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TERPENES Natural Products Lab. HYEONKYUNG CHO 2013.05.31 2013-5 TERPENES | HYEONKYUNG CHO

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INDEX

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4 Diterpenes

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Approximately 5000 naturally abundant acyclic and cyclic diterpenes derived from the parent phytane are known (-)-(3R,7R,11R)-phytanoic acid : Oil slate, butter 1,3(20)-phytadiene : tabacco (E)-1,3-phytadiene : zooplankton Phytol : chlorophyll, vitamine E, K , Plaunotol : Croton sublyratus ( , prostaglandin , ) , 4.1 Phytane

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4.2 Cyclophytanes 1,6-cyclophytane : From Straw flower Helichrysum heterolasium 10,15-cyclophytane Vitamin A series Isolated from the Okinawa sponge Agelas nakamurai Antibacterial, anticonvulsant

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Named from Cistus labdaniferus growing in Mediterranean countries 4.3 Bicyclophytanes 4.3.1 Labdanes Constituents of Pinaceae ( ) and Cupressaceae ( ) Juniperus communis Expectorant ( ) Constitunets of Tabacco Coleus forskolii Inotropic, vasodilatory activities

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4.3 Bicyclophytanes 4.3.2 Rearranged Labdanes Halimane named from Halimium viscosum, Halimium umbellatum Clerodane Constituents of various Solidago species Antifeedant, antibacterial activity Isolated from H. viscosum and H. umbellatum Antibacterial recovered from the Okinawa sponge Solidago juncea Teucrium fragile Salvia melissodora Ajuga reptans

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4.4 Tricyclophytanes 4.4.1 Pimaranes and Isopimaranes

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4.4 Tricyclophytanes 4.4.1 Pimaranes and Isopimaranes Pine trees contain pimarane derivatives American rosin Cryptopinone Pimaric acid Erythroxylon monogynum Aralia racemosa Pimarane : Pine trees Isopimarane : pine, juniper species Pinus silvestris Juniperus thurifera Podocarpane podocarpus Azadirachta indica Bitter-tasting Extracts : mouthwashes, skin creams Neem oil : Devadarane Toxic Produced by fungus trichothecium roseum In the wood of Erythroxylon monogynum ErythroxylaneRosane In alga Laurencia obtusa Parguarane

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4.4 Tricyclophytanes 4.4.2 Cassanes, Cleistanthanes, Isocopalanes From the bark of Erythrophleum species Anaesthetics, cardiotonics, antihypertonics, induce cardiac arrest Cassane

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4.4 Tricyclophytanes 4.4.2 Cassanes, Cleistanthanes, Isocopalanes Cleistanthane Amphibolis antarctica Pogostemon auricularis Cunurea spruceana Cleistanthus schlechteri Isocopalanes are found in various sponges act as an antileukemic and antiviral ( , )

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4.4 Tricyclophytanes 4.4.3 Abietanes and Totaranes Pine, Juniper tree Pinus palustris Pinus silvestris Pine, Larch tree Abietane

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4.4 Tricyclophytanes 4.4.3 Abietanes and Totaranes Pinus pallasiana Bitter substance, from Salvia carnosa Antioxidant Abietane derivatives with benzenoid ring C : active substances Isolated from rosemary 13,16-cycloabietane Leaves of African Coleus species 17(15-16) -abeo-abietane Plectranthus lanuginosis Totarane Podocarpus totara

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4.5 Tetraclophytanes 4.5.1 Survey

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4.5 Tetracyclophytanes 4.5.2 Beyeranes : name from Beyeria leschenaultii Erythroxylon monogynum Spirostachys africana Stevia arictata 4.5.3 Kauranes and Villanovanes Aristolochia triangularisRoasted coffee Antibacterial, Antineoplastic activities Fungus Gibberella fujikuroi Antiinflammatory Coffea arabica Villanovane : rare diterpenes First isolated from Villanova titicaensis Kaurane

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4.5 Tetracyclophytanes 4.5.4 Atisanes : basic skeleton of various diterpene alkaloids Aconitum heterophyllumEuphorbiaceae ( ) Erythroxylon monogynum Sideritis serrata 4.5.5 Gibberellanes Role as plant growth hormones : regulate the degradation of chlorophyll, Formation fruits used in agriculture Japanese fungus Gibberella fujikuroi 4.5.6 Grayanotoxane Neurotoxic constituents

