Supporting Information Half a Century of Hawaiian ...

Supporting Information

Half a Century of Hawaiian Marine Natural Products* Kehau A. Hagiwara1, Anthony D. Wright1, 2

Affiliations

1

DKI-College of Pharmacy, University of Hawaii at Hilo, Hilo, Hawaii, USA

2

Right Consulting, Hilo, Hawaii, USA

Correspondence

Anthony D. Wright Right Consulting 15 Amauulu Road Hilo, 96720 Hawaii USA [email protected]

*Dedicated to the pioneering marine natural products research into marine organisms of Hawaiian origin undertaken by the research groups led by Richard E. Moore and Paul J. Scheuer.

© Georg Thieme Verlag KG · DOI 10.1055/s-0042-105876 · Planta Med · Hagiwara KA et al.

Table 1S. Hawaiian Marine Natural Products - 1964 to July 2015 - Organized by Major Taxonomic Groupings Highest Taxonomic Level Major Taxonomic Group Collection Location Cpd # Compound Name Reported Algae Brown Alga Dictyopteris plagiogramma Waikiki, Oahu 1 Dictyopterene A Dictyopteris australis Dictyopteris plagiogramma Waikiki, Oahu 2 Dictyopterene B Dictyopteris australis Dictyopteris plagiogramma Waikiki, Oahu 3 trans,cis,cis-1,3,5,8-Undecatetraene Dictyopteris australis Dictyopteris plagiogramma Waikiki, Oahu 4 Dictyopterene C' Dictyopteris australis Dictyopteris plagiogramma Waikiki, Oahu 5 Dictyopterene D' Dictyopteris australis Dictyopteris plagiogramma Waikiki, Oahu Ectocarpene Dictyopteris australis Dictyopteris plagiogramma Waikiki, Oahu 6 trans,trans,cis-1,3,5,8-Undecatetraene Dictyopteris australis Dictyopteris plagiogramma Waikiki, Oahu 7 trans,cis-Undeca-1,3,5-triene Dictyopteris australis Dictyopteris plagiogramma Waikiki, Oahu 8 trans,trans-Undeca-1,3,5-triene Dictyopteris australis Dictyopteris plagiogramma State of Hawaii 9 S-(3-Oxoundecyl) thioacetate Dictyopteris australis Dictyopteris plagiogramma State of Hawaii 10 bis-(3-Oxoundecyl) disulphide Dictyopteris australis Dictyopteris plagiogramma State of Hawaii 11 3-Hexyl-4,5-dithiacycloheptanone Dictyopteris australis Dictyopteris plagiogramma State of Hawaii 12 S-(trans-3-Oxoundec-4-enyl) thioacetate Dictyopteris australis Dictyopteris plagiogramma State of Hawaii 13 bis-(3-Oxoundecyl) trisulphide Dictyopteris australis Dictyopteris plagiogramma State of Hawaii 14 bis-(3-Oxoundecyl) tetrasulphide Dictyopteris australis Dictyopteris plagiogramma State of Hawaii 15 (-)-bis-(3-Acetoxyundec-5-enyl) disulphide Dictyopteris australis Dictyopteris plagiogramma State of Hawaii 16 (-)-bis-(3-Acetoxyundec-5-enyl) thioacetate Dictyopteris australis Dictyopteris plagiogramma State of Hawaii 17 (+)-(R)-4-Butylcyclohepta-2,6-dienone Dictyopteris australis Dictyopteris plagiogramma State of Hawaii 18 (+)-(R)-6-Butylcyclohepta-2,4-dienone Dictyopteris australis Kahala Beach, Oahu Dictyota acutiloba 19 Dictyoxepin Ala Moana Beach, Oahu Kahala Beach, Oahu 20 Dictyolene Dictyota acutiloba Ala Moana Beach, Oahu Tunnels Beach, Kauai 21 Acutilol A Dictyota acutiloba Dictyota acutiloba Tunnels Beach, Kauai 22 Acutilol A acetate Dictyota acutiloba Tunnels Beach, Kauai 23 Acutilol B Dictyota crenulata Hauula Beach, Oahu 24 Dictyodial Dictyota crenulata Kualoa Beach, Oahu 25 b-Crenulal Dictyota crenulata Sanadaol Kualoa Beach, Oahu 26 4b-Hydroxydictyodial A Dictyota crenulata Dictyota crenulata Kualoa Beach, Oahu 27 18,O-Dihydro-4b-hydroxydictyodial Red Alga Kahala Beach, Oahu 28 Nidificene Laurencia nidifica Laurencia nidifica Kahala Beach, Oahu 29 Nidifidiene Laurencia nidifica Kahala Beach, Oahu 30 Laurinterol Laurencia nidifica Kahala Beach, Oahu 31 Nidifidienol Diamond Head, Oahu Laurencia nidifica 32 3-Methyl-5-(2,3,6-trimethylcyclohexa-2,5-dien-1-yl)pent-1-en-3-ol Black Point, Oahu Diamond Head, Oahu 33 3-Methyl-5-(2,3,6-trimethylphenyl)pent-1-en-3-ol Laurencia nidifica Black Point, Oahu State of Hawaii 34 Nidifocene Laurencia nidifica Laurencia nidifica State of Hawaii 35 2(S),9a(S)-8,10,10-Trimethyl-2,3,4,5,9,9a-hexahydro-6H-2,5a-methanobenzo[b]oxepine Laurencia nidifica Oahu-South coast 36 cis-Maneonene A Laurencia nidifica Oahu-South coast 37 cis-Maneonene B Laurencia nidifica Oahu-South coast 38 trans-Maneonene B coast © GeorgLaurencia Thiemenidifica Verlag KG · DOIOahu-South 10.1055/s-0042-105876 · Planta 39 Med · iso-Maneonene Hagiwara KAAet al. Laurencia nidifica Oahu-South coast 40 iso-Maneonene B

