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

Polyterpenes and Prenylquinones INDEX Diterpenes Sesterterpenes Triterpenes Tetraterpenes Polyterpenes and Prenylquinones

4 Diterpenes

4.1 Phytane 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, K의 일부, 모든 식물 존재 Plaunotol : 태국의 대극과 약초 Croton sublyratus에서 얻어진 항궤양활성 (위 점막 혈류증가, prostaglandin 합성촉진, 점액 생성촉진)이 강한 화합물로 위염, 위궤양 치료약으로 사용됨

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 I

Constitunets of Tabacco Inotropic, vasodilatory activities 4.3 Bicyclophytanes 4.3.1 Labdanes Named from Cistus labdaniferus growing in Mediterranean countries Constituents of Pinaceae (소나무과) and Cupressaceae (측백나무과) Expectorant (거담제) Constitunets of Tabacco I 눈잣나무 스트로브잣나무 유럽 소나무 Juniperus communis Coleus forskolii Inotropic, vasodilatory activities

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

4.4.1 Pimaranes and Isopimaranes 4.4 Tricyclophytanes 4.4.1 Pimaranes and Isopimaranes I

Erythroxylon monogynum 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 I Pinus silvestris Juniperus thurifera Podocarpane Devadarane Parguarane Rosane Erythroxylane Azadirachta indica Bitter-tasting Extracts : mouthwashes, skin creams Neem oil : 농약 In alga Laurencia obtusa podocarpus Toxic Produced by fungus trichothecium roseum In the wood of Erythroxylon monogynum

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

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

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

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

4.5 Tetraclophytanes 4.5.1 Survey I

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

4.5.4 Atisanes : basic skeleton of various diterpene alkaloids 4.5 Tetracyclophytanes 4.5.4 Atisanes : basic skeleton of various diterpene alkaloids Erythroxylon monogynum Aconitum heterophyllum Euphorbiaceae (대극과) Sideritis serrata 4.5.5 Gibberellanes I 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

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

4.6 Cembranes and Cyclocembranes 4.6.1 Survey I

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

4.6 Cembranes and Cyclocembranes 4.6.5 Jatrophanes : name from Jatropha gossypiifolia Antineoplastic and antileukemic 4.6.6 Tiglianes : constituents of various Euphorbiaceae J. gossypiifolia I Euphorbia esula E. Helioscopia E. maddeni 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

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

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

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

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

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

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

4.8 Ginkgolides Leaves of Ginkgo biloba 노화나 외상에 의한 뇌장해의 개선, 쇼크증상 완화, 천식의 치료에 이용 Ginkgolide : 특이적인 혈소판활성화인자 antagonist I

Sesterterpenes 5

5.1 Acyclic Sesterterpenes The acyclic representatives are derived from 3,7,11,15,19-pentamethylicosane C25H52 Rarely occur in higher plants 감자잎 Ircinia oros Antibacterial Cacospongia scalaris

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

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

Triterterpenes 6

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

6.2 Tetracyclic Triterpenes, Gonane Type 6.2.1 Survey

6.2 Tetracyclic Triterpenes, Gonane Type 6.2.2 Protostanes and Fusidanes : in fungal metabolites Immunosuppressive antibacterial properties Therapy of wound infection Antibacterial 6.2.3 Dammaranes

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

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

6.3 Pentacyclic Triterpenes, Baccharane Type 6.3.1 Survey

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

Antileukemic, cytotoxic activity, 유화제 Antiinflammatory properties 6.3 Pentacyclic Triterpenes, Baccharane Type Taraxeranes, Multifloranes, Baueranes Glutinanes, Friedelanes, Pachysananes Ursane Antileukemic, cytotoxic activity, 유화제 Wax coats of apples Antiinflammatory properties Taraxastanes

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

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

6.5 Other Pentacyclic Triterpenes 6.5.1 Survey WAGNER-MEERWEIN rearrangement

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

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

Tetraterpenes 7

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

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

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

7.3 Diapocarotenoids

Cause allergic reaction Fragrance of passion flower 7.4 Megastigmanes C13-isoprenoids as partial structure of abscisic acid and of β-carotene Smelling degradation products in flower Used in perfumery Cause allergic reaction tobacco Fragrance of passion flower 당근, 토마토, 담배 Bulgarian oil of rose Flavor of black tea

Polyterpenes and Prenylquinones 8

Serving as sun protection for halophilic bacteria in salt lakes 8.1 Polyterpenes 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

8.2 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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