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4.6 Cembranes and Cyclocembranes 4.6.1 Survey : various bi- and tricyclic diterpenes are derived from the monocyclic cembrane

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4.6 Cembranes and Cyclocembranes 4.6.1 Survey

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4.6 Cembranes and Cyclocembranes 4.6.2 Cembranes Pheromone, Odorless constituents From Boswellia serrata From Nicotiana tobacum ( ) 4.6.3 Casbanes : rare in higher plants Antifungal Ricinus communis Croton nitens 4.6.4 Lathyranes : for the most part, isolated from Euphorbiaceae Euphorbia lathyris E. jolkini Skin-irritating Antineoplastic

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4.6 Cembranes and Cyclocembranes 4.6.5 Jatrophanes : name from Jatropha gossypiifolia Antineoplastic and antileukemic J. gossypiifolia E. Helioscopia E. maddeniEuphorbia esula 4.6.6 Tiglianes : constituents of various Euphorbiaceae 4.6.7 Rhamnofolanes and Daphnanes 4.6.8 Eunicellanes and Asbestinanes : marine origin Antineoplastic and antileukemic Croton rhamnifolius Jatropha species Rarely occur in plants

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4.6 Cembranes and Cyclocembranes 4.6.9 Briaranes : found in marine organisms 4.6.10 Dolabellanes : Cytotoxic, ichthyotoxic Insecticide Briareum polyanthes Antiviral Antiinflammatory Clavularia Dolabella california Dictyota Brown alga Dictyota dichotoma Liverwort Plagiochila acanthophylla Fungus Fusicoccum amygdali 4.6.11 Dolastanes : Metabolites of algae and corals Dictyota linearis D. cervicornis Clavularia inflata 4.6.12 Fusicoccanes : Metabolites of fungi, liverworts and algae act as growth regulators

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4.6 Cembranes and Cyclocembranes 4.6.13 Verticillanes and Taxanes Sciadopitys verticillata , , Chemotherapy of leukemia and various types of cancer From Taxaceae 4.6.14 Trinervitanes and Kempanes : defense pheromones

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4.7 Prenylsesquiterpenes 4.7.1 Xenicanes and Xeniaphyllanes : in algae and coral Isoprenyl residue extends one of the side chains of a sesquiterpene

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4.7 Prenylsesquiterpenes 4.7.2 Prenylgermacranes and Lobanes : metabolites of some marine organism

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4.7 Prenylsesquiterpenes 4.7.3 Prenyleudesmanes and Bifloranes Rarely abundant In the alga Frequently found Marine organisms, plants, insects

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Activity agaist Herpes simplex virus 4.7 Prenylsesquiterpenes 4.7.4 Sacculatanes : in various liverwort 4.7.5 Prenylguaianes Sphenolobanes

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4.8 Ginkgolides Leaves of Ginkgo biloba , , Ginkgolide : antagonist

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5 Sesterterpenes

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5.1 Acyclic Sesterterpenes The acyclic representatives are derived from 3,7,11,15,19-pentamethylicosane C 25 H 52 Rarely occur in higher plants Ircinia oros Antibacterial Cacospongia scalaris

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5.2 Monocyclic Sesterterpenes Found in various marine sponges Isolated from the sponge Analgesic, antiinflammatory and immunosuppressive properties Found in the waxes and secretions of insects 5.3 Polycyclic Sesterterpenes 5.3.1 Bicyclic Sesterterpenes : derived from some sesquiterpenes Isolated from sponge Dysidea species

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5.3 Polycyclic Sesterterpenes 5.3.2 Tricyclic Sesterterpenes 5.3.3 Tetra- and Pentacyclic Sesterterpenes Antibacterial and Phytotoxic activities Occur in marine sponges Antiinflammatory activity

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6 Triterterpenes

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6.1 Linear Triterpenes About 5000 naturally abundant triterpenes are documented Most of these are derived from squalane and squalene Biosynthetic precursor of polycyclic triterpenes Protostane and dammarane start from two different conformers of the carbenium ion

