136540-09-5

Upstream product

• 2382-96-9 benzo[d]oxazole-2-(3H)-thione 
• 100-61-8 N-methylaniline 
• 6631-42-1 N-phenyl-1,3-benzoxazol-2-amine 
• 74-88-4 methyl iodide 
• 615-18-9 2-chloro-1,3-benzoxazole 
• 121-69-7 N,N-dimethyl-aniline 
• 51-19-4 2-aminophenol hydrochloride 
• 273-53-0 benzoxazole 

Relevant academic research and scientific papers

Unexpected dealkylation during nucleophilic substitution: Synthesis of 2-N,N-dialkylamino benzoxazoles and benzothiazoles

Mild reaction conditions are described for the preparation of a number of 2-alkyl- and 2-arylaminobenzoxazoles and benzothiazoles from 2-chlorobenzoxazole and 2-chlorobenzothiazole and N-methyl or other simple N-alkyl tertiary amines. The reaction proceeds neat or in THF solution and involves dealkylation of the amine reactant by nucleophilic substitution by chloride. In the case of N-methylpyrrolidine and N-methylpiperidine demethylation was not observed and the major product was formed by ring opening to give chlorobutyl- and chloropentyl-methylamino substituted benzoxazoles and benzothiazoles. Treatment of the chlorobutyl derivative with iodide in acetone afforded the new 1H,2H,3H,4H,5H-[1,3]diazepino[2,1-b][1,3]benzoxazol-6-ium ring system. (C) 2000 Elsevier Science Ltd.

Synthesis of 2-Deoxy-C-Glycosides via Iridium-Catalyzed sp2 and sp3 C—H Glycosylation with Unfunctionalized Glycals?

A new protocol for the synthesis of 2-deoxy-C-aryl-glycosides and 2-deoxy-C-alkyl-glycosides via iridium-catalyzed directed C—H glycosylation with glycals is reported. The method is amenable for both the C2 C—H glycosylation of indoles and the methyl C—H glycosylation of secondary methyl amines under the control of an N-linked benzoxazole directing group. The benzoxazole group can be cleanly removed by the treatment of KOH or LiAlH4.

Buchwald-Hartwig Amination of Coordinating Heterocycles Enabled by Large-but-Flexible Pd-BIAN-NHC Catalysts**

A new class of large-but-flexible Pd-BIAN-NHC catalysts (BIAN=acenaphthoimidazolylidene, NHC=N-heterocyclic carbene) has been rationally designed to enable the challenging Buchwald-Hartwig amination of coordinating heterocycles. This robust class of BIAN-NHC catalysts permits cross-coupling under practical aerobic conditions of a variety of heterocycles with aryl, alkyl, and heteroarylamines, including historically challenging oxazoles and thiazoles as well as electron-deficient heterocycles containing multiple heteroatoms with BIAN-INon (N,N′-bis(2,6-di(4-heptyl)phenyl)-7H-acenaphtho[1,2-d]imidazol-8-ylidene) as the most effective ligand. Studies on the ligand structure and electronic properties of the carbene center are reported. The study should facilitate the discovery of even more active catalyst systems based on the unique BIAN-NHC scaffold.

Cu(acac)2 catalyzed oxidative C-H bond amination of azoles with amines under base-free conditions

This work reports a simple and efficient methodology for oxidative C-H bond amination of azoles with aromatic/aliphatic amines using copper-bis- acetylacetonate complex catalyst. The catalyst works very well in the absence of external acid or base and requires only molecular oxygen as an oxidant. The methodology is applicable for the oxidative C-H bond amination of various azoles with different types of aromatic/aliphatic amines for the synthesis of various aminoheterocycles with good to excellent yields.

Copper-catalyzed oxidative C-H, N-H coupling of azoles and thiophenes

CH, NH coupling of azole and thiophene derivatives takes place in the presence of a catalytic amount of Cu(OAc)2 and an additive. The reaction of azoles smoothly occurs with several amines and amides catalyzed by 20 mol % of Cu(OAc)2-2PPh3 and 4 equiv of NaOAc under O2 or in the presence of Ag2CO3 under N 2. The coupling reaction leads to a facile synthesis of a N-substituted analogue of 2,5-diarylthiazole, which shows photoluminescent properties with extended π-conjugation. Spectroscopic characteristics of the obtained thiazole derivatives are discussed by measurements of UV-vis absorption and photoluminescent spectra. Under the reaction conditions using Ag 2CO3 as an additive and Cu(OAc)2-2PPh 3 as a catalyst, thiophene derivatives also react with 2-pyrrolidone to undergo CH, NH amidation.

Direct amination of azoles via catalytic C-H, N-H Coupling

C-H, N-H Coupling of azoles takes place with several amines in the presence of a copper catalyst to undergo amination at the 2-position. The reaction of benzothiazole with N-methylaniline in the presence of sodium acetate and 20 mol % Cu(0Ac)2

Selectivity in the Consecutive SNAr-Dequaternization Reactions of Heteroaromatic Chlorides with Tertiary Amines under High Pressure

Consecutive SNAr-dealkylation reactions of heteroaromatic chlorides such as 2-chloro-5-trifluoromethylpyridine and 2-chlorobenzothiazole with tertiary amines took place under high pressure in a highly selective fashion; some synthetic potential