General Structure Class

Ref #

Lipid

1

Lipid

2

Lipid

2

Lipid

3

Lipid

3

Lipid

4

Lipid

3

Lipid

3

Lipid

3

Lipid

5

Lipid

5

Lipid

5

Lipid

5

Lipid

6

Lipid

6

Lipid

7

Lipid

7

Lipid

8

Lipid

8

Diterpene

10

Diterpene

10

Diterpene Diterpene Diterpene Diterpene Diterpene Diterpene Diterpene

11 11 11 12 13 14 15 15

Sesquiterpene Sesquiterpene Sesquiterpene Sesquiterpene

16 16 16 17

Sesquiterpene

18

Sesquiterpene

18

Sesquiterpene Sesquiterpene C15 Acetogenin C15 Acetogenin C15 Acetogenin C15 Acetogenin C15 Acetogenin

19 19 20 20 20 21 21

Laurencia nidifica Laurencia nidifica Laurencia nidifica Laurencia majuscula Laurencia majuscula Laurencia majuscula Laurencia majuscula Laurencia majuscula Amansia glomerata

41 42 43 44 45 46 47 48 49

cis-Maneonene C (+)-Selin-4,7(11)-diene (+)-2(S)-N-Acetamido-3(R)-acetoxyoctadecan-1-ol (E)-4,4'-Dibromo-5-ethyl-5'-(pent-2-en-4-yn-1-yl)octahydro-2,2'-bifuran Kahukuene A Kahukuene B Ma'ilione allo-Isoobtusol (-)-2(S)-Amino-3-(R)-Hydroxyoctadec-4(E)-en-1-ol

C15 Acetogenin Sesquiterpene Lipid C15 Acetogenin Diterpene Diterpene Norsesquiterpene Sesquiterpene Lipid

21 22 24 25 26 26 27 27 24

50

Fragilamide

Alkaloid

33

51

Martensine A

Alkaloid

33

Gracilaria coronopifolia Gracilaria coronopifolia Gracilaria coronopifolia Gracilaria coronopifolia Gracilaria coronopifolia Gracilaria coronopifolia Gracilaria coronopifolia Gracilaria coronopifolia Gracilaria coronopifolia Chondrococcus hornemanni (Porteria hornemanni) Chondrococcus hornemanni (Porteria hornemanni) Chondrococcus hornemanni (Porteria hornemanni) Chondrococcus hornemanni (Porteria hornemanni) Chondrococcus hornemanni (Porteria hornemanni) Tricleocarpa fragilis Tricleocarpa fragilis Tricleocarpa fragilis Tricleocarpa fragilis Tricleocarpa fragilis Tricleocarpa fragilis Tricleocarpa fragilis Tricleocarpa fragilis Tricleocarpa fragilis Tricleocarpa fragilis

