53001-06-2Relevant articles and documents
Palladium(II)-Catalyzed Aminotrifluoromethoxylation of Alkenes: Mechanistic Insight into the Effect of N-Protecting Groups
Chen, Chaohuang,Chen, Pinhong,Hou, Chuanqi,Liu, Guosheng
, p. 346 - 350 (2020/05/25)
An efficient palladium-catalyzed regioselective 5-exo aminotrifluoromethoxylation of alkenes has been established herein, which provides a practical route towards the synthesis of OCF3-containing pyrrolidines. tert-Butyloxycarbonyl (Boc) as an amino protecting group plays a significant role in both the chemo- and regioselectivities. In addition, preliminary mechanistic studies reveal that the amino protecting group of substrates and the counter anion of palladium catalyst play critical roles in reaction efficiency presumably due to an isomerization of alkyl- Pd(II) intermediates. Moreover, the asymmetric 5-exo aminotrifluoromethoxylation reaction has also been achieved by introducing a sterically bulky pyridinyl-oxazoline ligand.
Asymmetric "clip-Cycle" Synthesis of Pyrrolidines and Spiropyrrolidines
Maddocks, Christopher J.,Ermanis, Kristaps,Clarke, Paul A.
, p. 8116 - 8121 (2020/11/02)
The development of an asymmetric "clip-cycle"synthesis of 2,2- and 3,3-disubstituted pyrrolidines and spiropyrrolidines, which are increasingly important scaffolds in drug discovery programs, is reported. Cbz-protected bis-homoallylic amines were activate
Copper-Catalyzed Carbonylative Synthesis of β-Homoprolines from N-Fluoro-sulfonamides
Wu, Xiao-Feng,Yin, Zhiping,Zhang, Youcan
supporting information, p. 1889 - 1893 (2020/03/24)
A new methodology for the carbonylative transformation of N-fluoro-sulfonamides into N-sulfonyl-β-homoproline esters has been described. In the presence of a catalytic amount of Cu(OTf)2, a range of β-homoproline derivatives were prepared in moderate to good yield. The reaction proceeds via the intramolecular cyclization and intermolecular carbonylation of a free carbon radical. Notably, this procedure offers the possibility to build potential functionalized bioactive molecules.
Experimental and Computational Mechanistic Studies of the β-Diketiminatoiron(II)-Catalysed Hydroamination of Primary Aminoalkenes
Lepori, Clément,Bernoud, Elise,Guillot, Régis,Tobisch, Sven,Hannedouche, Jér?me
supporting information, p. 835 - 844 (2019/01/09)
A comprehensive mechanistic study by means of complementary experimental and computational approaches of the exo-cyclohydroamination of primary aminoalkenes mediated by the recently reported β-diketiminatoiron(II) complex B is presented. Kinetic analysis
Aerobic intramolecular aminothiocyanation of unactivated alkenes promoted by in situ generated iodine thiocyanate
Feng, Yangyang,Hussain, Muhammad Ijaz,Zhang, Xiaohui,Shi, Jian,Hu, Wen,Xiong, Yan
, p. 2669 - 2676 (2018/05/04)
Aerobic intramolecular aminothiocyanation of unactivated alkenes has been developed by in situ generated iodine thiocyanate under open-flask conditions. This protocol provides a concise and efficient method for synthesizing SCN-containing pyrrolidine, piperidine and indoline derivatives with isolated yields of up to 87%. Furthermore, mixing iodine and sodium thiocyanate with oxygen afforded iodine thiocyanate (ISCN) and dithiocyanatoiodate [I(SCN)2]- which were testified by liquid chromatography mass spectrometry. A mechanistic investigation indicates that iodonium ion and sulfonium ion intermediates might be involved in this transformation.
One-pot Construction of Difluorinated Pyrrolizidine and Indolizidine Scaffolds via Copper-Catalyzed Radical Cascade Annulation
Wang, Xiaoyang,Li, Miao,Yang, Yanyan,Guo, Minjie,Tang, Xiangyang,Wang, Guangwei
, p. 2151 - 2156 (2018/04/26)
A convenient approach to the synthesis of diverse difluorinated nitrogen-containing polycycles via a copper-catalyzed radical cascade annulation of amine-containing olefins and ethyl bromodifluoroacetate was developed. Three new bonds, including a Csp3 ?CF2 and two C?N bonds, are forged simultaneously in this strategy. Through this strategy, a series of difluorinated pyrrolizidine and indolizidine derivatives have been conveniently synthesized in good yields. (Figure presented.).
Enantioselective Pd(II)-Catalyzed Intramolecular Oxidative 6- endo Aminoacetoxylation of Unactivated Alkenes
Qi, Xiaoxu,Chen, Chaohuang,Hou, Chuanqi,Fu, Liang,Chen, Pinhong,Liu, Guosheng
, p. 7415 - 7419 (2018/06/08)
A novel asymmetric 6-endo aminoacetoxylation of unactivated alkenes by palladium catalysis, which yields chiral β-acetoxylated piperidines with excellent chemo-, regio- and enantioselectivities under very mild reaction conditions, has been established herein by employing a new designed pyridine-oxazoline (Pyox) ligand. Importantly, introducing a sterically bulky group into the C-6 position of Pyox is crucial to enhance the reactivity of the aminoacetoxylation of alkenes.
Pd-Catalyzed Intramolecular Aminoalkylation of Unactivated Alkenes: Access to Diverse N-Heterocycles
Ye, Liu,Lo, Kai-Yip,Gu, Qiangshuai,Yang, Dan
, p. 308 - 311 (2017/04/21)
A highly efficient palladium-catalyzed intramolecular aminoalkylation of unactivated alkenes in the absence of an external ligand and oxidant is described. New C-N and C(sp3)-C(sp3) bonds are formed simultaneously. This general transformation allows for construction of diverse N-heterocycles. Mechanistic studies show that the process may involve a four-membered Pd(alkyl)amido intermediate.
Palladium-Catalyzed Aerobic Oxidative Cyclization of Aliphatic Alkenyl Amides for the Construction of Pyrrolizidine and Indolizidine Derivatives
Lo, Kai-Yip,Ye, Liu,Yang, Dan
, p. 1570 - 1575 (2017/08/11)
An efficient palladium-catalyzed aerobic oxidative cyclization has been developed to synthesize a variety of pyrrolizidine and indolizidine derivatives from simple aliphatic alkenyl amides in moderate to good yields. The reaction features the capability of accessing various N-heterocycles and the use of molecular oxygen (1 atm) as the green oxidant.
Switchable Stereoselectivity in Bromoaminocyclization of Olefins: Using Br?nsted Acids of Anionic Chiral Cobalt(III) Complexes
Jiang, Hua-Jie,Liu, Kun,Yu, Jie,Zhang, Ling,Gong, Liu-Zhu
, p. 11931 - 11935 (2017/09/20)
Br?nsted acids of anionic chiral CoIII complexes act as bifunctional phase-transfer catalysts to shuttle the substrates across the solvent interface and control stereoselectivity. The diastereomeric chiral CoIII-templated Br?nsted ac
