16636-96-7Relevant articles and documents
Synthesis of a Sterically Demanding Dispiropiperidine and Its Application in Monoamidodialkyl Zincate Complexes
Morisako, Shogo,Shang, Rong,Yamamoto, Yohsuke
, p. 10767 - 10773 (2016)
The new sterically hindered piperidine analog, dispiro[cyclohexane-2,2′-piperidine-6′,2″-cyclohexane] (CPC(H), 2), and its N-methylated derivative CPC(Me) (3) were synthesized from commercially available starting materials in short steps. The N-lithiated amide LiCPC (4) was also isolated from 2 as a cyclictrimer in single crystals and showed slightly larger steric hindrance than that of lithium 2,2,6,6-tetramethylpiperidide (LiTMP) in the competitive methylation reaction with methyl trifluoromethanesulfonate. In addition, the heterobimetallic heteroleptic zincate complexes [Li(μ-NR2)(μ-Et)Zn(Et)] (NR2 = CPC, 5, and NR2 = TMP, 6) were obtained as THF- and TMEDA-coordinated monomer 5·(THF)2, 6·(THF)2, 5·TMEDA, and 6·TMEDA (THF = tetrahydrofuran, TMEDA = N,N,N′,N′-tetramethylethylenediamine). These molecular structures bearing different amido ligands in single crystals showed little structural differences from crystallographic studies. Diffusion-ordered spectroscopy (DOSY) revealed that the solution structures of the zincate complexes 5·(THF)2 and 6·(THF)2 only differ in the number of coordination THF molecules. In the deprotonation reactions with tert-butyl 3-bromobenzoate, the zincate complexes containing the CPC ligand [Li(μ-CPC)(μ-R)Zn(R)] (R = Et (5), tBu) showed moderately improved regioselectivity for the 6 position in comparison to those containing the TMP ligand [Li(μ-TMP)(μ-R)Zn(R)] (R = Et (6), tBu).
Three-Component Difunctionalization of Cyclohexenyl Triflates: Direct Access to Versatile Cyclohexenes via Cyclohexynes
Cho, Seoyoung,McLaren, E. J.,Wang, Qiu
supporting information, p. 26332 - 26336 (2021/11/10)
Difunctionalization of strained cyclic alkynes presents a powerful strategy to build richly functionalized cyclic alkenes in an expedient fashion. Herein we disclose an efficient and flexible approach to achieve carbohalogenation, dicarbofunctionalization, aminohalogenation and aminocarbonation of readily available cyclohexenyl triflates. We have demonstrated the novel use of zincate base/nucleophile system for effective formation of key cyclohexyne intermediates and selective addition of various carbon and nitrogen nucleophiles. Importantly, leveraging the resulting organozincates enables the incorporation of a broad range of electrophilic partners to deliver structurally diverse cyclohexene motifs. The importance and utility of this method is also exemplified by the modularity of this approach and the ease in which even highly complex polycyclic scaffolds can be accessed in one step.
Synthesis and structures of new binuclear zinc alkyl, aryl and aryloxo complexes
Sarazin, Yann,Wright, Joseph A.,Harding, Duncan A.J.,Martin, Eddy,Woodman, Timothy J.,Hughes, David L.,Bochmann, Manfred
, p. 1494 - 1501 (2008/09/18)
The synthesis of a series of binuclear zinc complexes with Cl, N and O bridges is reported. The reaction of EtZnCl with B(C6F5)3 in the presence of hexamethylbenzene affords the arene complex [Zn(μ-Cl)(C6F5)(η-C6Me6)]2 in which the C6Me6 ligand may be regarded as η3-bonded. The comproportionation of Zn[N(SiMe3)2]2 with ZnBut2 or Zn(C6F5)2 · toluene gave [ButZn{μ-N(SiMe3)2}]2 and [C6F5Zn{μ-N(SiMe3)2}]2, respectively, with three-coordinate zinc. The reaction of ZnEt2 with C6F5OH in the presence of pyridine gave [EtZn(μ-OC6F5)(py)]2, while ZnMe2 and C6F5OH followed by recrystallisation from THF gave [Zn(OC6F5)(μ-OC6F5)(THF)2]2 with five-coordinate zinc in a trigonal-bipyramidal geometry. The structures of these compounds have been determined.
