Short-Step Synthesis of Chenodiol from Stigmasterol
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United States Patent (19) (11) 4,055,601 Ehmann 45) Oct
United States Patent (19) (11) 4,055,601 Ehmann 45) Oct. 25, 1977 (54) PROCESS FOR THE OXDATION OF PRIMARY ALLYLCALCOHOLS OTHER PUBLICATIONS Djerassi, "Organic Reactions', vol. VI, chapt. 5, pp. 75 Inventor: William J. Ehmann, Orange Park, 207-234. Fla. Adkins, et al., "J. Amer. Chem. Soc.' vol. 71, pp. (73) Assignee: SCM Corporation, New York, N.Y. 3622-3629. Batty et al., "Chem. Society Journal' (1938), pp. 21 Appl. No.: 582,114 175-179. Filed: May 30, 1975 22 Primary Examiner-Bernard Helfin Related U.S. Application Data Attorney, Agent, or Firm-Richard H. Thomas 63) Continuation-in-part of Ser. No. 437,188, Jan. 28, 1974, 57 ABSTRACT abandoned. Improved conversions of 3-substituted and 3,3-disub (51) Int. Cl’.............................................. CO7C 45/16 stituted allyl alcohols to the corresponding aldehydes (52) U.S. C. ............................ 260/593 R, 260/603 C, are obtained in an Oppenauer oxidation process, under 260/347.8; 260/599; 260/600 R; 260/598 Oppenauer oxidation conditions, by carrying out the (58) Field of Search ............ 260/603 HF, 599, 603 C, oxidation employing furfural as the hydrogen acceptor. 260/593 R, 600 R, 598 The invention is particularly applicable to the oxidation of geraniol and nerol to citral, which can be converted (56) References Cited directly to pseudoionone without purification. U.S. PATENT DOCUMENTS 2,801,266 7/1957 Schinz ........................... 260/603 HF 13 Claims, No Drawings 4,055,601 1. tion produces water as a by-product which hydrolyzes PROCESS FOR THE OXDATION OF PRIMARY and consumes the aluminum catalyst. This requires ALLYLCALCOHOLS nearly stoichiometric quantities (as compared to cata lytic quantities) of the aluminum catalyst (notice page This application is a continuation-in-part of prior 224 of Djerassi, supra). -
Oxidation of Secondary Alcohols to Ketones
Oxidation of secondary alcohols to ketones The oxidation of secondary alcohols to ketones is an important oxidation reaction in organic chemistry. Where a secondary alcohol is oxidised, it is converted to a ketone. The hydrogen from the hydroxyl group is lost along with the hydrogen bonded to the second carbon. The remaining oxygen then forms double bonds with the carbon. This leaves a ketone, as R1–COR2. Ketones cannot normally be oxidised any further because this would involve breaking a C–C bond, which requires too much energy.[1] The reaction can occur using a variety of oxidants. Contents Potassium dichromate PCC (Pyridinium chlorochromate) Dess–Martin oxidation Swern oxidation Oppenauer oxidation Fétizon oxidation See also References Potassium dichromate A secondary alcohol can be oxidised into a ketone using acidified potassium dichromate and heating under 2− 3+ reflux. The orange-red dichromate ion, Cr2O7 , is reduced to the green Cr ion. This reaction was once used in an alcohol breath test. PCC (Pyridinium chlorochromate) PCC, when used in an organic solvent, can be used to oxidise a secondary alcohol into a ketone. It has the advantage of doing so selectively without the tendency to over-oxidise. Dess–Martin oxidation The Dess–Martin periodinane is a mild oxidant for the conversion of alcohols to aldehydes or ketones.[2] The reaction is performed under standard conditions, at room temperature, most often in dichloromethane. The reaction takes between half an hour and two hours to complete. The product is then separated from the spent periodinane.[3] Swern oxidation Swern oxidation oxidises secondary alcohols into ketones using oxalyl chloride and dimethylsulfoxide. -
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What’s On Your Mind? Percy Lavon Julian PhD — The Man Who Wouldn’t Give Up Richard J. Barohn In the Volume 2, Issue 1 of this journal, I told the story of Vivien Thomas, an incredibly bright and technically adept laboratory technician who had to take a role behind the physician Alfred Blalock, literally in the operating room where he would tell Dr. Blalock how to proceed in the new open heart surgeries Vivien developed, and throughout his whole life as he struggled as a black man in the scientific world. He is indeed a scientific hero worthy of honor for Black History Month. Let me tell you the story of another black pioneer in health care science that has touched millions of lives but Figure 1. Percy