Reactivity of 2-benzylpyridyl lithium toward benzonitrile derivatives: Addition versus elimination

doi:10.1016/j.jorganchem.2017.10.042

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	Reactivity of 2-benzylpyridyl lithium toward benzonitrile derivatives: Addition versus elimination
	Hao, Xiaomin 1; Qin, Lu 1; Xu, Mali 1; Chen, Xia 1,2
刊名	JOURNAL OF ORGANOMETALLIC CHEMISTRY
	2017-12-15
卷号	853 页码:168-177
关键词	2-benzylpyridyl Lithium Nitriles Addition Elimination Bimolecular Coupling Silyl Group Migration
ISSN号	0022-328X
DOI	10.1016/j.jorganchem.2017.10.042
英文摘要	This work investigated the reactivity of 2-benzylpyridyl lithium (2-Pyr) C(Ph)(R)Li (R - SiMe3, Li1; R - H, Li2) toward benzonitrile derivatives. Based on the different products, the reaction between lithium salts and nitriles might involve in addition, elimination and bimolecular coupling pathways, respectively. Treatment of Li1 with ArCN (Ar = Ph, p-Tolyl, o-Tolyl, p-OMePh) yielded an addition intermediate pyridyl- 1-aza-allyl-lithium [{(2-Pyr)C(Ph)C(Ar)N(SiMe3)}Li](2) (1, Ar = Ph) and its corresponding hydrolysis product 2-benzylpyridyl-ketone 2-5, respectively, in which the reaction involved in a 1,3-shift of -SiMe3 group to form a dimeric pyridyl-1-aza-allyl-lithium then followed by acidic hydrolysis. The MeOLi elimination reaction between Li2 and p-MeO(C6H4) CN resulted in formation of 4-(2-benzylpyridyl) benzonitrile 6. The reaction of Li2 with p-Me(C6H4) CN in the presence of TMEDA generated a 1: 2 hydrolysis adduct 2-benzylpyridyl-enaminone 7, however, in the absence of TMEDA it afforded a coupling product of bimolecular nitriles, 1-(4-methylphenyl)-2-cyanophenyl-ethanone 8. We speculated the reaction mechanisms in sequence. The crystal structures of 1 and 5-8 were analyzed. (C) 2017 Elsevier B.V. All rights reserved.
语种	英语
出版者	ELSEVIER SCIENCE SA
WOS记录号	WOS:000417654800021
内容类型	期刊论文
源URL	[http://ir.iccas.ac.cn/handle/121111/45287]
专题	中国科学院化学研究所
通讯作者	Chen, Xia
作者单位	1.Shanxi Univ, Sch Chem & Chem Engn, Taiyuan 030006, Peoples R China 2.Chinese Acad Sci, Changchun Inst Appl Chem, State Key Lab Polymer Phys & Chem, Changchun 130022, Jilin, Peoples R China
推荐引用方式 GB/T 7714	Hao, Xiaomin,Qin, Lu,Xu, Mali,et al. Reactivity of 2-benzylpyridyl lithium toward benzonitrile derivatives: Addition versus elimination[J]. JOURNAL OF ORGANOMETALLIC CHEMISTRY,2017,853:168-177.
APA	Hao, Xiaomin,Qin, Lu,Xu, Mali,&Chen, Xia.(2017).Reactivity of 2-benzylpyridyl lithium toward benzonitrile derivatives: Addition versus elimination.JOURNAL OF ORGANOMETALLIC CHEMISTRY,853,168-177.
MLA	Hao, Xiaomin,et al."Reactivity of 2-benzylpyridyl lithium toward benzonitrile derivatives: Addition versus elimination".JOURNAL OF ORGANOMETALLIC CHEMISTRY 853(2017):168-177.