Theoretical Studies of the Asymmetric Binary-Acid-Catalyzed tert-Aminocyclization Reaction: Origins of the C-sp3-H Activation and Stereoselectivity

doi:10.1002/asia.201200674

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	Theoretical Studies of the Asymmetric Binary-Acid-Catalyzed tert-Aminocyclization Reaction: Origins of the C-sp3-H Activation and Stereoselectivity
	Zhang, Long; Chen, Liujuan; Lv, Jian; Cheng, Jin-Pei; Luo, Sanzhong
刊名	CHEMISTRY-AN ASIAN JOURNAL
	2012-11-01
卷号	7 期号:11 页码:2569-2576
关键词	c?c?C?c?h Activation Density Functional Calculations Lewis Acids Phosphoric Acid Tert-aminocyclization
ISSN号	1861-4728
DOI	10.1002/asia.201200674
英文摘要	A mechanistic study of the tert-aminocyclization reaction was performed by using DFT calculations and labeling experiments. The results showed that the reaction proceeded through a rate-limiting-, stereospecific-, and suprafacial 1,5-H-transfer pathway, followed by a barrier-less C?C bond formation. The mode of stereocontrol for facial selection could be ruled out owing to the high activation energy of C?N bond rotation. The intrinsic feature of this Lewis acid activation was found to be the activation of the LUMO, as well as an intermediate-stabilization effect. The catalytically active species was believed to be a 1:1 complex of phosphoric acid and MgCl2, which was stabilized by a H...Cl hydrogen bond. The chiral catalytic complex selectively recognizes and activates one of the two helical conformations of substrate A, required for 1,5-suprafacial H-transfer, which dictates the stereoselectivity of the forming products.
语种	英语
出版者	WILEY-V C H VERLAG GMBH
WOS记录号	WOS:000309717300017
内容类型	期刊论文
源URL	[http://ir.iccas.ac.cn/handle/121111/47877]
专题	中国科学院化学研究所
通讯作者	Luo, Sanzhong
作者单位	Chinese Acad Sci, Beijing Natl Lab Mol Sci, CAS Key Mol Recognit & Funct Inst Chem, Beijing 100190, Peoples R China
推荐引用方式 GB/T 7714	Zhang, Long,Chen, Liujuan,Lv, Jian,et al. Theoretical Studies of the Asymmetric Binary-Acid-Catalyzed tert-Aminocyclization Reaction: Origins of the C-sp3-H Activation and Stereoselectivity[J]. CHEMISTRY-AN ASIAN JOURNAL,2012,7(11):2569-2576.
APA	Zhang, Long,Chen, Liujuan,Lv, Jian,Cheng, Jin-Pei,&Luo, Sanzhong.(2012).Theoretical Studies of the Asymmetric Binary-Acid-Catalyzed tert-Aminocyclization Reaction: Origins of the C-sp3-H Activation and Stereoselectivity.CHEMISTRY-AN ASIAN JOURNAL,7(11),2569-2576.
MLA	Zhang, Long,et al."Theoretical Studies of the Asymmetric Binary-Acid-Catalyzed tert-Aminocyclization Reaction: Origins of the C-sp3-H Activation and Stereoselectivity".CHEMISTRY-AN ASIAN JOURNAL 7.11(2012):2569-2576.