74137-36-3Relevant articles and documents
Synthesis and reactivities of new NCN-type pincer complexes of nickel
Cloutier, Jean-Philippe,Vabre, Boris,Moungang-Soum, Berline,Zargarian, Davit
, p. 133 - 145 (2015)
This report describes the preparation, characterization, and reactivities of a new family of Ni(II) complexes based on the pincer-type ligands R-NCNpz (κN,κC,κN-1,3-bis(pyrazole),5-R-C6H2; R = H, OMe). Ullman coupling of pyrazole with 1,3-diiodobenzene or 1,3-dibromo-5-methoxybenzene gave the compounds R-NC(H)Npz, which were refluxed in xylene with (i-PrCN)NiBr2 and NEt3 to give the complexes (NCNpz)NiBr (1) and (MeO-NCNpz)NiBr (2) via C-H nickelation. The aryloxide derivative (NCNpz)Ni(OAr) (3; Ar = 2,6-t-Bu2-4-Me-OC6H2) was prepared by treating the bromo precursor 1 with NaOAr, whereas the analogous reaction with NaOEt gave instead the protonated or ethoxy-functionalized ligand NC(H)Npz (major) and NC(OEt)Npz (minor). The new complexes 1-3 were fully characterized, including solid-state structures. Attempted oxidation of these complexes failed to give the target trivalent derivatives, leading instead to intractable, deeply colored Ni-containing solids, various ligand-derived side products, or an unusual I2 adduct. For example, treatment of 1 or 2 with N-bromosuccinimide gave sparingly soluble dark solids that appear to be paramagnetic, whereas 3 reacted with Br2 to give short-lived dark intermediates that decomposed over seconds to give ArOH. Reaction of the bromo complexes with aqueous H2O2 (30%) gave the functionalized ligands Br-NC(OH)Npz and NC(OH)Npz (from 1) or MeO-NC(OH)Npz (from 2), whereas 1 reacted with I2 to generate (NCNpz)NiBr·I2, an iodine adduct displaying weak Br-I interactions. Heating 1 in EtOH in air generated NC(OEt)Npz. This ligand derivatization could be extended to other alcohols (MeOH, i-PrOH, CF3CH2OH) and amines (morpholine, cyclohexylamine, aniline). Possible mechanistic scenarios for the observed oxidative, Ni-promoted Cipso-X bond formation reactions are discussed in the context of relevant literature precedents.
Nickel-Catalyzed Reversible Functional Group Metathesis between Aryl Nitriles and Aryl Thioethers
Delcaillau, Tristan,Boehm, Philip,Morandi, Bill
supporting information, p. 3723 - 3728 (2021/04/07)
We describe a new functional group metathesis between aryl nitriles and aryl thioethers. The catalytic system nickel/dcype is essential to achieve this fully reversible transformation in good to excellent yields. Furthermore, the cyanide- and thiol-free reaction shows high functional group tolerance and great efficiency for the late-stage derivatization of commercial molecules. Finally, synthetic applications demonstrate its versatility and utility in multistep synthesis.
A containing pyrimidine group rigid conjugated macrocyclic compound and its preparation method and application (by machine translation)
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Paragraph 0034; 0046; 0047, (2017/05/18)
The invention relates to a containing pyrimidine group rigid conjugated macrocyclic compound and its preparation method and application, structure of the compound of the general formula: wherein n=1, 2, 3, 4, 5. The preparation comprises: to the rigid part of the 3, 5 - dibromide fluoride as the raw material for the synthesis of 3, 5 - di bromo methyl ether, then tribromide the boron escapes methylation reaction for the synthesis of 3, 5 - two-bromophenol, the linear part of the 3 - chloro - 2 - chloromethyl propylene as the starting material, to obtain the linear part of the intermediate, after 3, 5 - b bromophenol under alkaline conditions with the linear part of the intermediate synthesis of 3, 5 - b bromophenylacetic long chain ether, using 3, 5 - b bromophenylacetic long chain ethergathers two boron mellowly with dual-frequency which Miyaura reaction on synthetic monomer II; monomer II with 5 - bromo - 2 through the Suzuki coupling reaction of iodine pyrimidine synthetic monomer III; the use of monomer II and monomer III Suzuki coupling to get through. The invention the resulting compounds as functional material application. (by machine translation)