Julian is seen here in this 1920 photo at who you may never have heard of, and while February DePauw University. was officially Black History month, we should consider any month or day a good time to honor great scientists of and was that year’s valedictorian, majoring in chemistry. all backgrounds. The scientists I will tell you about now He applied to graduate school at DePauw and at many will be of particular interest to neuromuscular health care other institutions around the country, but he was denied researchers and providers. admission. In 1960 he told this story as follows: Percy Lavon Julian, PhD was born in Montgomery, Alabama in 1899, the son of a railway mail clerk and the I shall never forget the week of anxious waiting in 1920 grandson of slaves. -
Steroid Interference with Antifungal Activity of Polyene Antibiotics
APPLIED MICROBIOLOGY, Nov., 1966 Vol. 14, No. 6 Copyright © 1966 American Society for Microbiology Printed in U.S.A. Steroid Interference with Antifungal Activity of Polyene Antibiotics WALTER A. ZYGMUNT AND PETER A. TAVORMINA Department of Microbiology and Natural Products Research, Mead Johnson & Company, Evansville, Indiana Received for publication 21 April 1966 ABSTRACT ZYGMUNT, WALTER A. (Mead Johnson & Co., Evansville, Ind.), AND PETER A. TAVORMINA. Steroid interference with antifungal activity of polyene antibiotics. Appl. Microbiol. 14:865-869. 1966.-Wide differences exist among the polyene antibiotics, nystatin, rimocidin, filipin, pimaricin, and amphotericin B, with ref- erence to steroid interference with their antifungal activities against Candida albicans. Of the numerous steroids tested, ergosterol was the only one which ef- fectively antagonized the antifungal activity of all five polyene antibiotics. The antifungal activities of nystatin and amphotericin B were the least subject to vitia- tion by the addition of steroids other than ergosterol, and those of filipin, rimo- cidin, and pimaricin were the most sensitive to interference. Attempts to delineate the structural requirements of steroids possessing polyene-neutralizing activity in growing cultures of C. albicans are discussed. The ultraviolet absorbance of certain antibiotic steroid combinations was also studied. It has been suggested (1, 9, 13) that the polyene While studying the effects of various steroids antibiotics become bound to the fungal cell mem- on the antimonilial activity of pimaricin, we brane and cause permeability changes with observed that ergostenol was almost as effective attendant depletion of essential cellular con- as the above A5-3/3-hydroxy steroids in antag- stituents. Loss of potassium and ammonium onizing pimaricin. -
The Coordinated Upregulated Expression of Genes Involved In
plants Article The Coordinated Upregulated Expression of Genes Involved in MEP, Chlorophyll, Carotenoid and Tocopherol Pathways, Mirrored the Corresponding Metabolite Contents in Rice Leaves during De-Etiolation Xin Jin 1,2,3,†, Can Baysal 3,†, Margit Drapal 4, Yanmin Sheng 5, Xin Huang 3, Wenshu He 3, Lianxuan Shi 6, Teresa Capell 3, Paul D. Fraser 4, Paul Christou 3,7 and Changfu Zhu 3,5,* 1 Gansu Provincial Key Laboratory of Aridland Crop Science, Gansu Agricultural University, Lanzhou 730070, China; [email protected] 2 College of Life Science and Technology, Gansu Agricultural University, Lanzhou 730070, China 3 Department of Plant Production and Forestry Science, University of Lleida-Agrotecnio CERCA Center, Av. Alcalde Rovira Roure, 191, 25198 Lleida, Spain; [email protected] (C.B.); [email protected] (X.H.); [email protected] (W.H.); [email protected] (T.C.); [email protected] (P.C.) 4 Biochemistry, School of Life Sciences and Environment, Royal Holloway University of London, Egham Hill, Egham, Surrey TW20 0EX, UK; [email protected] (M.D.); [email protected] (P.D.F.) 5 School of Life Sciences, Changchun Normal University, Changchun 130032, China; [email protected] 6 School of Life Sciences, Northeast Normal University, Changchun 130024, China; [email protected] 7 ICREA, Catalan Institute for Research and Advanced Studies, Passeig Lluís Companys 23, 08010 Barcelona, Spain Citation: Jin, X.; Baysal, C.; Drapal, * Correspondence: [email protected] M.; Sheng, Y.; Huang, X.; He, W.; Shi, † These authors contributed equally to this work. L.; Capell, T.; Fraser, P.D.; Christou, P.; et al. -
Orthologs of the Archaeal Isopentenyl Phosphate Kinase Regulate Terpenoid Production in Plants
