Dearomatizing anionic cyclization and novel skeletal rearrangement: High   yield formation of multiply substituted bicyclic or polycyclic   spirocyclopentadienes and phenanthrene derivatives from 4-aryl   1-lithio-1,3-butadienes

doi:10.1021/jo070160u

CORC > 北京大学 > 化学与分子工程学院

	Dearomatizing anionic cyclization and novel skeletal rearrangement: High yield formation of multiply substituted bicyclic or polycyclic spirocyclopentadienes and phenanthrene derivatives from 4-aryl 1-lithio-1,3-butadienes
	Liu, Lantao ; Wang, Zhihui ; Zhao, Fei ; Xi, Zhenfeng
刊名	journal of organic chemistry
	2007
关键词	ALKYL-N-BENZYLDIPHENYLPHOSPHINAMIDES METAL-MEDIATED DEAROMATIZATION PALLADIUM-CATALYZED ANNULATION NUCLEOPHILIC-ADDITION FLUORINATED NAPHTHALENE ORGANOLITHIUM REAGENTS RUTHENIUM COMPLEXES AROMATIC-COMPOUNDS ORGANIC-SYNTHESIS INTERNAL ALKYNES
DOI	10.1021/jo070160u
英文摘要	Both 4-phenyl 1-lithio-1,3-butadienes and 4-naphthyl 1-lithio-1,3-butadienes underwent highly efficient and selective intramolecular nucleophilic addition of the butadienyllithium to the aromatic rings, resulting in full dearomatization of the phenyl rings and partial dearomatization of the naphthyl rings. When the reactions were carried out at lower temperatures, ipso intramolecular nucleophilic attack took place exclusively to afford the spirocyclopentadiene derivatives upon hydrolysis or further treatment with a variety of electrophiles. 4-Naphthyl 1-lithio-1,3-butadienes and 4-phenyl 1-lithio-1,3-butadienes were found to proceed in this reaction under similar conditions, with the former being faster even at -78 degrees C. However, when the reaction of 4-naphthyl 1-lithio-1,3-butadienes was carried out at higher temperatures, such as 75 degrees C, an interesting skeletal rearrangement took place to afford the vicinal attack products, tetrasubstituted phenanthrenes, via a dearomatization/rearomatization process. Mechanistic investigation revealed that the kinetically favored ipso attack intermediates might undergo thermal skeletal rearrangement via 1,2-alkyl shift.; Chemistry, Organic; SCI(E); EI; 0; ARTICLE; 9; 3484-3491; 72
语种	英语
内容类型	期刊论文
源URL	[http://ir.pku.edu.cn/handle/20.500.11897/251465]
专题	化学与分子工程学院
推荐引用方式 GB/T 7714	Liu, Lantao,Wang, Zhihui,Zhao, Fei,et al. Dearomatizing anionic cyclization and novel skeletal rearrangement: High yield formation of multiply substituted bicyclic or polycyclic spirocyclopentadienes and phenanthrene derivatives from 4-aryl 1-lithio-1,3-butadienes[J]. journal of organic chemistry,2007.
APA	Liu, Lantao,Wang, Zhihui,Zhao, Fei,&Xi, Zhenfeng.(2007).Dearomatizing anionic cyclization and novel skeletal rearrangement: High yield formation of multiply substituted bicyclic or polycyclic spirocyclopentadienes and phenanthrene derivatives from 4-aryl 1-lithio-1,3-butadienes.journal of organic chemistry.
MLA	Liu, Lantao,et al."Dearomatizing anionic cyclization and novel skeletal rearrangement: High yield formation of multiply substituted bicyclic or polycyclic spirocyclopentadienes and phenanthrene derivatives from 4-aryl 1-lithio-1,3-butadienes".journal of organic chemistry (2007).