76842-14-3Relevant academic research and scientific papers
Catalyst-Controlled Regioselective Chlorination of Phenols and Anilines through a Lewis Basic Selenoether Catalyst
Dinh, Andrew N.,Maddox, Sean M.,Vaidya, Sagar D.,Saputra, Mirza A.,Nalbandian, Christopher J.,Gustafson, Jeffrey L.
, p. 13895 - 13905 (2020/11/03)
We report a highly efficient ortho-selective electrophilic chlorination of phenols utilizing a Lewis basic selenoether catalyst. The selenoether catalyst resulted in comparable selectivities to our previously reported bis-thiourea ortho-selective catalyst, with a catalyst loading as low as 1%. The new catalytic system also allowed us to extend this chemistry to obtain excellent ortho-selectivities for unprotected anilines. The selectivities of this reaction are up to >20:1 ortho/para, while the innate selectivities for phenols and anilines are approximately 1:4 ortho/para. A series of preliminary studies revealed that the substrates require a hydrogen-bonding moiety for selectivity.
NiCl2(dppe)-Catalyzed Geminal Dialkylation of Dithioacetals and Trimethylation of Ortho Thioesters
Tzeng, Yih-Ling,Yang, Ping-Fan,Mei, Nai-Wen,Yuan, Tien-Min,Yu, Chun-Chi,Luh, Tien-Yau
, p. 5289 - 5293 (2007/10/02)
NiCl2(dppe)-catalyzed cross-coupling of cinnamaldehyde dithioacetals gave the corresponding geminal dimethylation products in excellent yields.Allylic ortho thioesters afforded regioselectively the corresponding trimethylation products.The reaction may occur via an 18-electron ?-allyl intermediate, which undergoes facile reductive elimination to afford the geminal dimethylation product.Benzylic dithioacetals having an ortho amino group gave 2-isopropylanilines exclusively.The reaction of benzylic dithioacetals with EtMgBr under the same conditions yielded geminal diethylation products.
ONE-POT CHEMOSELECTIVE REDUCTIVE ALKYLATION OF NITROARENES: A NEW GENERAL METHOD OF SYNTHESIS OF ALKYLANILINES.
Bartoli, Giuseppe,Bosco, Marcella,Pozzo, Renato Dal,Petrini, Marino
, p. 4221 - 4226 (2007/10/02)
A New facile and general synthesis of alkylanilines by one-pot reductive alkylation of nitroarenes is reported.This method is based on the "in situ" reduction by hydrides (LiAlH4 or NaBH4) in the presence of catalytic amounts of Pd/C, of nitronate adducts arising from the conjugate addition of Grignard reagents to mononitroarenes.LiAlH4 showed to be a more efficient but less selective reducing agent than NaBH4.The reaction can be successfully applied to mono, homo and hetero bicyclic systems and allows to introduce a large variety of alkyl chains without isomerisation phenomena.