Orthologs of the archaeal isopentenyl phosphate kinase regulate terpenoid production in plants Laura K. Henrya, Michael Gutensohnb, Suzanne T. Thomasc, Joseph P. Noelc,d, and Natalia Dudarevaa,b,1 aDepartment of Biochemistry, Purdue University, West Lafayette, IN 47907; bDepartment of Horticulture and Landscape Architecture, Purdue University, West Lafayette, IN 47907; cJack H. Skirball Center for Chemical Biology and Proteomics, Salk Institute for Biological Studies, La Jolla, CA 92037; and dHoward Hughes Medical Institute, Salk Institute for Biological Studies, La Jolla, CA 92037 Edited by Rodney B. Croteau, Washington State University, Pullman, WA, and approved July 2, 2015 (received for review March 9, 2015) Terpenoids, compounds found in all domains of life, represent the distributed among the three domains of life: eukaryotes, archaea, largest class of natural products with essential roles in their hosts. and bacteria. Although the MEP pathway is found in most bacteria, All terpenoids originate from the five-carbon building blocks, the MVA pathway resides in the cytosol and peroxisomes of isopentenyl diphosphate (IPP) and its isomer dimethylallyl diphos- eukaryotic cells. Plants contain both the MEP and MVA pathways, phate (DMAPP), which can be derived from the mevalonic acid which act independently in plastids and cytosol/peroxisomes, re- (MVA) and methylerythritol phosphate (MEP) pathways. The ab- spectively (Fig. 1). Nevertheless, metabolic cross-talk between these sence of two components of the MVA pathway from archaeal two pathways occurs via the exchange of IPP—andtoalesserextent genomes led to the discovery of an alternative MVA pathway with of DMAPP—in both directions (1, 2). IPP and DMAPP are sub- isopentenyl phosphate kinase (IPK) catalyzing the final step, the sequently used in multiple compartments by short-chain prenyl- formation of IPP. -
Transfer Hydrogenations and Kinetic Resolutions Van Dirk Klomp
transferhydrogenations and kineticresolutions DirkKlomp transferhydrogenationsandkineticresolutions DirkKlomp Uitnodiging voorhetbijwonenvande openbareverdedigingvan hetproefschriften destellingenop maandag 13maart2006 13.00uur endedaaraan voorafgaandetoelichting voorniet-chemiciom 12.30uur indeSenaatszaalvande TechnischeUniversiteitDelft Mekelweg5teDelft Naafloopvande plechtigheidbentuookvan hartewelkomopdereceptie inhetzelfdegebouw. DirkKlomp Esdoornlaan32 1521EBWormerveer 075-6223403 [email protected] Stellingen behorende bij het proefschrift transfer hydrogenations and kinetic resolutions van Dirk Klomp 1- De door Kao et al. gebruikte structuurbepalende verbinding fructose voor de synthese van de mesoporeuze silica SBA-1 bepaalt niet de structuur van het materiaal. H.-M. Kao, C.-C. Ting, A. S. T. Chiang, C.-C. Teng, C.-H. Chen, Chem. Commun. 2005 ,1058-1060. 2- Het door Kim et al. gesuggereerde mechanisme voor de deactivering van het enzym α-CT in de hydrolyse van β-lactonen, waarbij het lacton opent op de 4-positie, is zeer onwaarschijnlijk. D. H. Kim, J. Park, S. J. Chung, J. D. Park, N.-K. Park, J. H. Han, Bioorg. Med. Chem. 2002 , 10 , 2553-2560. 3- Psychologisch gezien betekent de omschakeling door wetenschappelijke tijdschriften van papieren versies naar elektronische, een verlies aan kennis voor de wetenschapper. 4- Omdat de aarde langzamer gaat draaien is soms de toevoeging van schrikkelsecondes noodzakelijk. Wetenschappers die deze secondes pas willen toevoegen op het moment dat ze zijn opgespaard tot een schrikkeluur, omdat de toevoegingen storingen kunnen veroorzaken in elektronische apparatuur, hebben de menselijke factor uit het oog verloren. 5- In de weekeindes waarin een nieuw boek over Harry Potter uitkomt, is het aantal kinderen dat op de eerstehulpafdeling van het ziekenhuis belandt bijna half zo groot als in andere weekeindes. Gwilym et al. hebben de afname over de lange termijn waarschijnlijk onderschat. -
Self-Assembly of Naturally Occurring Stigmasterol in Liquids Yielding A
