Synthesis of triquinacene and some of its derivatives

Deslongchamps, Pierre; Cheriyan, Ukken O.; Lambert, Yvon; Mercier, Jean‐Claude; Ruest, Luc; Russo, Robert V.; Soucy, Pierre

doi:10.1139/v78-274

Cited by 38 publications

(14 citation statements)

References 15 publications

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“…The hydrocarbon 1 was prepared by using the established procedure of Deslongchamps et al and purified thoroughly (see Experimental Section). The energy of combustion measurements, performed as described previously, gave = 57.51 ± 0.70 kcal/mol for triquinacene ( 1 ).…”

Section: Resultsmentioning

confidence: 99%

An Experimental Thermochemical and Theoretical Study of Triquinacene: Definitive Disproof of Its Neutral Homoaromaticity

et al. 1998

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The enthalpy of formation ( = 57.51 ± 0.70 kcal/mol) of triquinacene (1), newly determined by measuring its energy of combustion in a microcalorimeter, is about 4 kcal/mol higher than that previously reported and corresponds to ab initio and density functional theory computational results. As a consequence, the previously derived homoaromatic stabilization energy (claimed to be 4.5 kcal/mol) from enthalpy of hydrogenation measurements is not present in 1. The lack of homoaromaticity in 1 is supported by evaluation of geometric, energetic, and magnetic criteria. In contrast, the isomerization transition state from diademane (5) to 1 is highly aromatic on the basis of the same criteria. The enthalpy of isomerization of 5 to 1 was experimentally determined by differential scanning calorimetry (DSC) to be −29.4 ± 0.3 kcal/mol (measured at 368.2 K). The enthalpy of activation for this rearrangement as determined from the DSC measurements (28.4 ± 0.2 kcal/mol) is 2.5 kcal/mol higher than the value computed at B3LYP/6-311+G**+ZPE.

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Section: Resultsmentioning

confidence: 99%

An Experimental Thermochemical and Theoretical Study of Triquinacene: Definitive Disproof of Its Neutral Homoaromaticity

et al. 1998

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“…The chemistry of the polyquinanes was described in several impressive surveys, such as Trost's[88] and Paquette's[89,90] review articles, the research towards dodecahedrane by Paquette[91] and Prinzbach[92] was highly impressive, and Greenberg and Liebman had published their inspiring book on strained organic molecules [93]. A number of groups, including Deslongchamps et al.,[94] Jacobson,[95] de Meijere et al.,[96] Cook et al [97]. and Serratosa et al [98].…”

Section: Cyclization Reactions In Solution: From Simple Indanes To Cementioning

confidence: 99%

From Fragmentation to Construction—from Void to Massive: Fascination with Organic Mass Spectrometry and the Synthesis of Novel Three‐Dimensional Polycyclic Aromatic Hydrocarbons

Kuck

2015

The Chemical Record

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Detailed insights gained from our research into the gas-phase chemistry of ionized and protonated diphenylalkanes and their congeners, obtained by extended synthesis of isotopically labeled model compounds and mass spectrometry, are presented and merged with those acquired during our development of a new family of polycyclic hydrocarbons, the centropolyindanes. Aside from a Personal Account that describes "two scientific lives in one", it is demonstrated, on the one hand, how our understanding of organic chemistry can help to shed light on the details of mass spectrometric fragmentation and to unravel, in a more fundamental way, the unimolecular reactivity of gaseous ions. On the other hand, it is shown how unexpected reactivity of related ions in solution, being subject to the very same fundamentals of organic chemistry, can lead to the construction of novel and, in part, unique three-dimensional polycyclic structures that may contribute to future research in material science. Two such apparently independent fields of organic chemistry may be seen as joint contributions of the art of science.

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“…All reactions were carried out under an inert atmosphere in oven-dried glassware. Triquinacene ( 3 ) was prepared according to the published procedure 6b…”

Section: Methodsmentioning

confidence: 99%

“…These are ideal prerequisites for exo -face selectivity in any electrophilic addition to its three double bonds. In this report we describe the highly selective synthesis of all - exo -triepoxy- and all - exo -oligohydroxytriquinane derivatives from readily accessible triquinacene 3 …”

Section: Introductionmentioning

confidence: 99%

Highly Exo-Selective Epoxidation and Hydroxylation of Triquinacene and Its Derivatives: all-exo-Hexahydroxytriquinane

et al. 1998

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Epoxidation of triquinacene 3 with dimethyldioxirane proceeded with a high degree of exo-face selectivity to give a quantitative yield of a 1:1.5 mixture of all-exo-4a and endo,exo,exo-triepoxytriquinane 4b. Subsequent lithium aluminum hydride reduction of the all-exo-triepoxide 4a gave all-exo-2,5,8-5a and all-exo-2,5,9-trihydroxytriquinane 5b, respectively. The straightforward 3-fold dihydroxylation of triquinacene 3 led exclusively to the all-exo-hexahydroxytriquinane 8 in one step. X-ray crystal structure analyses confirmed the configuration of the triepoxide 4b and the hexaacetate 9 of the hexol 8.

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Synthesis of triquinacene and some of its derivatives

Abstract: Several routes for the synthesis of triquinacene (1) and 2,3-dihydrotriquinacen-2-one (3) are described using Thiele's acid as starting material.

Cited by 38 publications

References 15 publications

An Experimental Thermochemical and Theoretical Study of Triquinacene: Definitive Disproof of Its Neutral Homoaromaticity

An Experimental Thermochemical and Theoretical Study of Triquinacene: Definitive Disproof of Its Neutral Homoaromaticity

From Fragmentation to Construction—from Void to Massive: Fascination with Organic Mass Spectrometry and the Synthesis of Novel Three‐Dimensional Polycyclic Aromatic Hydrocarbons

Highly Exo-Selective Epoxidation and Hydroxylation of Triquinacene and Its Derivatives: all-exo-Hexahydroxytriquinane

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