ChemInform Abstract: Synthesis and Conversions of Some Dienes with a Caryophyllane Skeleton in Acidic Media.

Khomenko, T. M.; Корчагина, Д. В.; Gatilov, Yu. V.; Bagryanskaya, Yu. I.; Ткачев, А. В.; Vyalkov, A. I.; Kun, O. B.; Salenko, V. L.; Dubovenko, Zh. V.; Barkhash, V. A.

doi:10.1002/chin.199115247

Cited by 4 publications

(4 citation statements)

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“…Next, we shifted our attention toward exploring the viability of our hDA proposal outlined in Scheme a. The potential dienophile 11 was accessed in two steps from 1 (Scheme b) . Reaction of 11 with 12 under unoptimized reaction conditions provided a mixture of 1′,9‐ epi ‐psiguadial B ( 21 ), and an unassigned minor diastereoisomer, in a combined 23 % yield.…”

Section: Figurementioning

confidence: 99%

One‐Step Multigram‐Scale Biomimetic Synthesis of Psiguadial B

et al. 2017

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A gram-scale synthesis of psiguadial B, a purported inhibitor of human hepatoma cell growth, has been achieved in one step by a biomimetic three-component coupling of caryophyllene, benzaldehyde, and diformylphloroglucinol. This cascade reaction is catalyzed by N,N'-dimethylethylenediamine, and proceeds at ambient temperature to generate four stereocenters, two rings, one C-O bond, and three C-C bonds. Combined computational and experimental investigations suggest the biosynthesis of the natural product is non-enzyme mediated, and is the result of a Michael addition between caryophyllene and a reactive ortho-quinone methide, followed by two sequential intramolecular cationic cyclization events.

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Section: Figurementioning

confidence: 99%

One‐Step Multigram‐Scale Biomimetic Synthesis of Psiguadial B

et al. 2017

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“…This isomer is not too surprising given the structural similarity between it and b-caryolanol, the principal product generated in the sulfuric acid process. Other reports have shown that 8 can be generated from caryophyllene, either by hydrochlorination/dechlorination 43 or by reaction with mercury acetate. 44 Except for 9, all of the other significant products including 5-7 are the principal hydrocarbon products generated with sulfuric acid.…”

Section: Paper Pccpmentioning

confidence: 99%

High-density biosynthetic fuels: the intersection of heterogeneous catalysis and metabolic engineering

Harvey

Meylemans

Gough

et al. 2014

Phys. Chem. Chem. Phys.

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Biosynthetic valencene, premnaspirodiene, and natural caryophyllene were hydrogenated and evaluated as high performance fuels. The parent sesquiterpenes were then isomerized to complex mixtures of hydrocarbons with the heterogeneous acid catalyst Nafion SAC-13. High density fuels with net heats of combustion ranging from 133-141 000 Btu gal(-1), or up to 13% higher than commercial jet fuel could be generated by this approach. The products of caryophyllene isomerization were primarily tricyclic hydrocarbons which after hydrogenation increased the fuel density by 6%. The isomerization of valencene and premnaspirodiene also generated a variety of sesquiterpenes, but in both cases the dominant product was δ-selinene. Ab initio calculations were conducted to determine the total electronic energies for the reactants and products. In all cases the results were in excellent agreement with the experimental distribution of isomers. The cetane numbers for the sesquiterpane fuels ranged from 20-32 and were highly dependent on the isomer distribution. Specific distillation cuts may have the potential to act as high density diesel fuels, while use of these hydrocarbons as additives to jet fuel will increase the range and/or time of flight of aircraft. In addition to the ability to generate high performance renewable fuels, the powerful combination of metabolic engineering and heterogeneous catalysis will allow for the preparation of a variety of sesquiterpenes with potential for pharmaceutical, flavor, and fragrance applications.

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“…[25,29,30] Robertson and co-workers treated isocaryophyllene ( 44 ) with sulfuric acid in diethyl ether to obtain α-neoclovene ( 49 ) and tricyclic olefin 37 , which resembles the tricyclic core of the presilphiperfolanols (Scheme 9A). Since these early studies, Collado was able to favor the formation of olefin 37 by employing silica-supported FeCl 3 .…”

Section: Synthetic Studies Toward the Presilphiperfolanol Natural mentioning

confidence: 99%

“…[25b] Further work by Khomenko and co-workers has produced alcohol-containing tricyclic structures that more closely resemble the presilphiperfolanols. [30] Treatment of isocaryophyllene ( 44 ) with fluorosulfonic acid and sulfuryl fluorochloride at −100 °C followed by a careful quenching of the acidic solution led to the formation of tricyclic alchohol 4 in 16% yield (Scheme 9B). The structure was assigned based on 1 H and 13 C NMR studies and confirmed by single crystal X-ray diffraction.…”

Section: Synthetic Studies Toward the Presilphiperfolanol Natural mentioning

confidence: 99%

Biosynthesis and Chemical Synthesis of Presilphiperfolanol Natural Products

Hong

Stoltz

2014

Angew Chem Int Ed

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Presilphiperfolanols constitute a family of biosynthetically important sesquiterpenes that can rearrange to diverse sesquiterpenoid skeletons. While the origin of these natural products can be traced to simple linear terpene precursors, the details of the enzymatic cyclization mechanism that form the stereochemically dense tricyclic skeleton have required extensive biochemical, computational, and synthetic investigation. Parallel efforts to prepare the unique and intriguing structures of these compounds by total synthesis have also inspired novel strategies, resulting in two synthetic approaches and two completed syntheses. While the biosynthesis and chemical synthesis studies performed to date have provided much insight into the role and properties of these molecules, new questions regarding the biosynthesis of newer members of the family and subtle details of the cyclization mechanism have yet to be explored.

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ChemInform Abstract: Synthesis and Conversions of Some Dienes with a Caryophyllane Skeleton in Acidic Media.

Cited by 4 publications

References 0 publications

One‐Step Multigram‐Scale Biomimetic Synthesis of Psiguadial B

One‐Step Multigram‐Scale Biomimetic Synthesis of Psiguadial B

High-density biosynthetic fuels: the intersection of heterogeneous catalysis and metabolic engineering

Biosynthesis and Chemical Synthesis of Presilphiperfolanol Natural Products

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