Oahu-South coast State of Hawaii Port Allen, Kauai North Shore, Oahu Kahuku, Oahu Kahuku, Oahu Maili Point Park, Waianae, Oahu Maili Point Park, Waianae, Oahu Black Point, Oahu Black Point, Oahu Mokuleia, Oahu Black Point, Oahu Mokuleia, Oahu Black Point, Oahu Mokuleia, Oahu Waiehu, Maui Waiehu, Maui Waiehu, Maui Waiehu, Maui Waiehu, Maui Waiehu, Maui Waiehu, Maui Waiehu, Maui Waiehu, Maui Black Point, Oahu Halona Blowhole, Oahu Black Point, Oahu Halona Blowhole, Oahu Black Point, Oahu Halona Blowhole, Oahu Black Point, Oahu Halona Blowhole, Oahu Black Point, Oahu Halona Blowhole, Oahu Nanakuli Beach, Oahu Nanakuli Beach, Oahu Nanakuli Beach, Oahu Nanakuli Beach, Oahu Nanakuli Beach, Oahu Nanakuli Beach, Oahu Nanakuli Beach, Oahu Nanakuli Beach, Oahu Nanakuli Beach, Oahu Nanakuli Beach, Oahu

65

Chondrocolactone

Monoterpene

42

66 67 68 69 70 71 72 73 74 75

Methyl-3b,23(R)-dihydroxycycloart-24-en-28-oate-3-sulfate Methyl-3b-hydroxy-23-oxocycloart-24-en-28-oate-3-sulfate Cycloart-24-en-3b,23(R),28-triol-3-sulfate 3b,28-Dihydroxycycloart-24-en-23-one-3-sulfate Cycloart-24-en-3b,23(R)-diol-3-sulfate 3b-Hydroxycycloart-24-en-23-one-3-sulfate Methyl-3b,23(R)-dihydroxy-29-nor-cycloart-24-en-28-oate-3-sulfate Methyl-3b-hydroxy-23-oxo-29-nor-cycloart-24-en-28-oate-3-sulfate Methyl-3b,23(R)-dihydroxy-29-nor-lanosta-8,24-dien-28-oate-3-sulfate Methyl-3b-hydroxy-23-oxo-29-nor-lanosta-8,24-dien-28-oate-3-sulfate

Triterpene Triterpenoid Triterpene Triterpene Triterpene Triterpene Triterpene Triterpene Triterpene Triterpene

43 43 43 43 43 43 43 43 43 43

Bryopsis sp. Bryopsis sp. Bryopsis sp. Bryopsis sp. Bryopsis sp. Bryopsis sp. Bryopsis sp. Bryopsis sp. Bryopsis sp. Bryopsis sp.

Black Point, Oahu Black Point, Oahu Black Point, Oahu Black Point, Oahu Waianae Boat Harbor, Oahu Waianae Boat Harbor, Oahu Kewalo Basin, Oahu Kewalo Basin, Oahu Kahala Bay, Oahu Kahala Bay, Oahu

76 77 78 79 80 81 82 83 84 85

Kahalalide F Kahalalide A Kahalalide B Kahalalide G Kahalalide K Kahalalide O Kahalalide P Kahalalide Q 5-OHKF norKA

Cyclic Peptide Cyclic Peptide Peptide Peptide Cyclic Peptide Peptide Cyclic Peptide Cyclic Peptide Cyclic Peptide Cyclic Peptide

44 45 45 45 46 47 48

Symbiodinium sp. Symbiodinium sp. Symbiodinium sp. Symbiodinium sp. Symbiodinium sp. Symbiodinium sp. Symbiodinium sp. Symbiodinium sp.

