagent, Earth-abundant manganese as the catalyst, high functional-group compatibility and high chemoselectivity, setting the stage for late-stage azidation of bioactive compounds. Detailed mechanistic studies by experiment, spectrophotometry and cyclic voltammetry provided strong support for metal-catalyzed aliphatic radical formation, along with subsequent azidyl radical transfer within a manganese(iii/iv) manifold.
Site-Selective Copper-Catalyzed Azidation of Benzylic C-H Bonds
Suh, Sung-Eun,Chen, Si-Jie,Mandal, Mukunda,Guzei, Ilia A.,Cramer, Christopher J.,Stahl, Shannon S.
supporting information, p. 11388 - 11393 (2020/07/21)
Site selectivity represents a key challenge for non-directed C-H functionalization, even when the C-H bond is intrinsically reactive. Here, we report a copper-catalyzed method for benzylic C-H azidation of diverse molecules. Experimental and density functional theory studies suggest the benzyl radical reacts with a CuII-azide species via a radical-polar crossover pathway. Comparison of this method with other C-H azidation methods highlights its unique site selectivity, and conversions of the benzyl azide products into amine, triazole, tetrazole, and pyrrole functional groups highlight the broad utility of this method for target molecule synthesis and medicinal chemistry.
A Supramolecular Model for the Co-Catalytic Role of Nitro Compounds in Br?nsted Acid Catalyzed Reactions
Montalvo-Acosta, Joel J.,Dryzhakov, Marian,Richmond, Edward,Cecchini, Marco,Moran, Joseph
supporting information, p. 10976 - 10980 (2020/06/10)
Nitro compounds are known to change reaction rates and kinetic concentration dependence of Br?nsted-acid-catalyzed reactions. Yet, no mechanistic model exists to account for these observations. In this work, an atomistic model for the catalytically active
Catalytic B(C6F5)3[rad]H2O-promoted defluorinative functionalization of tertiary aliphatic fluorides
Dryzhakov, Marian,Richmond, Edward,Li, Guang,Moran, Joseph
, p. 45 - 51 (2016/12/06)
A B(C6F5)3[rad]H2O-catalyzed defluorinative functionalization of tertiary aliphatic fluorides is described that proceeds under benign reaction conditions. The synthetic utility of the method is exemplified throu
Nitro-assisted Br?nsted acid catalysis: Application to a challenging catalytic azidation
Dryzhakov, Marian,Hellal, Malik,Wolf, Eléna,Falk, Florian C.,Moran, Joseph
supporting information, p. 9555 - 9558 (2015/08/18)
A cocatalytic effect of nitro compounds is described for the B(C6F5)3·H2O catalyzed azidation of tertiary aliphatic alcohols, enabling catalyst turnover for the first time and with a broad range of substrates. K
Conversion of tertiary alcohols to tert-alkyl azides by way of quinone-mediated oxidation-reduction condensation using alkyl diphenylphosphinites
Kuroda, Kiichi,Hayashi, Yujiro,Mukaiyama, Teruaki
, p. 6358 - 6364 (2008/02/05)
A novel method for the preparation of alkyl azides from alcohols by way of oxidation-reduction condensation is described. In this reaction, the sterically-hindered tert-alkyl phosphinites that are prepared from the corresponding alcohols are converted int
Cobalt-catalyzed synthesis of tertiary azides from α,α- disubstituted olefins under mild conditions using commercially available reagents
Gaspar, Boris,Waser, Jerome,Carreira, Erick M.
, p. 3839 - 3845 (2008/09/17)
The use of commercially available azide sources is presented for the cobalt-catalyzed hydroazidation reaction. α,α-Disubstituted olefins with a variety of functional groups were employed as substrates, providing tertiary azides in useful yields. Georg Thi
Hydrazines and azides via the metal-catalyzed hydrohydrazination and hydroazidation of olefins
Waser, Jerome,Gaspar, Boris,Nambu, Hisanori,Carreira, Erick M.
, p. 11693 - 11712 (2007/10/03)
The discovery, study, and implementation of the Co- and Mn-catalyzed hydrohydrazination and hydroazidation reactions of olefins are reported. These reactions are equivalent to direct hydroaminations of C-C double bonds with protected hydrazines or hydrazoic acid but are based on a different concept in which the H and the N atoms come from two different reagents, a silane and an oxidizing nitrogen source (azodicarboxylate or sulfonyl azide). The hydrohydrazination reaction using di-tert-butyl azodicarboxylate is characterized by its ease of use, large functional group tolerance, and broad scope, including mono-, di-, tri-, and tetrasubstituted olefins. Key to the development of the hydroazidation reaction was the use of sulfonyl azides as nitrogen sources and the activating effect of tert-butyl hydroperoxide. The reaction was found to be efficient for the functionalization of mono-, di-, and trisubstituted olefins, and only a few functional groups are not tolerated. The alkyl azides obtained are versatile intermediates and can be transformed to the free amines or triazoles without isolation of the azides. Preliminary mechanistic investigations suggest a rate-limiting hydrocobaltation of the alkene, followed by an amination reaction. Radical intermediates cannot be ruled out and may be involved.
Preparation of tert-alkyl azides from tertiary alcohols by way of benzoquinone-mediated oxidation-reduction condensation
Kuroda, Kiichi,Kaneko, Nobuya,Hayashi, Yujiro,Mukaiyama, Teruaki
, p. 1432 - 1433 (2007/10/03)
A novel method for the preparation of alkyl azides from alcohols by way of oxidation-reduction condensation is described. According to this reaction, the sterically hindered tert-alkyl phosphinites that are prepared from the corresponding alcohols are con
