80377-02-2Relevant articles and documents
Atomic Pt-Catalyzed Heterogeneous Anti-Markovnikov C-N Formation: Pt10Activating N-H for Pt1δ+-Activated C-C Attack
Ma, Xiaodan,An, Zhe,Song, Hongyan,Shu, Xin,Xiang, Xu,He, Jing
, p. 9017 - 9027 (2020/12/23)
C-N formation is of great significance to synthetic chemistry, as N-containing products are widely used in chemistry, medicine, and biology. Addition of an amine to an unsaturated carbon-carbon bond is a simple yet effective route to produce new C-N bonds. But how to effectively conduct an anti-Markovnikov addition with high selectivity has been a great challenge. Here, we proposed a strategy for highly regioselective C-N addition via hydroamination by using supported Pt. It has been identified that atomic-scale Pt is the active site for C-N addition with Pt12+ for Markovnikov C-N formation and atomic Pt (Pt1δ+ and Pt10) contributing to anti-Markovnikov C-N formation. A selectivity of up to 92% to the anti-Markovnikov product has been achieved with atomic Pt in the addition of styrene and pyrrolidine. A cooperating catalysis for the anti-Markovnikov C-N formation between Pt1δ+ and Pt10 has been revealed. The reaction mechanism has been studied by EPR spectra and in situ FT-IR spectra of adsorption/desorption of styrene and/or pyrrolidine. It has been demonstrated that Pt10 activates amine to be electrophilic, while Pt1δ+ activates C-C by π-bonding to make β-C nucleophilic. The attack of nucleophilic β-C to electrophilic amine affords the anti-Markovnikov addition. This strategy proves highly effective to a variety of substrates in anti-Markovnikov C-N formation, including aromatic/aliphatic amines reacting with aromatic olefins, aromatic/aliphatic olefins with aromatic amines, and linear aliphatic olefins with secondary aliphatic amines. It is believed that the results provide evidence for the function of varied chemical states in monatomic catalysis.
Mild and Selective Cobalt-Catalyzed Chemodivergent Transfer Hydrogenation of Nitriles
Shao, Zhihui,Fu, Shaomin,Wei, Mufeng,Zhou, Shaolin,Liu, Qiang
supporting information, p. 14653 - 14657 (2016/11/23)
Herein, we describe a selective cobalt-catalyzed chemodivergent transfer hydrogenation of nitriles to synthesize primary, secondary, and tertiary amines. The solvent effect plays a key role for the selectivity control. The general applicability of this procedure was highlighted by the synthesis of more than 70 amine products bearing various functional groups in high chemoselectivity. Moreover, this mild system achieved >2000 TONs (turnover numbers) for the transfer hydrogenation of nitriles.
The facile preparation of primary and secondary amines via an improved Fukuyama-Mitsunobu procedure. Application to the synthesis of a lung-targeted gene delivery agent
Guisado, Cristina,Waterhouse, Jodie E.,Price, Wayne S.,Jorgensen, Michael R.,Miller, Andrew D.
, p. 1049 - 1057 (2007/10/03)
An efficient modification of the Fukuyama-Mitsunobu procedure has been developed whereby primary or secondary amines can be synthesized from alkyl alcohols and the corresponding nosyl-protected/activated amine. Most importantly, the use of the DTBAD and diphenylpyridinylphosphine, as Mitsunobu reagents, generates reaction by-products that can be easily removed, providing a remarkably clean product mixture. This improved technique was implemented in the synthesis of a complex lipopeptide designed to target α 9β1-integrin proteins predominant on upper airway epithelial cells. The Royal Society of Chemistry 2005.