RSC Advances View Article Online PAPER View Journal | View Issue Self-assembly of naturally occurring stigmasterol in liquids yielding a fibrillar network and gel† Cite this: RSC Adv., 2020, 10,4755 Braja Gopal Bag * and Abir Chandan Barai Stigmasterol, a naturally occurring 6-6-6-5 monohydroxy phytosterol, was extracted from the leaves of Indian medicinal plant Roscoea purpurea, commonly known as Kakoli. In continuation of our studies on the self-assembly properties of naturally occurring terpenoids, herein, we report the first self-assembly properties of this phytosterol in different organic liquids. The molecule self-assembled in organic liquids yielding supramolecular gels in most of the liquids studied via the formation of fibers and belt-like architechtures of nano-to micrometer diameter. Characterization of the self-assemblies carried out by using scanning electron microscopy, transmission electron microscopy, atomic force microscopy, optical microscopy, FTIR and X-ray diffraction studies indicated fibrillar network and belt-like structures. A model for the self-assembly of stigmasterol has been proposed based on molecular modeling studies, Received 10th December 2019 X-ray diffraction data and FTIR studies. Rheology studies indicated that the gels were of high mechanical Creative Commons Attribution-NonCommercial 3.0 Unported Licence. Accepted 21st January 2020 strength. Fluorophores such as rhodamine B, carboxy fluorescein including the anticancer drug DOI: 10.1039/c9ra10376g doxorubicin could be loaded in the gels. Moreover, release of the loaded fluorophores including the rsc.li/rsc-advances drug has also been demonstrated from the gel phase into aqueous medium. 1. Introduction templates for cell growth, inorganic structures,25 cosmetics and food industries.7 Chemical gels26–28 include both synthetic Terpenoids including steroids are the major components of polymeric gels as wells as biopolymers which are based on plant secondary metabolites. -
Chemical Constituents of Plants from the Genus Patrinia
Natural Product Sciences 19(2) : 77-119 (2013) Chemical Constituents of Plants from the Genus Patrinia Ju Sun Kim and Sam Sik Kang* Natural Products Research Institute and College of Pharmacy, Seoul National University, Seoul 151-742, Korea Abstract − The genus Patrinia, belonging to the Valerianaceae family, includes ca. 20 species of herbaceous plants with yellow or white flowers, distributed in Korea, China, Siberia, and Japan. Among them, P. scabiosaefolia (yellow Patrinia), P. saniculaefolia, P. villosa (white Patrinia), and P. rupestris are found in Korea. Several members of this genus have long been used in folk medicine for the treatment of inflammation, wound healing, ascetics, and abdominal pain after childbirth. Thus far, ca. 217 constituents, namely flavonoids, iridoids, triterpenes, saponins, and others have been identified in this genus. Crude extract and isolated compounds have been found to exhibit anticancer, anti-inflammatory, antioxidant, antifungal, antibacterial, cytotoxic activities, lending support to the rationale behind several of its traditional uses. The present review compiles information concerning the phytochemistry and biological activities of Patrinia, with particular emphasis on P. villosa, as studied by our research group. Keywords − Valerianaceae, Patrinia species, Natural products chemistry, Biological activities Introduction of the compounds/extracts obtained from this plants. Patrinia is a genus of herbaceous plants in the Chemical Constituents Valerianaceae family. There are about 20 species native to grassy mountain habitats in China, Siberia, and Japan. The reported chemical constituents from the genus Among them, P. scabiosaefolia (yellow Patrinia), P. Patrinia number, thus far, approximtely 217, include saniculaefolia, P. villosa (white Patrinia), and P. rupestris flavonoids, iridoids, triterpenes, saponins, steroids, and a are found in Korea (Lee, 1989; Bae, 2000). -
Bio-Guided Isolation, Purification and Chemical Characterization of Epigallocatechin
mac har olo P gy Osuntokun et al., Biochem Pharmacol (Los Angel) 2018, 7.1 : & O y r p t e s DOI: 10.4172/2167-0501.1000240 i n A m c e c h e c s Open Access o i s Biochemistry & Pharmacology: B ISSN: 2167-0501 Research Article Open Access Bio-guided Isolation, Purification and Chemical Characterization of Epigallocatechin; Epicatechin, Stigmasterol, Phytosterol from of Ethyl Acetate Stem Bark Fraction of Spondias mombin (Linn.) Oludare Temitope Osuntokun1*, T.O Idowu2 and Gamberini Maria Cristina3 1Department of Microbiology, Faculty of Science, Adekunle Ajasin University, Akungba Akoko, P.M.B 001, Ondo State, Nigeria 2Department of Pharmaceutical Chemistry, Obafemi Awolowo University, Nigeria 3Department of Life Sciences, University of Modena and Reggio Emilia, via G. Campi 103, 41125 Modena, Italy Abstract Spondias mombin (Linn.) is a widely cultivated edible plant used in folkloric medicine for the treatment of severe infection and health disorders. This research work was carried out to isolation, purification and chemical characterization the bioactive constituents of the ethyl acetate stem bark fraction of Spondias mombin (Linn.), a medicinally important plant of the Anacardiaceae family. This study revealed the presence of flavonoid and steroids, which have been found to be important hormone regulators which possess antimicrobial, anti-inflammatory, antioxidant properties. The chemical investigation resulted in the isolation of (C15H14O6.) 