Reactivity of Organolithium Reagents to 2,3,4,5-Tetraphenylcyclopentadienone and Crystal Structures of Addition Products

doi:10.1007/s40242-015-5219-7

Chemical Research in Chinese Universities ›› 2015, Vol. 31 ›› Issue (5): 736-741.doi: 10.1007/s40242-015-5219-7

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Reactivity of Organolithium Reagents to 2,3,4,5-Tetraphenylcyclopentadienone and Crystal Structures of Addition Products

ZHANG Xiaoyong^1,2, HAN Limin¹, ZHU Ning¹, GAO Yuanyuan¹, SUO Quanling¹

1. Chemical Engineering College, Inner Mongolia University of Technology, Hohhot 010051, P. R. China;
2. Department of Chemistry, Baotou Teacher's College, Baotou 014030, P. R. China

Received:2015-06-01 Revised:2015-06-12 Online:2015-10-01 Published:2015-07-06
Contact: SUO Quanling, E-mail: szj010062@163.com E-mail:szj010062@163.com
Supported by:
Supported by the National Natural Science Foundation of China(Nos.21266019, 21062011) and the Inner Mongolia Autonomous Region Higher Scientific Research Project, China(No.NJZY14060).

Abstract

Abstract:

The conjugate addition reactions of four organolithium reagents to 2,3,4,5-tetraphenylcyclopentadienone (tetracyclone) were investigated to reveal the reactivity of organolithium reagents to tetracyclone. The results show that 1,2-addition products 2,3,4,5-tetraphenyl-1-(2-thienyl)-2,4-cyclopentadien-1-ol(1), 1-n-butyl-2,3,4,5-tetraphenyl-2,4-cyclopentadien-1-ol(2) and 1,2,3,4,5-pentaphenyl-2,4-cyclopentadien-1-ol(3) were synthesized in excellent yields while tetracyclone reacted with 2-thienyllithium, n-butyllithium and phenyllithium, respectively. Interestingly, three 1,2-, 1,4- and 1,6-addition isomers 1-tert-butyl-2,3,4,5-tetraphenyl-2,4-cyclopentadien-1-ol(4), 4-tert-butyl-2,3,4,5-tetraphenyl-2-cyclopenten-l-one(5) and 2-tert-butyl-2,3,4,5-tetraphenyl-3-cyclopenten-l-one(6), were simultaneously obtained by the conjugate addition reaction of tert-butyllithium with larger steric hindrance to tetracyclone. Compounds 1-6 were characterized by ¹H and ¹³C NMR spectra, Fourier transform infrared(FTIR) spectra and mass spectra(MS). The crystal and molecular structures of compounds 1, 2 and isomers 5, 6 were determined by X-ray single crystal diffraction technique. The results imply that the steric hindrance of tert-butyllithium probably play a key role in controlling the conjugate addition reaction. The conjugate addition mechanism of organolithium reagents to tetracyclone was proposed.

Key words: Conjugate addition reaction, 2,3,4,5-Tetraphenylcyclopentadienone, Organolithium reagent, Steric hindrance

ZHANG Xiaoyong, HAN Limin, ZHU Ning, GAO Yuanyuan, SUO Quanling. Reactivity of Organolithium Reagents to 2,3,4,5-Tetraphenylcyclopentadienone and Crystal Structures of Addition Products[J]. Chemical Research in Chinese Universities, 2015, 31(5): 736-741.

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Reactivity of Organolithium Reagents to 2,3,4,5-Tetraphenylcyclopentadienone and Crystal Structures of Addition Products

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