24539-28-4Relevant articles and documents
Systematic Substitution on the Cubane Nucleus: Steric and Electronic Effects
Eaton, Philip E.,Xiong, Yusheng,Zhou, Jian Ping
, p. 4277 - 4281 (1992)
Effective methodology for the synthesis of cubanes with novel substitution patterns is presented.The use of an electron-withdrawing group to accelerate ortho-metalation of amide-activated cubanes is described, as is the effect of the steric bulk of the activating group on the degree of ortho-metalation.
Free-radical polymerization and ring-expansion of a cubane acrylate: A unique low-shrink polymer
McGonagle, Alison E.,Savage, G. Paul
, p. 145 - 149 (2009)
A pendant cubane substituent has been incorporated into an acrylate polymer side chain to give poly[methyl 4-(acryloyloxymethyl)cubane carboxylate]. Treating this polymer with a rhodium(i) salt triggers a catalytic, ring-opening rearrangement of the cubane substructure to cyclooctatetraene, with a concomitant expansion in molecular volume. This system offers a unique opportunity to reverse the shrinkage associated with polymerization.
Thermo-cage opening of 4-iodo-1-vinylcubane to a novel styrene derivative
Carroll, Vincent M.,Harpp, David N.,Priefer, Ronny
, p. 2677 - 2680 (2008)
Cubane (1) and its derivatives have been cited for exhibiting unusual properties, including explosive and antiviral activity. An additional characteristic of these compounds is their tendency to undergo cage opening under certain conditions. In our attempt to polymerize 4-iodo-1-vinylcubane (4), 4-vinyl-trans-β-iodostyrene (10) was formed quantitatively. By examining both the thermolytic and Lewis acid-assisted rates, a possible mechanism for the rearrangement of 4→10 has been proposed.
Barton decarboxylation of cubane-1,4-dicarboxylic acid: Optimized procedures for cubanecarboxylic acid and cubane
Eaton,Nodari,Tsanaktsidis,Upadhyaya
, p. 501 - 502 (1995)
Cubane-1,4-dicarboxylic acid (3) and its monomethyl ester 2 were converted to cubanecarboxylic acid (4) and cubane (5), respectively, by homolytic decomposition of the corresponding thiohydroxamic esters.
Determining the necessity of phenyl ring π-character in warfarin
Xing, Hui,Houston, Sevan D.,Chen, Xuejie,Jin, Da-Yun,Savage, G. Paul,Tie, Jian-Ke,Williams, Craig M.
, p. 1954 - 1956 (2019)
Despite the difficulty in administering a safe dose regimen and reports of emerging resistance, warfarin (1) remains the most widely-used oral anticoagulant for the prevention and treatment of thrombosis in humans globally. Systematic substitution of the warfarin phenyl ring with either 1,3,5,7-cyclooctatetraene (COT) (2), cubane (3), cyclohexane (4) or cyclooctane (5) and subsequent evaluation against the target enzyme, vitamin K epoxide reductase (VKOR), facilitated interrogation of both steric and electronic properties of the phenyl pharmacophore. The tolerance of VKOR to further functional group modification (carboxylate 14, PTAD adduct 15) was also investigated. The results demonstrate the importance of both annulene conferred π-interactions and ring size in the activity of warfarin.
Highly efficient, selective and ultrasound-assisted monohydrolysis of polyhedral diesters in co-solvent
Zhang,Zhu,Anh,Song
, p. 7351 - 7354 (2013)
In this work, a new procedure for the selective monohydrolysis of polyhedral diesters is reported. The optimal conditions with regard to the catalytic activity, quantity of catalyst, ultrasound irradiation power, solvents and both the reaction and separation temperatures were examined. A series of polyhedral monoesters were obtained in high yield using 1-2 mol % of p-toluene sulphonic acid in a co-solvent under ultrasonic irradiation. This work not only leads to a practical synthetic method for polyhedral monoesters, but also provides a new approach to acid-catalyzed selective monohydrolysis.
Indoleamine 2,3-dioxygenase inhibitor
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Paragraph 0217-0220, (2020/12/30)
The invention provides a novel compound capable of inhibiting activity of indoleamine 2,3-dioxygenase (IDO), a pharmaceutical composition containing the compound, a preparation method of the compoundand application of the compound in preparation of drugs for treating proliferative diseases, infectious diseases, immune-related diseases and/or inflammatory diseases.
Thermal and Sensitiveness Determination of Cubanes: Towards Cubane-Based Fuels for Infrared Countermeasures
Dallaston, Madeleine A.,Brusnahan, Jason S.,Wall, Craig,Williams, Craig M.
supporting information, p. 8344 - 8352 (2019/06/04)
As infrared seeking technology evolves, threats are better able to distinguish defensive infrared (IR) flares from true targets. Spectrally matched flares, which generally employ carbon-based fuels, are better able to decoy some advanced missiles by more closely mimicking the IR emission of the target. Cubane is a high-energy carbon-based scaffold which may be suitable for use as a fuel in spectrally matched flares. The enthalpy of formation and strain energy of a series of cubanes was predicted in silico, and their thermal and impact stability examined. All were found to undergo highly exothermic decomposition in sealed cell differential scanning calorimetry, and two cubanes subsequently underwent quantitative sensitiveness testing. Despite their F of I values being in the secondary explosive range, cubane-1,4-dicarboxylic acid (F of I=70) and 4-carbamoylcubane-1-carboxylic acid (F of I=90) were identified as potentially useful fuels for pyrotechnic infrared countermeasure flare formulations.
Cyclooctatetraene: A Bioactive Cubane Paradigm Complement
Xing, Hui,Houston, Sevan D.,Chen, Xuejie,Ghassabian, Sussan,Fahrenhorst-Jones, Tyler,Kuo, Andy,Murray, Cody-Ellen P.,Conn, Kyna-Anne,Jaeschke, Kara N.,Jin, Da-Yun,Pasay, Cielo,Bernhardt, Paul V.,Burns, Jed M.,Tsanaktsidis, John,Savage, G. Paul,Boyle, Glen M.,De Voss, James J.,McCarthy, James,Walter, Gimme H.,Burne, Thomas H. J.,Smith, Maree T.,Tie, Jian-Ke,Williams, Craig M.
supporting information, p. 2729 - 2734 (2019/02/03)
Cubane was recently validated as a phenyl ring (bio)isostere, but highly strained caged carbocyclic systems lack π character, which is often critical for mediating key biological interactions. This electronic property restriction associated with cubane has been addressed herein with cyclooctatetraene (COT), using known pharmaceutical and agrochemical compounds as templates. COT either outperformed or matched cubane in multiple cases suggesting that versatile complementarity exists between the two systems for enhanced bioactive molecule discovery.
Cyclooctatetraenes through Valence Isomerization of Cubanes: Scope and Limitations
Houston, Sevan D.,Xing, Hui,Bernhardt, Paul V.,Vanden Berg, Timothy J.,Tsanaktsidis, John,Savage, G. Paul,Williams, Craig M.
supporting information, p. 2735 - 2739 (2019/02/07)
The scope and limitations of Eaton's rhodium(I)-catalyzed valence isomerization of cubane to cyclooctatetraene (COT) were investigated in the context of functional group tolerability, multiple substitution modes and the ability of cubane-alcohols to undergo one-pot tandem Ley–Griffith Wittig reactions in the absence of a transition metal catalyst.
