General One-Pot Reductive gem-Bis-Alkylation of Tertiary Lactams/Amides: Rapid Construction of 1-Azaspirocycles and Formal Total Synthesis of (+/-)-Cephalotaxine

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	General One-Pot Reductive gem-Bis-Alkylation of Tertiary Lactams/Amides: Rapid Construction of 1-Azaspirocycles and Formal Total Synthesis of (+/-)-Cephalotaxine
	Xiao, Kai-Jiong ; Luo, Jie-Min ; Xia, Xiao-Er ; Wang, Yu ; Huang, Pei-Qiang ; Huang PQ(黄培强)
刊名	http://dx.doi.org/10.1002/chem.201302096
	2013
关键词	SEQUENTIAL ADDITION-REACTIONS RING-CLOSING METATHESIS TRICYCLIC MARINE ALKALOIDS HIGHLY EFFICIENT SYNTHESIS HARRINGTONIA VAR. NANA AMIDE BOND FORMATION GRIGNARD-REAGENTS TRIFLIC ANHYDRIDE SECONDARY AMIDES CEPHALOTAXUS ALKALOIDS
英文摘要	National Basic Research Program (973 Program) of China [2010CB833200]; NSF of China [21072160, 20832005]; Program for Changjiang Scholars and Innovative Research Team in University (PCSIRT) of Ministry of Education, China; Amides are a class of highly stable and readily available compounds. The amide functional group constitutes a class of powerful directing/activating and protecting group for CC bond formation. Tertiary tert-alkylamine, including 1-azaspirocycle is a key structural feature found in many bioactive natural products and pharmaceuticals. The transformation of amides into tert-alkylamines generally requires several steps. In this paper, we report the full details of the first general method for the direct transformation of tertiary lactams/amides into tert-alkylamines. The method is based on in situ activation of amide with triflic anhydride/2,6-di-tert-butyl-4-methylpyridine (DTBMP), followed by successive addition of two organometallic reagents of the same or different kinds to form two CC bonds. Both alkyl and functionalized organometallic reagents and enolates can be used as the nucleophiles. The method displayed excellent 1,2- and good 1,3-asymmetric induction. Construction of 1-azaspirocycles from lactams required only two steps or even one-step by direct spiroannelation of lactams. The power of the method was demonstrated by a concise formal total synthesis of racemic cephalotaxine.
语种	英语
出版者	WILEY-V C H VERLAG GMBH
内容类型	期刊论文
源URL	[http://dspace.xmu.edu.cn/handle/2288/88898]
专题	化学化工－已发表论文
推荐引用方式 GB/T 7714	Xiao, Kai-Jiong,Luo, Jie-Min,Xia, Xiao-Er,et al. General One-Pot Reductive gem-Bis-Alkylation of Tertiary Lactams/Amides: Rapid Construction of 1-Azaspirocycles and Formal Total Synthesis of (+/-)-Cephalotaxine[J]. http://dx.doi.org/10.1002/chem.201302096,2013.
APA	Xiao, Kai-Jiong,Luo, Jie-Min,Xia, Xiao-Er,Wang, Yu,Huang, Pei-Qiang,&黄培强.(2013).General One-Pot Reductive gem-Bis-Alkylation of Tertiary Lactams/Amides: Rapid Construction of 1-Azaspirocycles and Formal Total Synthesis of (+/-)-Cephalotaxine.http://dx.doi.org/10.1002/chem.201302096.
MLA	Xiao, Kai-Jiong,et al."General One-Pot Reductive gem-Bis-Alkylation of Tertiary Lactams/Amides: Rapid Construction of 1-Azaspirocycles and Formal Total Synthesis of (+/-)-Cephalotaxine".http://dx.doi.org/10.1002/chem.201302096 (2013).