Structure and synthesis of archangelin. Spectral methods for distinguishing bergaptyl from isobergaptyl ethers

Bates, Robert B.; Eckert, D. J.; Paknikar, S. K.; Thalacker, V.P.

doi:10.1016/s0040-4039(01)94168-1

Cited by 5 publications

(1 citation statement)

References 14 publications

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“…By means of 1 H NMR analysis, it was finally established that the correct connectivity of quinone substituents exhibits a methyl group and a hydrogen atom on the same side of the quinone. [12][13][14][15] With the connectivity described, it was possible to report the first total synthesis of perezone. [16] The determination of the chemical structure of perezone allowed to propose an adequate mechanism for the formation of pipitzols, whose structure had been determined shortly before by Romo et al [1] Initially they established that the product of the reaction consisted of a mixture of two diasteromers, in which all the stereogenic centers formed in the reaction had opposite configurations, but since the stereogenic center at C8 (of R configuration, Fig.…”

Section: (A) (B)mentioning

confidence: 99%

Understanding Experimental Facts for the Transformation of Perezone into α- and β-pipitzols

Soto Suárez,

Cuevas González Bravo,

Murillo Herrera

et al. 2024

J. Mex. Chem. Soc.

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Under thermal conditions perezone, a sesquiterpene quinone, forms an equimolar amount of a- and β-pipitzol through an intermolecular cycloaddition reaction. Computational calculations at M06-2x/6-311++G(2d,2p) level of theory of the transition states and the associated reaction paths allow justifying the experimental observations. Only exo adducts are observed experimentally, which is in line with the calculated energy difference of 6.5 kcal/mol between the transition states associated with the endo and exo adducts. Activation free energy was accurately predicted, those the uncatalyzed thermal process of cycloaddition requires 37.0 kcal/mol. The study of the potential energy surface allows to establish the existence of folded conformers of perezone in the potential energy surface. Resumen. En condiciones térmicas la perezona, una quinona sesquiterpénica, forma, cantidades equimolares de a- y β-pipitzoles a través de una reacción de cicloadición intramolecular. A nivel M06-2x/6-311++G(2d,2p) el cálculo de los estados de transición y de las trayectorias de reacción asociadas permiten justificar los resultados observados. Desde el punto de vista experimental sólo se forman los aductos exo y no los endo pues los estados de transición relacionados muestran una diferencia energética de 6.5 kcal/mol. La energía de activación calculada para el procedo desprovisto de catálisis es de 37.0 kcal/mol. El estudio de la superficie de energía potencial permite establecer la existencia de confórmeros plegados de la perezona.

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Section: (A) (B)mentioning

confidence: 99%

Understanding Experimental Facts for the Transformation of Perezone into α- and β-pipitzols

Soto Suárez,

Cuevas González Bravo,

Murillo Herrera

et al. 2024

J. Mex. Chem. Soc.

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ChemInform Abstract: STRUKTUR UND SYNTH. VON ARCHANGELIN, SPEKTROSKOPISCHE METHODEN ZUR UNTERSCHEIDUNG VON BERGAPTYL‐ UND ISOBERGAPTYL‐AETHERN

Bates¹,

Eckert²,

Paknikar³

et al. 1972

Chemischer Informationsdienst

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An efficient synthetic method for β‐cyclolavandulal and its corresponding alcohol

Oda

Isobe

Hayashi

et al. 1996

Recl. Trav. Chim. Pays‐Bas

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8M. Odu et ul./ An eficient synthetic method for ~-cycloluuundulul und its corresponding alcohol Red. Trav. Chim. Pays- Bas 115,438-440 (1996) Abstract. 3,3-Dimethylcyclohexanone (5) was efficiently converted to methyl P-cyclolavandulate (6) in 74% yield in three steps, one of which included the preparation of P-methyl a,P-unsaturated esters by coupling lithium dimethylcuprate with enol phosphates of P-0x0 esters. Reduction of 6 with LiAlH, gave P-cyclolavandulol(2) in 94% yield and oxidation of 2 with pyridinium chlorochromate in the presence of molecular sieves afforded the title aldehyde quantitatively.

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Structure and synthesis of archangelin. Spectral methods for distinguishing bergaptyl from isobergaptyl ethers

Cited by 5 publications

References 14 publications

Understanding Experimental Facts for the Transformation of Perezone into α- and β-pipitzols

Understanding Experimental Facts for the Transformation of Perezone into α- and β-pipitzols

ChemInform Abstract: STRUKTUR UND SYNTH. VON ARCHANGELIN, SPEKTROSKOPISCHE METHODEN ZUR UNTERSCHEIDUNG VON BERGAPTYL‐ UND ISOBERGAPTYL‐AETHERN

An efficient synthetic method for β‐cyclolavandulal and its corresponding alcohol

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