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6.2.1 Survey 6.2 Tetracyclic Triterpenes, Gonane Type

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6.2.2 Protostanes and Fusidanes : in fungal metabolites -Immunosuppressive antibacterial properties -Therapy of wound infection Antibacterial 6.2.3 Dammaranes

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6.2 Tetracyclic Triterpenes, Gonane Type 6.2.4 Apotirucallanes : insecticide ( ) 6.2.5 Tirucallanes and Euphanes : found in Euphorbiaceae 6.2.6 Lanostanes

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6.2 Tetracyclic Triterpenes, Gonane Type 6.2.7 Cycloartanes Estrogen substitute , 6.2.8 Cucurbitanes : from cucurbitaceae ( ) Anti-hypertonic, anti rheumatic, and active against HIV Inhibit the growth of human tumor cells

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6.3 Pentacyclic Triterpenes, Baccharane Type 6.3.1 Survey

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6.3 Pentacyclic Triterpenes, Baccharane Type 6.3.2 Lupanes Active against HIV and melanoma ( ) Antibacterial and reduce cholesterol levels 6.3.3 Oleanaes

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6.3 Pentacyclic Triterpenes, Baccharane Type Taraxeranes, Multifloranes, BaueranesGlutinanes, Friedelanes, Pachysananes Ursan e Antileukemic, cytotoxic activity, Wax coats of apples Antiinflammatory properties Taraxastanes

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6.4 Pentacyclic Triterpenes, Hopane Type 6.4.1 Survey 2,7-, 6,11-, 10,15-, 14,19-, and 18,22- cyclization

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6.4 Pentacyclic Triterpenes, Hopane Type 6.4.2 Hopanes and Neohopanes Substituting cholesterol in the cell walls of bacteria 6.4.3 Fernanes 6.4.4 Adiananes and Filicanes 6.4.5 Gammaceranes

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6.5 Other Pentacyclic Triterpenes 6.5.1 Survey WAGNER-MEERWEIN rearrangement

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6.5 Other Pentacyclic Triterpenes 6.5.2 Stictanes and Arborinanes 6.5.3 Onoceranes and Serratanes

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Component of ambergris ( ) Used in perfumery Essence for fixing delicate odors 6.6 Iridals : Unusual triterpenoid aldehydes

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7 Tetraterpenes

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7.1 Carotenoids About 200 naturally abundant tetraterpenes are known as carotenoids, because all of them represent structural derivatives of -carotene with 11 to 12 conjugated CC double bonds Tomatoes Carrots Minor constituent of Carrots, rare in other plants

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7.1 Carotenoids Carotenoids occur in the leaves, shoots, and roots of all higher plants They serve as color filters for photosynthesis in the leaves of plants, giving rise to the yellow and red color of the leaves during fall Many fruits such as paprika contain various carotenoids The animal organism metabolizes carotenoids received with food, as it is unable to synthesize these compounds de novo Ultimately, carotenoids and their metabolites are found as chromoproteins Some carotenoids are vitamin A active in the human and mammal organisim

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7.2 Apocarotenoids Terpenoids formally arising from carotenoids by separation of terminal fragments are referred to as apocarotenoids

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7.3 Diapocarotenoids

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7.4 Megastigmanes C 13 -isoprenoids as partial structure of abscisic acid and of -carotene Smelling degradation products in flower Used in perfumery Cause allergic reaction , , Bulgarian oil of rose Fragrance of passion flowertobacco Flavor of black tea

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8 Polyterpenes and Prenylquinones

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Isoprenoids with more than eight isoprene units are classified as polyterpenes In bacteria, polyterpenols stabilize the cell walls and perform other physiological functions Serving as sun protection for halophilic bacteria in salt lakes 8.1 Polyterpenes

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8.2 Prenylquinones Contain terpenyl groups with up to ten isoprene units Ingested with food originating from all green plants Oxidative phosphorylation, Biosynthesis of glycoproteins in the liver Coagulation agents for blood Vitamin K Occurs in fruits, vegetables and nuts Antiinflammatory, antirheumatic properties Vitamin E

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