Coconut Island, Oahu Coconut Island, Oahu Coconut Island, Oahu Coconut Island, Oahu Coconut Island, Oahu Coconut Island, Oahu Coconut Island, Oahu Coconut Island, Oahu

86 87 88 89 90 91 92

Zooxanthellamide A Zooxanthellamide B Zooxanthellamide C-1 Zooxanthellamide C-2 Zooxanthellamide C-3 Zooxanthellamide C-4 Zooxanthellamide C-5

Polyketide Polyketide Polyketide Polyketide Polyketide Polyketide Polyketide

51 52 53 53 53 53 53

93

Puupehenone

Meroterpene

57

Martensia fragilis Martensia fragilis Martensia fragilis

52

Martensine B

Alkaloid

33

53 54 55 56 57 58 59 60

Manauealide A Manauealide B Manauealide C Debromoaplysiatoxin Anhydrodebromoaplysiatoxin Malyngamide M Malyngamide N Malyngamide I acetate

Macrolide Macrolide Macrolide Macrolide Macrolide Amide Amide Amide

35 35 35 36 37 38 38 38 39

61

(3S)-cis-Octa-1,5-dien-3-ol

Lipid

40

62

Chondrocole A

Monoterpene

41

63

Chondrocole B

Monoterpene

41

64

Chondrocole A (Revised)

Monoterpene

42

Green Alga

49

Microalga (Protista)

Sponges Order Chondrosiida

Chondrosia chucalla

Lanai

Oahu © Georg Thieme Verlag KG · DOIBlowhole, 10.1055/s-0042-105876 · Planta Med · Hagiwara KA et al.

Chondrosia chucalla Order Dictyoceratida

Hippospongia metachromia Dactylospongia sp. Dactylospongia sp. Dysidea fragilis Dysidea fragilis Dysidea fragilis Dysidea fragilis Hyrtios sp.

Hyrtios sp.

Hyrtios sp. Hyrtios sp. Hyrtios sp. Hyrtios sp. Spongia oceania

Lanai Blowhole, Oahu Lanai Blowhole, Oahu Shark's Cove, Oahu Auau Channel, Maui Auau Channel, Maui Kaneohe Bay, Oahu Kaneohe Bay, Oahu Kaneohe Bay, Oahu Kaneohe Bay, Oahu Between Maui and Molokini Crater Maui Oahu-North Coast Oahu-West Coast Between Maui and Molokini Crater Maui Oahu-North Coast Oahu-West Coast Between Maui and Molokini Crater Maui Oahu-North Coast Oahu-West Coast Brennecke's Ledge, Kauai Auau Channel, Maui Auau Channel, Maui Maui-South Coast

94

4a(S),6a(S),10a(S),10b(R)-7,7,10a-Trimethyl-3-oxo-4a,5,6,6a,7,8,9,10,10a,10b-decahydro-3Hbenzo[f]chromene-2-carbaldehyde

Meroterpene

57

95

Ilimaquinone

Sesquiterpene

58

96 97 98 99 100 101

Puupehenol Methoxypuupehenol dimer Upial Upiol Nakafuran-8 Nakafuran-9

Meroterpene Meroterpene Sesquiterpenoid Sesquiterpene Sesquiterpene Sesquiterpene

