title: 1,2,3,4-Tetrasubstituted cyclopentadienes and their applications for metallocenes: efficient synthesis through zirconocene- and CuCl-mediated intermolecular coupling of two alkynes and one diiodomethane.
abstract: 1,2,3,4-Tetrasubstituted cyclopentadienes and indene derivatives with identical or different substituents were obtained in good to excellent isolated yields through a zirconocene- and CuCl-mediated intermolecular coupling process. This synthetic procedure involved three organic partners, including one CH2 I2 , and two different or identical alkynes. Two alkynes or one diyne undergo Cp2Zr(II)-mediated (Cp = η(5)-C5H5) pair-selective reductive coupling to afford the corresponding zirconacyclopentadiene derivatives, which react, in the presence of CuCl and 1,3-dimethyl-3,4,5,6-tetrahydro-2(1 H)-pyrimidinone (DMPU), with CH2I2 through intermolecular followed by intramolecular coupling to afford the cyclopentadiene derivatives. An application of the prepared tetrasubstituted cyclopentadiene derivatives was demonstrated by the facile synthesis of the corresponding zirconocene complexes [((4R)Cp)2ZrCl2] and [((4R)Cp)2ZrR'2] (R' = Me, Et, or nBu). The unique 1,2,3,4-tetrasubstituted cyclopentadiene ligands and the corresponding metallocenes are expected to have further applications in organometallic chemistry and organic synthesis.
authors: Beijing National Laboratory for Molecular Sciences (BNLMS), College of Chemistry, Peking University, Beijing 100871, PR China.
authors: Weizhi
authors: W
authors: Geng
authors: Chao
authors: C
authors: Wang
authors: Jie
authors: J
authors: Guang
authors: Wei
authors: W
authors: Hao
authors: Wen-Xiong
authors: WX
authors: Zhang
authors: Zhenfeng
authors: Z
authors: Xi