101137-69-3Relevant articles and documents
Protocol for Palladium/ N-Heterocyclic Carbene-Catalyzed Suzuki-Miyaura Cross-Coupling of Amides by N-C(O) Activation
Lei, Peng,Li, Guangchen,Ling, Yun,An, Jie,Nolan, Steven P.,Szostak, Michal
, p. 682 - 687 (2021)
Amides are among the most important and ubiquitous functional groups in organic chemistry and process development. In this Practical Synthetic Procedure, a protocol for the Suzuki-Miyaura cross-coupling of amides by selective N-C(O) bond activation catalyzed by commercially available, air-and moisture-stable palladium/N-heterocyclic carbene (NHC) complexes is described. The procedure described involves [Pd(IPr)(cin)Cl] [IPr = 2,6-(diisopropylphenyl)imidazol-2-ylidene, cin = cinnamyl] at 0.10 mol% at room temperature and is performed on decagram scale. Furthermore, a procedure for the synthesis of amide starting materials is accomplished via selective N-tert-butoxycarbonylation, which is the preferred method over N-Acylation. The present protocol carries advantages of operational simplicity, commercial availability of catalysts, and excellent conversions at low catalyst loadings. The method is generally useful for activation of N-C(O) amide bonds in a broad spectrum of amide precursors. The protocol should facilitate the implementation of amide cross-coupling reactions.
Rh-Catalyzed Base-Free Decarbonylative Borylation of Twisted Amides
Bie, Fusheng,Liu, Xuejing,Shi, Yijun,Cao, Han,Han, Ying,Szostak, Michal,Liu, Chengwei,Liu, Xuejing,Szostak, Michal,Liu, Chengwei
, p. 15676 - 15685 (2020)
We report the rhodium-catalyzed base-free decarbonylative borylation of twisted amides. The synthesis of versatile arylboronate esters from aryl twisted amides is achieved via decarbonylative rhodium(I) catalysis and highly selective N-C(O) insertion. The method is notable for a very practical, additive-free Rh(I) catalyst system. The method shows broad functional group tolerance and excellent substrate scope, including site-selective decarbonylative borylation/Heck cross-coupling via divergent N-C/C-Br cleavage and late-stage pharmaceutical borylation.
Palladium-Catalyzed Aerobic Oxidative Coupling of Amides with Arylboronic Acids by Cooperative Catalysis
Li, Yue,Wu, Hongxiang,Zeng, Zhuo
, p. 4357 - 4361 (2019)
The first fluoride and palladium co-catalyzed conversion of amide to ester through an aerobic oxidative coupling pathway is reported. This new approach presents a practical process that employs easily available oxygen and commercially available arylboronic acids as coupling partners, uses a wide range of N- tosylamides, and proceeds under mild reaction conditions. This protocol demonstrates broad functional group tolerance, and provides an alternative option to synthesize esters from N-tosylamides which obtained by simply N-functionalization of secondary amides.
2-Methyltetrahydrofuran (2-MeTHF): A Green Solvent for Pd?NHC-Catalyzed Amide and Ester Suzuki-Miyaura Cross-Coupling by N?C/O?C Cleavage
Lei, Peng,Ling, Yun,An, Jie,Nolan, Steven P.,Szostak, Michal
, p. 5654 - 5660 (2019)
The palladium-NHC-catalyzed (NHC=N-heterocyclic carbene) Suzuki-Miyaura cross-coupling of amides and esters via highly chemoselective N?C(O) and O?C(O) cleavage with aryl boronic acids using green, sustainable and eco-friendly 2-methyltetrahydrofuran (2-MeTHF) is reported. A variety of amides and aryl esters were coupled with aryl boronic acids in high to excellent yields. This method employs commercially-available, air- and moisture-stable Pd(II) ?NHC precatalysts. Crucially, the use of 2-MeTHF leads to the highest TON reported to date in amide N?C(O) bond cross-coupling. This operationally-simple protocol was utilized in the synthesis a bioactive ketone intermediate, emphasizing the potential of 2-MeTHF as a green solvent in unconventional amide bond disconnection. Given the tremendous importance of amide bond cross-coupling strategies and the drive to maintain full sustainability in cross-coupling processes, we expect that the synthetic method will be of broad interest.
A General Method for Two-Step Transamidation of Secondary Amides Using Commercially Available, Air- and Moisture-Stable Palladium/NHC (N-Heterocyclic Carbene) Complexes
Meng, Guangrong,Lei, Peng,Szostak, Michal
, p. 2158 - 2161 (2017)
The first general method is reported for transamidation of secondary carboxamides catalyzed by Pd-NHC (NHC = N-heterocyclic carbene) complexes. Commercially available, air- and moisture-stable (NHC)Pd(R-allyl)Cl complexes can effect C-N cross-coupling of a wide range of N-Boc and N-Ts amides, obtained by selective amide N-functionalization, with non-nucleophilic anilines and sterically hindered amines in very good yields. The first use of versatile Pd-NHC complexes as catalysts is represented for transition-metal-catalyzed C(acyl)-N amination of amides by N-C activation.