59 59 60 60 61 61

102

21-Chloropuupehenol

Meroterpene

62

103

15-Oxopuupehenol

Meroterpene

62

104

Molokinenone

Meroterpene

62

105 106 107 108

Poipuol Au'auamine Peroxypuupehenone dimer Pokepola ester

Polyketide Meroterpene Meroterpene Phosphate Ester

Order Haplosclerida Kaneohe Bay, Oahu 109 24-Ethyl-Δ5,24(28),28-cholestatrien-3b-ol Puako, Hawaii 110 3,4-Dihydroxypregna-5,17-diene-10,2-carbolactone Puako, Hawaii 111 3,4-Dihydroxypregna-5,20-diene-10,2-carbolactone Puako, Hawaii 112 3,4-Dihydroxypregna-5,15-dien-20-one-10,2-carbolactone Order Homosclerophorida Plakortis sp. Between Lehua Rock and Niihau 113 Lehualide A Plakortis sp. Between Lehua Rock and Niihau 114 Lehualide B Plakortis sp. Between Lehua Rock and Niihau 115 Lehualide C Plakortis sp. Between Lehua Rock and Niihau 116 Lehualide D Order Poecilosclerida Order Poecilosclerida Maalea Bay, Maui 117 Kiheisterone A Order Poecilosclerida Maalea Bay, Maui 118 Kiheisterone B Strongylacidon sp. Maalea Bay, Maui 119 Kiheisterone C Strongylacidon sp. Maalea Bay, Maui 120 Kiheisterone D Strongylacidon sp. Maalea Bay, Maui 121 Kiheisterone E Order Suberitida Halichondria sp. Oahu-North Shore 122 (1R,4R,4aS,8aR)-4-Isocyano-1-isopropyl-4,7-dimethyl-1,2,3,4,4a,5,6,8a-octahydronaphthalene Halichondria sp. Oahu-North Shore 123 N-((1R,4R,4aR,8aS)-4-Isopropyl-1,6-dimethyl-1,2,3,4,4a,7,8,8a-octahydronaphthalen-1-yl)formamide Halichondria sp. Oahu-North Shore 124 (1R,4R,4aS,8aR)-1-Isopropyl-4-isothiocyanato-4,7-dimethyl-1,2,3,4,4a,5,6,8a-octahydronaphthalene Halichondria sp. Oahu-North Shore 125 (6E,10E)-3-Isocyano-3,7,11,15-tetramethylhexadeca-1,6,10,14-tetraene Halichondria sp. Oahu-North Shore 126 N-((6E,10E)-3,7,11,15-Tetramethylhexadeca-1,6,10,14-tetraen-3-yl)formamide Halichondria sp. Oahu-North Shore 127 (6E,10E)-3-Isothiocyanato-3,7,11,15-tetramethylhexadeca-1,6,10,14-tetraene Hymeniacidon sp. Pupukea, Oahu 128 9-Isocyanopupukeanane Terpios zeteki Kaneohe Bay, Oahu 129 5a-24-Norcholestan-3b-ol Ciocalypta sp. Pupukea, Oahu 130 7-Ammonio-7,8-dihydro-a-bisabolene Chloride Ciocalypta sp. Pupukea, Oahu 131 7-Isocyanato-7,8-dihydro-a-bisabolene Ciocalypta sp. Pupukea, Oahu 132 7-Isocyano-7,8-dihydro-a-bisabolene Ciocalypta sp. Ala Moana Beach, Oahu 133 Isocyanoneopupukeanane Order Verongida Order Verongida Molokai-South Shore 134 15-Cyanopuupehenol Kaunakakai Harbor, Molokai Psammaplysilla purpurea 135 Moloka'iamine Oahu-South Coast Maui-South Coast Kaunakakai Harbor, Molokai 136 5-Bromo-2,3-dihydroxy-6-methoxybenzaldehyde Psammaplysilla purpurea Oahu-South Coast Maui-South Coast Kaunakakai Harbor, Molokai 137 15-Cyanopuupehenone Psammaplysilla purpurea Oahu-South Coast Maui-South Coast Kaunakakai Harbor, Molokai 138 Chloropuupehenone Psammaplysilla purpurea Oahu-South Coast Maui-South Coast Kaunakakai Harbor, Molokai purpurea Coast © GeorgPsammaplysilla Thieme Verlag KG · DOIOahu-South 10.1055/s-0042-105876 · Planta139 Med · Puupehedione Hagiwara KA et al. Maui-South Coast Callyspongia diffusa Strongylophora sp. Strongylophora sp.

Steroid Steroid Steroid Steroid Polyketide Polyketide Polyketide Polyketide Steroid Steroid Steroid Steroid Steroid Sesquiterpene Sesquiterpene Sesquiterpene Diterpene Diterpene Diterpene Sesquiterpene Steroid Sesquiterpene Sesquiterpene Sesquiterpene Sesquiterpene Meroterpene

63 64 64 65 66 67 68 68 68 69 69 69 69 70 70 71 71 71 72-74 72-74 72-74 72-74 72-74 72-74 75 76 77 77 77 78 79

Brominated Phenol

80

Brominated Phenol

80

Meroterpene

80

Meroterpene

80

Meroterpene

80

Psammaplysilla purpurea Order Verongida Order Verongida Order Verongida

Mollusks Sea Hares

Kaunakakai Harbor, Molokai Oahu-South Coast Maui-South Coast Waianae, Oahu Kaunakakai Harbor, Molokai Waianae, Oahu Kaunakakai Harbor, Molokai Waianae, Oahu Kaunakakai Harbor, Molokai

