29601-75-0Relevant articles and documents
Synthesis of Axially Chiral Biaryl-2-amines by PdII-Catalyzed Free-Amine-Directed Atroposelective C?H Olefination
Zhan, Bei-Bei,Wang, Lei,Luo, Jun,Lin, Xu-Feng,Shi, Bing-Feng
supporting information, p. 3568 - 3572 (2020/02/05)
A simple and ubiquitously present group, free amine, is used as a directing group to synthesize axially chiral biaryl compounds by PdII-catalyzed atroposelective C?H olefination. A broad range of axially chiral biaryl-2-amines can be obtained in good yields with high enantioselectivities (up to 97 % ee). Chiral spiro phosphoric acid (SPA) proved to be an efficient ligand and the loading could be reduced to 1 mol % without erosion of enantiocontrol in gram-scale synthesis. The resulting axially chiral biaryl-2-amines also provide a platform for the synthesis of a set of chiral ligands.
NBE-Controlled Palladium-Catalyzed Interannular Selective C-H Silylation: Access to Divergent Silicon-Containing 1,1′-Biaryl-2-Acetamides
Li, Wenguang,Chen, Wenqi,Zhou, Bang,Xu, Yankun,Deng, Guobo,Liang, Yun,Yang, Yuan
supporting information, p. 2718 - 2722 (2019/04/16)
A novel palladium-catalyzed interannular selective C-H silylation of 1,1′-biaryl-2-acetamides is described. The combination of palladium catalyst with copper oxidant enables meta- or ortho-selective C-H silylation by employing hexamethyldisilane as a trimethylsilyl source, which relies on the control of NBE derivatives as a switch, thus providing straightforward access to divergent silicon-containing 1,1′-biaryl-2-acetamides.
"transition-metal-free" synthesis of carbazoles by photostimulated reactions of 2′-halo[1,1′-biphenyl]-2-amines
Guerra, Walter D.,Rossi, Roberto A.,Pierini, Adriana B.,Barolo, Silvia M.
, p. 928 - 941 (2015/01/30)
An efficient and simple protocol for the preparation of a series of 9H-carbazoles by photostimulated SRN1 substitution reactions is presented. Substituted 9H-carbazoles were synthesized in low to excellent yields (up to 96%) through an intramolecular C-N bond formation of 2′-halo[1,1′-biphenyl]-2-amines by the photoinitiated SRN1 mechanism under mild and "transition-metal-free" conditions. The biphenylamines used as substrates were obtained with isolated yields ranging from 21% to 84% by two approaches: (A) the cross-coupling Suzuki-Miyaura reaction and (B) the radical arylation of anilines. Some key aspects of the proposed mechanism were evaluated at the B3LYP/6-311+G? level.
Synthesis of triaryls: Hydroxy and amine dinaphthyl and diphenanthryl aryls by one-pot electron-transfer nucleophilic substitution reactions
Jimenez, Liliana B.,Torres, Natalia V.,Borioni, José L.,Pierini, Adriana B.
, p. 3614 - 3620 (2014/05/20)
A new one-pot synthetic route to achieve the preparation of hydroxy and amine binaphthyl and biphenanthryl aryls is here reported. This approach involves the reaction of 1,4-bromoiodobenzene, 4,4′-diiodobiphenyl, and 1,4- and 1,5-diiodonaphthalene with the anions of 2-naphthylamine, 2-naphthol, and 9-phenanthrylamine under irradiation in liquid ammonia. The reactions proceed to afford triaryl derivatives in moderate to good yields (～45% of 1,4-phenylene- and 1,4-naphthylene-1,1′-dinaphthalen-2-ols as well as 1,4-phenylene-1,1′-dinaphthalen-2-amine and 10,10′-diphenanthren-9- amine). Lower yields (27%) of polyaryl derivatives are obtained by reaction of 4,4′-diiodobiphenyl with anions of 2-naphthol and 9-phenanthrylamine.
