Nitroso Diels–Alder (NDA) reaction as an efficient tool for the functionalization of diene-containing natural products

Carosso, Serena; Miller, Marvin J.

doi:10.1039/c4ob01033g

Cited by 79 publications

(33 citation statements)

References 184 publications

(186 reference statements)

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“…The method combines both LLE and SPE to reduce the serum ion suppression of dihydroxyvitamin D. Organicnitroso compounds and their rich chemistry have been studied for more than 60 years, and broad applications have been found in organic synthesis, as derivatization reagents for drug discovery and other applications (39)(40)(41)(42). To the best of our knowledge, their utility for improving ionization efficiency has not been explored.…”

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confidence: 99%

A new sensitive LC/MS/MS analysis of vitamin D metabolites using a click derivatization reagent, 2-nitrosopyridine

Wan

Yang

Barnych

et al. 2017

Journal of Lipid Research

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This article is available online at http://www.jlr.orgIn 1943, vitamin D was recommended as an essential nutrient for the US public. People can acquire the precursors to the bioactive forms, vitamin D 3 and vitamin D 2 , from diet, supplements, and sunlight. In the liver, both forms of vitamin D are rapidly hydroxylated to corresponding 25-hydroxyvitamin D [25(OH)VitD]. Being a predominant metabolite, circulating 25(OH)VitD serves as the preferred surrogate biomarker of vitamin D nutritional status (1, 2). Low levels of 25(OH)VitD indicate low vitamin D nutritional intake, which is related to many diseases, such as osteomalacia, multiple sclerosis, Parkinson's disease, asthma, and other health risks, including muscle weakness, diabetes, and cognitive decline or Alzheimer's disease (3-7). Consequently, analytical techniques for measurement of 25(OH)VitD have been developed (8)(9)(10)(11)(12). In the kidney, 25(OH)VitD is further hydroxylated to 1,25-dihydroxyvitamin D [1,25(OH) 2 VitD]. 1,25(OH) 2 VitD is the major biologically active metabolite and plays an important role in decreasing the risk of many diseases, including common cancers, cardiovascular disease, autoimmune disease, and chronic kidney disease (13)(14)(15)(16)(17). Most recently, we have demonstrated that 1,25(OH) 2 VitD also appears to be important for the health of the eye (18). The influence that these biologically active forms of vitamin D have on these numerous diseases and associated organ systems 23 January 2017. Published, JLR Papers in Press, February 1, 2017 DOI 10.1194 26,26,27,27,(OH)VitD 3 ; ALTM, all laboratory trimmed mean; CUDA, 12-(3-cyclohexyl-ureido)-dodecanoic acid; DEQAS, Vitamin D External Quality Assessment Scheme; LLE-SPE, liquid-liquid extraction followed by solid-phase extraction; LLOQ, lower limit of quantification; MRM, multiple reaction monitoring; PTAD, 4-phenyl-1,2,4-triazole-3,5-dione; PyrNO, 2-nitrosopyridine; QC, quality control. This work was supported by the National Institutes of Health/National Eye Institute grant R01 EY021747 (to M.A.W.), National Institute of Environmental Health Sciences (NIEHS) grant R01 ES002710, NIEHS Superfund Research Program grant P42 ES004699 (to B.D.H.), the West Coast Metabolomics Center at UC Davis (National Institutes of Health/National Institute of Diabetes and Digestive and Kidney Diseases grant U24 DK097154), and National Institutes of Health/NIEHS grant 1K99ES024806-01 (to K.S.S.L.). Manuscript received 22 November 2016 and in revised form

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A new sensitive LC/MS/MS analysis of vitamin D metabolites using a click derivatization reagent, 2-nitrosopyridine

Wan

Yang

Barnych

et al. 2017

Journal of Lipid Research

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“…While we tried several dienophiles, nitrosobenzene 24,25) was quite reactive in the Diels-Alder reaction with 7e. The reaction was completed in hexane at 40°C, and afforded the bicyclic compound 12 in 90% yield (major-minor=79 : 11, Chart 5).…”

Section: Resultsmentioning

confidence: 99%

Construction of Optically Active Isotwistanes and Aminocyclitols Using Chiral Cyclohexadiene as a Common Intermediate

