597-55-7Relevant articles and documents
Nickel-Catalyzed Benzylic Substitution of Benzyl Esters with Malonates as a Soft Carbon Nucleophile
Tsuji, Hiroaki,Hashimoto, Keisuke,Kawatsura, Motoi
, p. 8837 - 8841 (2019/11/11)
The nickel-catalyzed benzylic substitution of benzyl alcohol derivatives with a soft carbon nucleophile is extremely rare compared to that with a hard carbon nucleophile. We have achieved the nickel-catalyzed benzylic substitution of benzyl esters with malonates as a soft carbon nucleophile. Primary and secondary benzyl 2,3,4,5,6-pentafluorobenzoates as well as a wide variety of malonate derivatives were well tolerated in the nickel-catalyzed reaction, providing the corresponding alkylation products in 46-86% yields (34 examples). Additionally, we propose a possible reaction mechanism that would undergo via the ??1- A nd ??3-benzylnickel intermediates.
Syntheses, Structures and Optoelectronic Properties of Spiroconjugated Cyclic Ketones
Wilbuer, Jennifer,Schnakenburg, Gregor,Esser, Birgit
, p. 2404 - 2412 (2016/06/01)
Synthetic investigations towards spiroconjugated ketones and derivatives thereof are presented. These studies led to the development of a short procedure for the synthesis of spiroconjugated tetraketone 1 in two steps with 10 % overall yield and the first-time synthesis of spirocyclic trindone 2. The optoelectronic properties of these compounds based on spectroscopic and electrochemical measurements in combination with DFT calculations as well as their molecular structures in the solid state are presented and discussed.
Overturning established chemoselectivities: Selective reduction of arenes over malonates and cyanoacetates by photoactivated organic electron donors
Doni, Eswararao,Mondal, Bhaskar,O'Sullivan, Steven,Tuttle, Tell,Murphy, John A.
supporting information, p. 10934 - 10937 (2013/08/23)
The prevalence of metal-based reducing reagents, including metals, metal complexes, and metal salts, has produced an empirical order of reactivity that governs our approach to chemical synthesis. However, this reactivity may be influenced by stabilization of transition states, intermediates, and products through substrate-metal bonding. This article reports that in the absence of such stabilizing interactions, established chemoselectivities can be overthrown. Thus, photoactivation of the recently developed neutral organic superelectron donor 5 selectively reduces alkyl-substituted benzene rings in the presence of activated esters and nitriles, in direct contrast to metal-based reductions, opening a new perspective on reactivity. The altered outcomes arising from the organic electron donors are attributed to selective interactions between the neutral organic donors and the arene rings of the substrates.
Mixed-ligand manganese(II)-phenolate complexes: Study of DNA cleavage, cytotoxic activity, and induction of apoptosis
Gao, En-Jun,Zhang, Ying,Lin, Lin,Wang, Ren-Shu,Dai, Lei,Liang, Qi,Zhu, Ming-Chang,Wang, Mei-Lin,Liu, Lei,He, Wen-Xuan,Zhang, Yan-Jin
experimental part, p. 3992 - 4005 (2012/03/10)
Two manganese complexes, [Mn(L1)2(dibe) 2](L1) (1) and [Mn(L2)2(dibe) 2] (2) (where L1= 2,2'- bipyridine (bipy), L 2=1,10-phenanthroline (phen)), were synthesized by using a carboxylic acid ligand (dibe= 2,2-dibenzylmalonate acid). The two complexes were characterized using IR, elemental analysis, and X-ray crystallography. Fluorescence analysis indicates that the two complexes can bind to HeLa cell DNA (HC-DNA), and gel electrophoresis assay demonstrates the ability of the complexes to cleave the HC-DNA. The two complexes exhibit cytotoxic specificity and significant cancer cell inhibitory rate. Furthermore, apoptotic tests demonstrate that these two complexes have apoptotic effects on HeLa cells. 2011 Taylor & Francis.
Folded H-stacking polymers by conformational control with 2-substituted trimethylene tethers
Watanabe, Jun-Ichi,Hoshino, Tohru,Nakamura, Yu-Suke,Sakai, Edo,Okamoto, Sentaro
body text, p. 6562 - 6569 (2011/11/12)
Oligomers and polymers of type [-CH2CHRCH2-(π)-] n comprising aryl units tethered by 2-substituted trimethylene were found to exist as a folding H-stacking structure in polar solvents such as CH3CN and in film,
The synthesis and crystal structure of β-substituted thiaporphyrins with novel cyclic substituents
Agarwal, Neeraj,Mishra, Sarada Prasad,Hung, Chen-Hsiung,Kumar, Anil,Ravikanth, Mangalampalli
, p. 1173 - 1180 (2007/10/03)
21,23-Dithiaporphyrins and 21-monothiaporphyrins with propane-1,3-diyldioxy and its derivatives at the β-thiophene carbons were synthesized and characterized. The cyclic substituents introduced at the β-thiophene carbons altered the electronic properties of the porphyrins. The X-ray structure for 2,3-bis(2,2-dibenzylpropane-1,3-diyldioxy) substituted 21-monothiaporphyrin showed a more planar structure compared to the saddle shaped structure reported for β-unsubstituted 21-monothiaporphyrins.
Alkylation of malonic and acetoacetic esters in an ionic liquid
Kryshtal, Galina V.,Zhdankina, Galina M.,Zlotin, Sergei G.
, p. 57 - 58 (2007/10/03)
1-Butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF6]) has been used as a recyclable medium in the alkylation of malonic and acetoacetic esters with alkyl, benzyl and prenyl halides.
Synthesis of a poly(ethylene glycol)-supported tetrakis ammonium salt: A recyclable phase-transfer catalyst of improved catalytic efficiency
Benaglia, Maurizio,Cinquini, Mauro,Cozzi, Franco,Tocco, Graziella
, p. 3391 - 3393 (2007/10/03)
The immobilization of four quaternary ammonium groups on a poly(ethylene glycol) support provided an efficient and recyclable phase-transfer catalyst.
Rational design of an electrochromic polymer with high contrast in the visible region: Dibenzyl substituted poly(3,4-propylenedioxythiophene)
Krishnamoorthy,Ambade,Kanungo,Contractor,Kumar
, p. 2909 - 2911 (2007/10/03)
A dibenzyl substituted poly(3,4-propylenedioxythiophene) was designed and synthesized, and exhibited a contrast of 89% at 632 nm with switching speeds of 400 ms and coloration efficiency of 575 cm2 C-1.
Synthesis, structure, and nucleophile-induced rearrangements of spiroketones
Maslak, Przemyslaw,Varadarajan, Sridhar,Burkey, Jeffrey D.
, p. 8201 - 8209 (2007/10/03)
Three tetraketones based on the 2,2'-spirobiindan-1,1',3,3'-tetraone skeleton were prepared and investigated. All three compounds show spiroconjugation between their perpendicular π-networks. The interaction results in lowering of the energy of the LUMO of the systems by ca. 0.2-0.3 eV as compared to non-spiroconjugated models. The spiroketones are susceptible to nucleophile-induced retro-Claisen condensations that lead to molecular rearrangements destroying spiro connectivity.