Direct intermolecular aniline ortho- arylation via benzyne intermediates
Truong, Thanh,Daugulis, Olafs
supporting information, p. 5964 - 5967 (2013/02/22)
A method for direct, transition-metal-free ortho-arylation of anilines by aryl chlorides, bromides, fluorides, and triflates has been developed. This methodology provides the most direct approach to 2-arylanilines since no protecting or directing groups on nitrogen are required. The arylation is functional-group tolerant, with alkene, ether, trifluoromethyl, dimethylamino, carbonyl, chloro, and cyano functionalities tolerated. Phenylation of enantiopure binaphthyldiamine affords a product with >99% ee.
Intramolecular oxidative C-N bond formation for the synthesis of carbazoles: Comparison of reactivity between the copper-catalyzed and metal-free conditions
Cho, Seung Hwan,Yoon, Jungho,Chang, Sukbok
supporting information; experimental part, p. 5996 - 6005 (2011/06/11)
New synthetic procedures for intramolecular oxidative C-N bond formation have been developed for the preparation of carbazoles starting from N-substituted amidobiphenyls under either Cu-catalyzed or metal-free conditions using hypervalent iodine(III) as an oxidant. Whereas iodobenzene diacetate or bis(trifluoroacetoxy)iodobenzene alone undergoes the reaction to provide carbazole products in moderate to low yields, combined use of copper(II) triflate and the iodine(III) species significantly improves the reaction efficiency, giving a more diverse range of products in good to excellent yields. On the basis of mechanistic studies including kinetic profile, isotope effects, and radical inhibition experiments, the copper species is proposed to catalytically activate the hypervalent iodine(III) oxidants. The synthetic utility of the present approach was nicely demonstrated in a direct synthesis of indolo[3,2-b]carbazole utilizing a double C-N bond formation.
Regiochemistry of the Coupling of Aryl Radicals with Nucleophiles Derived from the Naphthyl System. Experimental and Theoretical Studies
Pierini, Adriana B.,Baumgartner, Maria T.,Rossi, Roberto A.
, p. 580 - 586 (2007/10/02)
We here report the photostimulated reaction of unactived aromatic halides with ambident nucleophiles derived from the naphthyl system such as 1- and 2-naphthylamide, 2-naphthoxide, 2-naphthalenethiolate, and 2 naphthaleneselenate ions, by the SRN1 mechanism of nucleophilic substitution.According to our experimental results, C-arylation in position 1 of the naphthyl moiety is the only reaction observed with 2-naphthoxide ions and it is favored over N-arylation with 1- and 2-naphthylamide ions.Heteroatom arylation is preferred over C-arylation with 2-naphthalenethiolate ions while it is the only observed reaction with 2-naphthaleneselenate ions.A theoretical study was carried out to explain the regiochemistry of the system.In competition experiments, 2-naphthalenethiolate ions proved to be 1.8 +/- 0.2 times more reactive than 2-naphthoxide ions for C-substitution toward p-anisyl radicals in liquid ammonia.
PHOTOSTIMULATED REACTIONS OF HALOARENES WITH 2-NAPHTHYLAMIDE IONS. A FACILE SYNTHESIS OF 1-ARYL-2-NAPHTHYLAMINES.
Pierini, A.B.,Baumgartner, M.T.,Rossi, R.A.
, p. 4653 - 4656 (2007/10/02)
The photostimulated reactions of aryl iodides with 2-naphtylamide ions in liquid ammonia gave 1-aryl-2-naphthylamines as the major substitution product.This reaction is proposed to occur by the SRN1 mechanism of nucleophilic substitution.
DIPROTONATION OF NITROARENES
Ohta, Toshiharu,Shudo, Koichi,Okamoto, Toshihiko
, p. 325 - 328 (2007/10/02)
Cryoscopic measurements shows that 1-nitronaphthalene is diprotonated in trifluoromethanesulfonic acid (TFSA).The diprotonated nitronaphthalenes are N,N-dihydroxyiminiumnaphthalenium dications, wich are fully characterised by UV, 1H-, 13/