Harada

Kino

et al. 2016

CHEMICAL & PHARMACEUTICAL BULLETIN

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We have developed a new method for synthesizing chiral isotwistane and homoisotwistane skeletons as well as aminocyclitols in a highly stereoselective manner. These results were achieved through the use of a common intermediate, which was derived from the ytterbium-catalyzed asymmetric Diels-Alder reaction of Danishefsky diene.Key words isotwistane; homoisotwistane; aminocyclitol; Diels-Alder; asymmetric catalysis; hetero-DielsAlder Many biologically active compounds possess a cyclic skeleton with center chirality in their structure. Therefore, the stereoselective synthesis of optically active carbon frameworks is in high demand for synthetic and medicinal chemists. The Diels-Alder reaction has been widely used for this purpose to construct six-membered carbocycles, and the catalytic and enantioselective variant of this reaction has been studied for decades. 1) Our group reported the first example of the catalytic and asymmetric Diels-Alder reaction of Danishefsky diene (1) 2,3) (Chart 1). Functionalized cyclohexene 3 was obtained in optically pure form, and 3 could be transformed to cyclohexenone 4 in quantitative yield. Both functionalized compounds could be potential synthetic intermediates, and we have previously demonstrated the synthetic utility of this reaction. 4-7)In the present study, silyloxy-substituted cyclohexadiene 7 derived from 4 was shown to be a key intermediate for two types of synthetically useful chiral building blocks, i.e., the tricyclo[4.3.1.0 3,7 ] decane (isotwistane 8, n=1) and tricyclo[5.3.1.0 3,8 ] undecane (homoisotwistane 8, n=2) skeletons via the intramolecular Diels-Alder reaction, and aminocyclitol 10 via the intermolecular hetero-Diels-Alder reaction with nitrosobenzene (Chart 2). Results and DiscussionConstruction of Isotwistane and Homoisotwistane Skeletons Isotwistane is an all-carbon tricyclic compound, and its structural motif is found in natural products such as pupukeananes, [8][9][10][11][12] palhinines, [13][14][15] and seychellene. [16][17][18] These types of compounds with (homo) isotwistane skeleton were attracted by their potential for perfumery, and the difference of scent derived from their chirality could be an important research target. Due to the unique structure of isotwistanes, the total syntheses of biologically active compounds with isotwistane skeletons have been studied by many research groups. [19][20][21][22][23] Most of these studies have used the intramolecular DielsAlder reaction to build the fused structure of isotwistane. Based on these previous studies, we planned the synthesis of a chiral isotwistane skeleton by two Diels-Alder reactions: our asymmetric Diels-Alder reaction and a sequential intramolecular Diels-Alder reaction.Dienophiles 2a-d with an olefin in the side chain (R) were prepared. We expected that Lewis acidic activation of the dienophile would occur site-specifically only at the acyloxazolidinone moiety, and the Diels-Alder reaction would take place at the adjacent olefin. With the application of our ytterbium catalyst, 3) the asy...

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“…4‐Phenyl‐1,2,4‐triazoline‐3,5‐dione (PTAD) was selected as an appropriate reactant for stabilizing the triene structure close to the A‐ring side of vitamin D 2 (Burild, Frandsen, & Jakobsen, ; Eyles et al, ). (1 R ,3a R ,7a R )‐1‐((2 R , E )‐5,6‐Dimethylhept‐3‐en‐2‐yl)‐7a‐methyloctahydro‐4 H ‐inden‐4‐one (VD2‐1) was synthesized via ruthenium‐periodate oxidation reaction of a condensation product generated from an aza‐Diels‐Alder reaction (Carosso & Miller, ) of vitamin D 2 and PTAD (Fig. ).…”

Section: Methodsmentioning

confidence: 99%

Indene Compounds Synthetically Derived from Vitamin D Have Selective Antibacterial Action on Helicobacter pylori

Wanibuchi

Hosoda²,

Ihara

et al. 2018

Lipids

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Helicobacter pylori infects the human stomach and is closely linked with the development of gastric cancer. When detected, this pathogen can be eradicated from the human stomach using wide-spectrum antibiotics. However, year by year, H. pylori strains resistant to the antibacterial action of antibiotics have been increasing. The development of new antibacterial substances effective against drug-resistant H. pylori is urgently required. Our group has recently identified extremely selective bactericidal effects against H. pylori in (1R,3aR,7aR)-1-[(1R)-1,5-dimethylhexyl]octahydro-7a-methyl-4H-inden-4-one (VDP1) (otherwise known as Grundmann's ketone), an indene compound derived from the decomposition of vitamin D and proposed the antibacterial mechanism whereby VDP1 induces the bacteriolysis by interacting at least with PtdEtn (dimyristoyl-phosphatidylethanolamine [di-14:0 PtdEtn]) retaining two 14:0 fatty acids of the membrane lipid constituents. In this study, we synthesized new indene compounds ((1R,3aR,7aR)-1-((2R,E)-5,6-dimethylhept-3-en-2-yl)-7a-methyloctahydro-4H-inden-4-one [VD2-1], (1R,3aR,7aR)-1-((S)-1-hydroxypropan-2-yl)-7a-methyloctahydro-1H-inden-4-ol [VD2-2], and (1R,3aR,7aR)-7a-methyl-1-((R)-6-methylheptan-2-yl)octahydro-1H-inden-4-ol [VD3-1]) using either vitamin D or vitamin D as materials. VD2-1 and VD3-1 selectively disrupted the di-14:0 PtdEtn vesicles without destructing the vesicles of PtdEtn (dipalmitoyl-phosphatidylethanolamine) retaining two 16:0 fatty acids. In contrast, VD2-2, an indene compound lacking an alkyl group, had no influence on the structural stability of both PtdEtn vesicles. In addition, VD2-1 and VD3-1 exerted extremely selective bactericidal action against H. pylori without affecting the viability of commonplace bacteria. Meanwhile, VD2-2 almost forfeited the bactericidal effects on H. pylori. These results suggest that the alkyl group of the indene compounds has a crucial conformation to interact with di-14:0 PtdEtn of H. pylori membrane lipid constituents whereby the bacteriolysis is ultimately induced.

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Nitroso Diels–Alder (NDA) reaction as an efficient tool for the functionalization of diene-containing natural products

Cited by 79 publications

References 184 publications

A new sensitive LC/MS/MS analysis of vitamin D metabolites using a click derivatization reagent, 2-nitrosopyridine

A new sensitive LC/MS/MS analysis of vitamin D metabolites using a click derivatization reagent, 2-nitrosopyridine

Construction of Optically Active Isotwistanes and Aminocyclitols Using Chiral Cyclohexadiene as a Common Intermediate

Indene Compounds Synthetically Derived from Vitamin D Have Selective Antibacterial Action on Helicobacter pylori

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