150024-49-0Relevant articles and documents
Reconnaissance of reactivity of an Ag(II)SO4 one-electron oxidizer towards naphthalene derivatives
Budniak, Adam K.,Masny, Micha?,Prezelj, Kristina,Grzeszkiewicz, Miko?aj,Gawraczyński, Jakub,Dobrzycki, ?ukasz,Cyrański, Micha? K.,Ko?miński, Wiktor,Mazej, Zoran,Fija?kowski, Karol J.,Grochala, Wojciech,Leszczyński, Piotr J.
, p. 10742 - 10749 (2017)
We test divalent silver sulphate, Ag(ii)SO4 as a novel reagent for oxidative coupling of aromatic hydrocarbons under ambient temperature conditions. The applicability of the C(sp2)-C(sp2) coupling protocol is illustrated for naphthalene and its 1-substituted derivatives containing either electron donating (e.g. Me, MeO, or Ph) or electron-withdrawing groups (X = F?I), leading to 4,4′-disubstituted-1,1′-binaphthyls. Coupling of 2-bromo-naphthalene yields a mixture of 2,2′-, 2,7′-, and 7,7′-dibromo-1,1′-binaphthyls together with their trimeric and tetrameric analogues. The coupling of strongly electron-withdrawing 1-CF3-naphthalene provides the 5,5′-disubstituted-1,1′-binaphthyl derivative. The new method does not require the presence of halogen substituents, in contrast to most of the known C-C coupling methods, and it preserves them, if present. Ag(ii)SO4 may be easily electrochemically regenerated from the Ag(i)HSO4 byproduct. However, the C-C coupling method currently suffers from low yields, up to 17%, and it requires further optimization.
Syntheses of [5]-helicene by McMurry or carbenoid couplings
Dubois, Fabien,Gingras, Marc
, p. 5039 - 5040 (1998)
Short syntheses of [5]-helicene have been accomplished under thermal conditions, without using photochemistry and high dilution. Key reactions comprised a Mcmurry coupling of a dialdehyde or a carbenoid-type coupling of aromatic bis(bromomethyl) moieties. The last coupling provide a 72% yield of [5]-helicene on a gram-scale (15 min O°C).
Sulfoxides as 'traceless' resolving agents for the synthesis of atropisomers by dynamic or classical resolution
Clayden, Jonathan,Kubinski, Przemyslaw M.,Sammiceli, Federica,Helliwell, Madeleine,Diorazio, Louis
, p. 4387 - 4397 (2004)
Reacting (-)-menthyl sulfinate with an atropisomeric but racemic aryllithium gives two atropdiastereoisomeric sulfoxides. Separation (by chromatography or crystallisation) and sulfoxide-lithium exchange of each diastereoisomer regenerates the aryllithium in enantiomerically pure form which can be quenched with a range of electrophiles with retention of stereochemical integrity. Overall the reaction sequence is a resolution but without the need for an acidic or basic substituent - a 'traceless' method. In certain instances, for example when the nucleophile is an ortholithiated peri-substituted 1-naphthamide, the diastereoisomeric sulfoxides may be interconverted thermally. This allows a dynamic resolution, under thermodynamic control, and hence in principle can give yields of the final products of greater than 50%. The utility of the method is demonstrated by the synthesis of a known atropisomeric phosphine ligand.
A Srongly Binding, Helically Chiral Ligand System
Judice, J. Kevin,Keipert, Steven J.,Cram, Donald J.
, p. 1323 - 1325 (1993)
The syntheses, characterization and binding properties are described for two helically chiral ligand systems containing two phenanthroline units whose nitrogens are roughly tetrahedrally arranged in one system and potentially arrangeable that way in a second.
A new and efficient method for the synthesis of 2,2′-dibromo-1,1′-binaphthyl under microwave irradiation
Xu, Li-Wen,Li, Fu-Wei,Xia, Chun-Gu,Sun, Wei
, p. 2763 - 2767 (2003)
A very simple and efficient method to prepare 2,2′-dibromo-1,1′-binaphthyl via two-step procedure from β-naphthol in good yield under microwave irradiation is described.
