31600-86-9Relevant academic research and scientific papers
The molecular structure of 1-lithio-2-methoxybenzene in the solid state and in solution
Harder, Sjoerd,Boersma, Jaap,Brandsma, Lambert,Mier, Guido P. M. van,Kanters, Jan A.
, p. 1 - 16 (1989)
The X-ray structure of 1-lithio-2-methoxybenzene (2-methoxyphenyllithium) has been determined at 298 K by single crystal X-ray techniques.The compound crystallizes in the triclinic system with spacegroup p1.Cell dimensions: a 8.889(2), b 11.710(5), c 12.9
Asymmetric synthesis of metallocenes through enantioselective addition of organolithium reagents to 6-(dimethylamino)fulvene
Suzuka, Toshimasa,Ogasawara, Masamichi,Hayashi, Tamio
, p. 3355 - 3359 (2002)
Enantioselective addition of aryllithiums 2a-d (Ar = Ph (a), 2-MeC6H4 (b), 2-MeOC6H4 (c), 1-naphthyl (d)) to 6-(dimethylamino)fulvene (1) in the presence of (-)-sparteine in toluene at -78°C generated chiral cyclopentadienyllithiums (4) substituted with an N,N-dimethylamino(aryl)methyl group, where the enantioselectivities are 51, 91, 90, and 83% for 4a, 4b, 4c, and 4d, respectively. Treatment of the chiral cyclopentadienides 4 with FeCl2 or Fe(acac)2 gave ferrocenes, which contain an N,N-dimethylamino(aryl)methyl side chain on both of the cyclopentadienyl rings. The enantiomeric purity of the chiral ferrocenes 7 thus obtained is 99% ee or higher for those containing a 2-MeC6H4 (7b) or a 2-MeOC6H4 (7c) group.
Media effects in directed ortho metalation
Slocum,Reed,Jackson III,Friesen
, p. 265 - 267 (1996)
Rates and extents of directed ortho metalation (DoM) of anisole and p-methylanisole (p-MA) with n-BuLi have been measured in THF/n-hexane. About a 14% (v/v) solution of THF in the hydrocarbon provides an extent of metalation which exceeds that in neat THF
Double Porphyrin Cage Compounds
Elemans, Johannes A. A. W.,Klop, Jo?lle-Rose,Mabesoone, Mathijs F. J.,Meijer, Eline M.,Nolte, Roeland J. M.,Peters, Theo P. J.,Rowan, Alan E.,Stout, Kathleen,Visschers, Fabian L. L.,White, Paul B.,van den Berg, Jeroen
, p. 7087 - 7100 (2020/12/07)
The synthesis and characterization of double porphyrin cage compounds are described. They consist of two porphyrins that are each attached to a diphenylglycoluril-based clip molecule via four ethyleneoxy spacers, and are linked together by a single alkyl chain using “click”-chemistry. Following a newly developed multistep synthesis procedure we report three of these double porphyrin cages, linked by spacers of different lengths, i.e. 3, 5, and 11 carbon atoms. The structures of the double porphyrin cages were fully characterized by NMR, which revealed that they consist of mixtures of two diastereoisomers. Their zinc derivatives are capable of forming sandwich-like complexes with the ditopic ligand 1,4-diazabicyclo[2,2,2]octane (dabco).
Reductive Elimination from Phosphine-Ligated Alkylpalladium(II) Amido Complexes to Form sp3 Carbon-Nitrogen Bonds
Peacock, D. Matthew,Jiang, Quan,Hanley, Patrick S.,Cundari, Thomas R.,Hartwig, John F.
supporting information, p. 4893 - 4904 (2018/04/16)
We report the formation of phosphine-ligated alkylpalladium(II) amido complexes that undergo reductive elimination to form alkyl-nitrogen bonds and a combined experimental and computational investigation of the factors controlling the rates of these react
Synthesis of Benzosiloles by Intramolecular anti-Hydroarylation via ortho-C-H Activation of Aryloxyethynyl Silanes
Minami, Yasunori,Noguchi, Yuta,Hiyama, Tamejiro
supporting information, p. 14013 - 14016 (2017/10/17)
Straightforward synthesis of benzosiloles was achieved by the invention of Pd/acid-catalyzed intramolecular anti-hydroarylation of aryloxyethynyl(aryl)silanes via ortho-C-H bond activation. The aryloxy group bound to the ethynyl carbon is the key factor for this transformation.
