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Kinetics of the Strain-Promoted Oxidation-Controlled Cycloalkyne-1,2-quinone Cycloaddition: Experimental and Theoretical Studies

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Kinetics of the Strain-Promoted Oxidation-Controlled Cycloalkyne-1,2-quinone Cycloaddition: Experimental and Theoretical Studies

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dc.contributor.author	Escorihuela Fuentes, Jorge
dc.contributor.author	Das, Anita
dc.contributor.author	Looijen, Wilhelmus J. E.
dc.contributor.author	van Delft, Floris L.
dc.contributor.author	Aquino, Adelia J. A.
dc.contributor.author	Lischka, Hans
dc.contributor.author	Zuilhof, Han
dc.date.accessioned	2018-09-04T16:42:19Z
dc.date.available	2018-09-04T16:42:19Z
dc.date.issued	2018
dc.identifier.citation	Escorihuela Fuentes, Jorge Das, Anita Looijen, Wilhelmus J. E. van Delft, Floris L. Aquino, Adelia J. A. Lischka, Hans Zuilhof, Han 2018 Kinetics of the Strain-Promoted Oxidation-Controlled Cycloalkyne-1,2-quinone Cycloaddition: Experimental and Theoretical Studies Journal of Organic Chemistry 83 1 244 252
dc.identifier.uri	http://hdl.handle.net/10550/67396
dc.description.abstract	Stimulated by its success in both bioconjugation and surface modification, we studied the strain-promoted oxidation-controlled cycloalkyne-1,2-quinone cycloaddition (SPOCQ) in three ways. First, the second-order rate constants and activation parameters (ΔH⧧) were determined of various cyclooctynes reacting with 4-tert-butyl-1,2-quinone in a SPOCQ reaction, yielding values for ΔH⧧ of 4.5, 7.3, and 12.1 kcal/mol, for bicyclo[6.1.0]non-4-yne (BCN), cyclooctyne (OCT), and dibenzoazacyclooctyne (DIBAC), respectively. Second, their reaction paths were investigated in detail by a range of quantum mechanical calculations. Single-configuration theoretical methods, like various DFT and a range of MP2-based methods, typically overestimate this barrier by 3-8 kcal/mol (after inclusion of zero-point energy, thermal, and solvation corrections), whereas MP2 itself underestimates the barrier significantly. Only dispersion-corrected DFT methods like B97D (yielding 4.9, 6.4, and 12.1 kcal/mol for these three reactions) and high-level CCSD(T) and multireference multiconfiguration AQCC ab initio approaches (both yielding 8.2 kcal/mol for BCN) give good approximations of experimental data. Finally, the multireference methods show that the radical character in the TS is rather small, thus rationalizing the use of single-reference methods like B97D and SCS-MP2 as intrinsically valid approaches.
dc.language.iso	eng
dc.relation.ispartof	Journal of Organic Chemistry, 2018, vol. 83, num. 1, p. 244-252
dc.subject	Química orgànica
dc.title	Kinetics of the Strain-Promoted Oxidation-Controlled Cycloalkyne-1,2-quinone Cycloaddition: Experimental and Theoretical Studies
dc.type	journal article	es_ES
dc.date.updated	2018-09-04T16:42:19Z
dc.identifier.doi	10.1021/acs.joc.7b02614
dc.identifier.idgrec	126745
dc.rights.accessRights	open access	es_ES