A highly diastereoselective route to dinaphtho [c,e][1,2] oxaphosphinines and their application as ligands in homogeneous catalysis
Shuklov, Ivan A.,Dubrovina, Natalia V.,Jiao, Haijun,Spannenberg, Anke,Boerner, Armin
, p. 1669 - 1680 (2010)
A new and facile method for the synthesis of 6H-dinaphtho[c,e][1,2] oxaphosphinines starting from dinaphthol (BINOL) is described. The ring-opening of an intermediary dinaphtho[2,1-b;1′,2′-d]furan proceeds with extremely high diastereoselectivity and forms the thermodynamically most stable product. The stereochemistry was elucidated by 31P NMR spectroscopy and X-ray structural analysis. Epimerization at the stereogenic P-centre did not take place. DFT calculations were performed to determine the dihedral angles of several dinaphtho[c,e][1,2]oxaphosphinines and to explain the observed loss of stereochemistry during the total synthesis from, the starting enantiopure BINOL. The synthetic potential of 6-chloro-6H-dinaphtho[c,e][1,2]oxaphosphinine was corroborated in its reactions with phenols to afford the corresponding phosphonites. These were successfully applied as ligands in the Rh-catalysed hydroformylation of three terminal olefins.
Synthesis method of 2, 2 '-bisdiphenylphosphino-1, 1'-binaphthalene
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, (2020/09/12)
The invention relates to a synthesis method of 2, 2 '-bisdiphenylphosphino-1, 1'-binaphthalene, which is realized by the following steps: step 1, carrying out BUCHERER reaction on 1, 1 '-binaphthyl-2-naphthol to generate 1, 1'-binaphthyl-2, 2 '-diamine; 2, subjecting 1, 1 '-binaphthyl-2, 2'-diamine to a Sandmeyer reaction to generate binaphthyl dibromide; and 3, carrying out a Grignard reaction onthe binaphthyl dibromide and diphenyl phosphine chloride to generate 2, 2 '-bisdiphenylphosphino-1, 1'-binaphthalene (BINAP). Bulk chemical raw materials are used and are low in price and easy to obtain, and the production cost is effectively reduced; the method has the advantages of easily available raw materials, high reaction yield, simple post-treatment, facilitation of industrial amplification, and strong industrial application prospect.
Mixed er-NHC/phosphine Pd(ii) complexes and their catalytic activity in the Buchwald-Hartwig reaction under solvent-free conditions
Ageshina, Alexandra A.,Sterligov, Grigorii K.,Rzhevskiy, Sergey A.,Topchiy, Maxim A.,Chesnokov, Gleb A.,Gribanov, Pavel S.,Nechaev, Mikhail S.,Asachenko, Andrey F.,Bermeshev, Maxim V.,Melnikova, Elizaveta K.
supporting information, p. 3447 - 3452 (2019/04/30)
A series of novel (NHC)PdCl2-PR3 complexes were synthesized and fully characterized by 1H, 13C, 31P NMR and FT-IR spectroscopy. These complexes showed high catalytic activity toward solvent-free Buchwald-Hartwig amination. Both primary and secondary amines were efficiently utilized under the same reaction conditions. The solvent-free synthesis of valuable N-aryl carbazoles and similar N-heterocyclic systems was described.
Highly sterically hindered binaphthalene-based monophosphane ligands: Synthesis and application in stereoselective Suzuki-Miyaura reactions
Meskova, Michaela,Putala, Martin
, p. 894 - 902 (2013/09/23)
A series of new sterically hindered (R)-(2′-aryl-1,1′- binaphthalene-2-yl)phosphanes with ortho-substituted phenyls as aryl groups were prepared via Negishi monoarylation of enantiopure 2,2′-dibromo-1, 1′-binaphthalene followed by lithiation and quenching with diphenylphosphanyl or dicyclohexylphosphanyl chloride. These ligands were applied to the stereoselective Suzuki-Miyaura coupling for the preparation of substituted biaryls. The enantioselectivity correlated positively when increasing the hindrance of the 2′-aryl group of the ligand. Using the best performing diphenylphosphane ligand with a 2,6-dimethoxyphenyl aryl group, various arylnaphthalenes were prepared in high to excellent yields (68-99%) with low to good ee (12-75% ee), the latter being comparable to the best values reported when using other chiral monophosphane ligands.