Palladium-Catalyzed, Site-Selective Direct Allylation of Aryl C-H Bonds by Silver-Mediated C-H Activation: A Synthetic and Mechanistic Investigation
Lee, Sarah Yunmi,Hartwig, John F.
supporting information, p. 15278 - 15284 (2016/12/06)
We describe a method for the site-selective construction of a C(aryl)-C(sp3) bond by the palladium-catalyzed direct allylation of arenes with allylic pivalates in the presence of AgOPiv to afford the linear (E)-allylated arene with excellent regioselectivity; this reaction occurs with arenes that have not undergone site-selective and stereoselective direct allylation previously, such as monofluorobenzenes and non-fluorinated arenes. Mechanistic studies indicate that AgOPiv ligated by a phosphine reacts with the arene to form an arylsilver(I) species, presumably through a concerted metalation-deprotonation pathway. The activated aryl moiety is then transferred to an allylpalladium(II) intermediate formed by oxidative addition of the allylic pivalate to the Pd(0) complex. Subsequent reductive elimination furnishes the allyl-aryl coupled product. The aforementioned proposed intermediates, including an arylsilver complex, have been isolated, structurally characterized, and determined to be chemically and kinetically competent to undergo the proposed elementary steps of the catalytic cycle.
Copper-catalysed cross-coupling of arylzirconium reagents with aryl and heteroaryl iodides
Thapa, Surendra,Basnet, Prakash,Gurung, Santosh K.,Giri, Ramesh
supporting information, p. 4009 - 4012 (2015/03/30)
An unprecedented CuI-catalysed cross-coupling of arylzirconium reagents with aryl and heteroaryl iodides is reported. Mechanistic studies with a Cp2ZrAr2 complex revealed that Cp2Zr(Ar)(Cl) is the reactive species that undergoes transmetalation with (PN-1)CuI. In addition, experiments with radical probes indicated that the reaction proceeds via a non-radical pathway. This journal is
METHOD FOR PRODUCING LINEAR AND/OR CYCLIC CARBONATE ESTERS
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Paragraph 0106-0109, (2016/11/17)
Preparing linear and/or cyclic carbonate ester, comprises reacting an epoxide with carbon dioxide in the presence of a catalyst. The catalyst comprises a metal complex (IIa) or (IIb) with a ligand (IIc). The metal (IIa) is present in an oxidation state of >= 0. Preparing linear and/or cyclic carbonate ester, comprises reacting an epoxide with carbon dioxide in the presence of a catalyst. The catalyst comprises a metal complex of formula (M) (IIa) or (MA) (IIb) with a ligand of formula (L) (Iic). The metal (IIa) is present in an oxidation state of >= 0. A : halo, carboxylate, phenoxide, sulfonate, phosphonate, alkyl, alkoxy or amido; L : (Ia) or (Ib), where OH groups may be deprotonated; R1-R4 : H, 1-22C alkyl, 5-12C cycloalkyl, 7-14C aralkyl or 7-14C alkylaryl or 6-14C aryl; X : amine moiety of formula (II) or alkane moiety of formula (III); R5 : 1-22C alkyl, 5-12C cycloalkyl, 7-14C aralkyl, or 7-14C alkylaryl, 6-14C aryl, or optionally alkyl-substituted pyridyl or pyridylmethyl; R6, R7 : H, 1-22C alkyl, 5-12C cycloalkyl, 7-C14-aralkyl or alkylaryl, 6-14C aryl or -COOR8; and R8 : 1-8C alkyl. Independent claims are also included for: (1) the polymeric carbonate ester, which is obtained by the reaction of cyclic epoxide with carbon dioxide by the above mentioned method, where the number average molecular weight of polymeric carbonate ester determined by gel permeation chromatography is >= 500 g/mole to = 5000 g/mole and the polydispersity index is >= 1 to = 1.5; and (2) a metal complex of formula (XIX) or (XX). M1 : Cr(III)-A, Co(III)-A or Zn(II). [Image] [Image] [Image].
Stereostructure and thermodynamic stability of atropisomers of ortho-substituted 2,2′-diaryl-1,1′-binaphthalenes
Ehn, Marcel,Vassilev, Nikolay Georgiev,Kasak, Peter,Horvath, Branislav,Filo, Juraj,Mereiter, Kurt,Rakovsky, Erik,Putala, Martin
, p. 1303 - 1311 (2013/11/19)
A series of ortho-substituted 2,2′-aryl-1,1′-binaphthalenes were prepared via Negishi arylation of 2,2′-diiodo-1,1′- binaphthalene in good to high yields (65-95%) as an equilibrium mixtures of up to three atropisomers (unlike,unlike, like,unlike, and like,like). Thermodynamic stability parameters of the atropisomers were evaluated from VT NMR spectra by regression analysis. The DFT parameters calculated using CAM-B3LYP functional comprising solvent permittivity were, apart from the toluene solution, which was expected to interact with the aromatic solute, in qualitative agreement with the experimental values. In the case of the ditolyl derivative, the population of the atropisomers was confirmed by CD spectroscopy via comparison with the population-weighted averaged spectrum computed using the M06 functional. X-ray structure analyses of particular atropisomers of the dianisyl, dianilinyl, and dinaphthyl derivatives are also presented and discussed.
