13426-49-8Relevant articles and documents
Site-specific incorporation of quadricyclane into a protein and photocleavage of the quadricyclane ligation adduct
Tomlin, Frederick M.,Gordon, Chelsea G.,Han, Yisu,Wu, Taia S.,Sletten, Ellen M.,Bertozzi, Carolyn R.
, p. 5280 - 5290 (2018)
The quadricyclane (QC) ligation is a bioorthogonal reaction between a quadricyclane moiety and a nickel bis(dithiolene) derivative. Here we show that a QC amino acid can be incorporated into a protein site-specifically using the pyrrolysine-based genetic
Tandem Ring-Opening–Ring-Closing Metathesis for Functional Metathesis Catalysts
Nagarkar, Amit A.,Yasir, Mohammad,Crochet, Aurelien,Fromm, Katharina M.,Kilbinger, Andreas F. M.
, p. 12343 - 12346 (2016/10/13)
Use of a tandem ring-opening–ring-closing metathesis (RORCM) strategy for the synthesis of functional metathesis catalysts is reported. Ring opening of 7-substituted norbornenes and subsequent ring-closing metathesis forming a thermodynamically stable 6-membered ring lead to a very efficient synthesis of new catalysts from commercially available Grubbs’ catalysts. Hydroxy functionalized Grubbs’ first- as well as third-generation catalysts have been synthesized. Mechanistic studies have been performed to elucidate the order of attack of the olefinic bonds. This strategy was also used to synthesize the ruthenium methylidene complex.
Photodissociation Dynamics of Cyclopropenylidene, c-C3H2
Schuurman, Michael S.,Giegerich, Jens,Pachner, Kai,Lang, Daniel,Kiendl, Benjamin,MacDonell, Ryan J.,Krueger, Anke,Fischer, Ingo
, p. 14486 - 14495 (2015/10/05)
In this joint experimental and theoretical study we characterize the complete dynamical "life cycle" associated with the photoexcitation of the singlet carbene cyclopropenylidene to the lowest lying optically bright excited electronic state: from the initial creation of an excited-state wavepacket to the ultimate fragmentation of the molecule on the vibrationally hot ground electronic state. Cyclopropenylidene is prepared in this work using an improved synthetic pathway for the preparation of the precursor quadricyclane, thereby greatly simplifying the assignment of the molecular origin of the measured photofragments. The excitation process and subsequent non-adiabatic dynamics have been previously investigated employing time-resolved photoelectron spectroscopy and are now complemented with high-level ab initio trajectory simulations that elucidate the specific vibronic relaxation pathways. Lastly, the fragmentation channels accessed by the molecule following internal conversion are probed using velocity map imaging (VMI) so that the identity of the fragmentation products and their corresponding energy distributions can be definitively assigned.
COMPOSITIONS AND METHODS FOR QUADRICYCLANE MODIFICATION OF BIOMOLECULES
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Paragraph 0301, (2013/09/26)
The present disclosure features a strain-promoted [2+2+2] reaction that can be carried out under physiological conditions. In general, the reaction involves reacting a pi-electrophile with a low lying LUMO with a quadricyclane on a biomolecule, generating
A bioorthogonal quadricyclane ligation
Sletten, Ellen M.,Bertozzi, Carolyn R.
supporting information; experimental part, p. 17570 - 17573 (2012/01/04)
New additions to the bioorthogonal chemistry compendium can advance biological research by enabling multiplexed analysis of biomolecules in complex systems. Here we introduce the quadricyclane ligation, a new bioorthogonal reaction between the highly strained hydrocarbon quadricyclane and Ni bis(dithiolene) reagents. This reaction has a second-order rate constant of 0.25 M-1 s-1, on par with fast bioorthogonal reactions of azides, and proceeds readily in aqueous environments. Ni bis(dithiolene) probes selectively labeled quadricyclane-modified bovine serum albumin, even in the presence of cell lysate. We have demonstrated that the quadricyclane ligation is compatible with, and orthogonal to, strain-promoted azide-alkyne cycloaddition and oxime ligation chemistries by performing all three reactions in one pot on differentially functionalized protein substrates. The quadricyclane ligation joins a small but growing list of tools for the selective covalent modification of biomolecules.
Ruthenium(II)-catalyzed [2+2] cycloadditions of anti 7-substituted norbornenes
Jordan, Robert W.,Le Marquand, Paul,Tam, William
, p. 80 - 86 (2008/09/17)
The ruthenium(II)-catalyzed [2+2] cycloadditions of anti 7-substituted norbornenes with an alkyne were investigated. The cycloadditions were found to proceed with a high degree of stereoselectivity, giving only the exo stereoisomers in moderate to good yields using an improved protocol. Comparative rate studies between a variety of anti 7-substituted norbornenes and an alkyne revealed that the reactivity of the alkene component decreases dramatically as the alkene becomes more electron deficient. Wiley-VCH Verlag GmbH & Co. KGaA, 2008.
Catalysis of the thermal quadricyclane -> norbornadiene isomersation by mercury(II) halides
Rood, I. D. Ch.,Klumpp, G. W.
, p. 303 - 304 (2007/10/02)
Quadricyclanes are rapidly isomerised to norbornadienes by Hg(II) halides under very mild conditions, corner-mercuration being assumed to be the essential step.With quadricyclane and 3-tert-butyl-quadricyclane, zero-order kinetics were found.