5, 7, 3', 4'-pentahydroxy flavanol (Epicatechin), (C15H14O7.) Epigallocatechin (C29H48O.), Stigmasterol phytosterol. It is here reported isolated from Spondias mombin for the first time, this makes the Spondias mombin very important medicinal plant in Nigeria and west Africa. EGC and EC arts as a strong inhibitor of HIV replication in cultured peripheral blood cells and inhibition of HIV-1 reverse transcriptase in vitro. -
The Use of Mutants and Inhibitors to Study Sterol Biosynthesis in Plants
bioRxiv preprint doi: https://doi.org/10.1101/784272; this version posted September 26, 2019. The copyright holder for this preprint (which was not certified by peer review) is the author/funder, who has granted bioRxiv a license to display the preprint in perpetuity. It is made available under aCC-BY 4.0 International license. 1 Title page 2 Title: The use of mutants and inhibitors to study sterol 3 biosynthesis in plants 4 5 Authors: Kjell De Vriese1,2, Jacob Pollier1,2,3, Alain Goossens1,2, Tom Beeckman1,2, Steffen 6 Vanneste1,2,4,* 7 Affiliations: 8 1: Department of Plant Biotechnology and Bioinformatics, Ghent University, Technologiepark 71, 9052 Ghent, 9 Belgium 10 2: VIB Center for Plant Systems Biology, VIB, Technologiepark 71, 9052 Ghent, Belgium 11 3: VIB Metabolomics Core, Technologiepark 71, 9052 Ghent, Belgium 12 4: Lab of Plant Growth Analysis, Ghent University Global Campus, Songdomunhwa-Ro, 119, Yeonsu-gu, Incheon 13 21985, Republic of Korea 14 15 e-mails: 16 K.D.V: [email protected] 17 J.P: [email protected] 18 A.G. [email protected] 19 T.B. [email protected] 20 S.V. [email protected] 21 22 *Corresponding author 23 Tel: +32 9 33 13844 24 Date of submission: sept 26th 2019 25 Number of Figures:3 in colour 26 Word count: 6126 27 28 1 bioRxiv preprint doi: https://doi.org/10.1101/784272; this version posted September 26, 2019. The copyright holder for this preprint (which was not certified by peer review) is the author/funder, who has granted bioRxiv a license to display the preprint in perpetuity. -
Sitosterol/Stigmasterol Ratio Caused by the Plant Parasitic Nematode Meloidogyne Incognita
plants Article Changes in the Plant β-Sitosterol/Stigmasterol Ratio Caused by the Plant Parasitic Nematode Meloidogyne incognita Alessandro Cabianca 1 , Laurin Müller 1 , Katharina Pawlowski 2 and Paul Dahlin 1,* 1 Agroscope, Research Division, Plant Protection, Phytopathology and Zoology in Fruit and Vegetable Production, 8820 Wädenswil, Switzerland; [email protected] (A.C.); [email protected] (L.M.) 2 Department of Ecology, Environment and Plant Sciences, Stockholm University, 106 91 Stockholm, Sweden; [email protected] * Correspondence: [email protected] Abstract: Sterols play a key role in various physiological processes of plants. Commonly, stigmasterol, β-sitosterol and campesterol represent the main plant sterols, and cholesterol is often reported as a trace sterol. Changes in plant sterols, especially in β-sitosterol/stigmasterol levels, can be induced by different biotic and abiotic factors. Plant parasitic nematodes, such as the root-knot nematode Meloidogyne incognita, are devastating pathogens known to circumvent plant defense mechanisms. In this study, we investigated the changes in sterols of agricultural important crops, Brassica juncea (brown mustard), Cucumis sativus (cucumber), Glycine max (soybean), Solanum lycopersicum (tomato) and Zea mays (corn), 21 days post inoculation (dpi) with M. incognita. The main changes affected the β-sitosterol/stigmasterol ratio, with an increase of β-sitosterol and a decrease of stigmasterol in S. lycopersicum, G. max, C. sativus and Z. mays. Furthermore, cholesterol levels increased in tomato, cucumber and corn, while cholesterol levels often were below the detection limit in the respective uninfected plants. To better understand the changes in the β-sitosterol/stigmasterol ratio, gene Citation: Cabianca, A.; Müller, L.; expression analysis was conducted in tomato cv.