62618-20-6Relevant academic research and scientific papers
Au-catalyzed biaryl coupling to generate 5- to 9-membered rings: Turnover-limiting reductive elimination versus π-complexation
Corrie, Tom J. A.,Ball, Liam T.,Russell, Christopher A.,Lloyd-Jones, Guy C.
supporting information, p. 245 - 254 (2017/05/29)
The intramolecular gold-catalyzed arylation of arenes by aryl-trimethylsilanes has been investigated from both mechanistic and preparative aspects. The reaction generates 5- to 9-membered rings, and of the 44 examples studied, 10 include a heteroatom (N, O). Tethering of the arene to the arylsilane provides not only a tool to probe the impact of the conformational flexibility of Ar-Au-Ar intermediates, via systematic modulation of the length of aryl-aryl linkage, but also the ability to arylate neutral and electron-poor arenes-substrates that do not react at all in the intermolecular process. Rendering the arylation intramolecular also results in phenomenologically simpler reaction kinetics, and overall these features have facilitated a detailed study of linear free energy relationships, kinetic isotope effects, and the first quantitative experimental data on the effects of aryl electron demand and conformational freedom on the rate of reductive elimination from diaryl-gold(III) species. The turnover-limiting step for the formation of a series of fluorene derivatives is sensitive to the reactivity of the arene and changes from reductive elimination to π-complexation for arenes bearing strongly electron-withdrawing substituents (σ > 0.43). Reductive elimination is accelerated by electron-donating substituents (ρ = -2.0) on one or both rings, with the individual σ-values being additive in nature. Longer and more flexible tethers between the two aryl rings result in faster reductive elimination from Ar-Au(X)-Ar and lead to the π-complexation of the arene by Ar-AuX2 becoming the turnover-limiting step.
Dimetallation of phenylacetylene. Synthesis of ortho-susbtituted derivatives of phenylacetylene, benzoselenophene and benzotellurophene
Brandsma, L.,Hommes, H.,Verkruijsse, H. D.,Jong, R. L. P. de
, p. 226 - 230 (2007/10/02)
Phenylacetylene can be dimetallated in two ways. o-K-C6H4-CC-Li is formed by treating phenylacetylene at -70 deg C with two equivalents of butyllithium and one equivalent of potassium tert-butoxide in a mixture of tetrahydrofuran and hexane.The dimetallation with BuLi*N,N,N',N'-tetramethylethanediamine (TMEDA) affords a mixture of about 15percent (m + p)-Li-C6H4-CCLi and 85percent o-LiC6H4-CC-Li.Ortho-K-C6H4-CC-Li can be transformed into the dilithio or di-Grignard derivatives by addition of anhydrous lithium bromide or magnesium bromide etherate.Reaction of the dilithio derivative with elemental selenium and tellurium, followed by successive addition of tert-butyl alcohol and hexamethylphosphoric triamide (HMPT), gives benzoselenophene and benzotellurophene in good yields.Regiospecific functionalization of the nucleus via dimetal derivatives succeeds in the case of alkylation, halogenation, sulfenylation and acylation (with dimethylformamide and dimethylacetamide).Trimethylchlorosilane, chloromethyl methyl ether, aldehydes and ketones do not however react regiospecifically.
Dimetallation of Phenylacetylene. Selective ortho-Substitution
Hommes, Hendrik,Verkruijsse, Hermann D.,Brandsma, Lambert
, p. 366 - 367 (2007/10/02)
Reaction of lithium phenylacetylide with the complex BuLi-ButOK in a mixture of tetrahydrofuran and hexane leads to the ortho-metallated phenylacetylide; subsequent addition of methyl iodide, dimethyl disulphide, trimethylchlorosilane, and sele