140

Dipuuphetriol

Meroterpene

80

141

N-Methylceratinamine

Brominated Phenol

81

142

Wai'anaeamine A

Brominated Phenol

81

143

Wai'anaeamine B

Brominated Phenol

81

Psammaplysin A Mololipids Aplysamine 3 Aplysamine 4 Aplysamine 5

Brominated Phenol Lipid Brominated Phenol Brominated Phenol Brominated Phenol

81 82 83 84 84

Order Verongida Psammaplysilla purpurea Psammaplysilla purpurea Psammaplysilla purpurea

Kaunakakai Harbor, Molokai Kihei, Maui Kihei, Maui Kihei, Maui

144 145 146 147 148

Stylocheilus longicauda Stylocheilus longicauda Stylocheilus longicauda Stylocheilus longicauda Stylocheilus longicauda Stylocheilus longicauda Stylocheilus longicauda Stylocheilus longicauda Stylocheilus longicauda Stylocheilus longicauda Aplysia oculifera Aplysia oculifera Phyllidia varicosa Chromodoris youngbleuthi Chromodoris youngbleuthi Chromodoris youngbleuthi

Kaneohe Bay, Oahu Kaneohe Bay, Oahu Kaneohe Bay, Oahu

149 150 151

Aplysiatoxin Aplysiatoxin Acetate Debromoaplysiatoxin Acetate

Macrolide Macrolide Macrolide

152 153 154 155 156 157 158 159 160 161 162 163

Stylocheilamide Makalika ester Makalikone ester Malyngamide O Malyngamide P Lyngbyatoxin A acetate ( E)-Ocellenyne ( Z)-Ocellenyne 2-Isocyanopupukeanane 12-Deacetylscalaradial 12-Deacetyl-12-episcalaradial 12-Deacetyl-18-epi-12-oxoscalaradial

Amide Ester Ester Lipid Lipid Alkaloid C15 Acetogenin C15 Acetogenin Sesquiterpene Sesquiterpene Sesquiterpene Sesquiterpene

164

Olepupuane

Sesquiterpene

91

165

(1R,9aS,9bR)-3-Methoxy-6,6,9a-trimethyl-1,3,5,5a,6,7,8,9,9a,9b-decahydronaphtho[1,2-c]furan-1-yl acetate

Sesquiterpene

91

Onchidium verruculatum

Kaneohe Bay, Oahu Black Point, Oahu Black Point, Oahu Black Point, Oahu Black Point, Oahu Black Point, Oahu Pupukea, Oahu Pupukea, Oahu Pupukea, Oahu Pupukea, Oahu Pupukea, Oahu Pupukea, Oahu Ala Moana Beach, Oahu Fort Kamehameha, Oahu Pupukea, Oahu Ala Moana Beach, Oahu Fort Kamehameha, Oahu Pupukea, Oahu Portlock, Oahu

36 36 36 84 85 86 86 87 87 86 88 88 89 90 90 90

166

Ester

92

Onchidium verruculatum

Portlock, Oahu

167

Ester

92

Ester

92

Ester

92

Macrolide Macrolide Macrolide Alkaloid Polypropionate Polypropionate Peptide Peptide Peptide Peptide Peptide Peptide Peptide Macrolide Peptide Peptide Peptide Peptide Peptide Peptide Peptide Peptide Peptide

93 93 94 95 96 96 97 98 99 99 99 99 99 99 100 101 45 45 45 102 102 103 103

Dendrodoris nigra Dendrodoris tuberculosa Dendrodoris nigra Dendrodoris tuberculosa

Ilikonapyrone (2S,3S,4S,5S,8S,E)-8-(6-Ethyl-3,5-dimethyl-4-oxo-4H-pyran-2-yl)-2-(6-((2R,3R)-3-hydroxypentan-2-yl)-3,5dimethyl-4-oxo-4H-pyran-2-yl)-4,6-dimethylnon-6-ene-3,5-diyl dipropionate 2-Ethyl-6-((2S,6S,7R,8S,E)-7-hydroxy-8-(6-((2R,3R)-3-hydroxypentan-2-yl)-3,5-dimethyl-4-oxo-4H-pyran-2Portlock, Oahu 168 Onchidium verruculatum yl)-4,6-dimethyl-5-oxonon-3-en-2-yl)-3,5-dimethyl-4H-pyran-4-one 2-Ethyl-6-((S,E)-4-(2-((S)-1-(2-((R)-1-(6-((2R,3R)-3-hydroxypentan-2-yl)-3,5-dimethyl-4-oxo-4H-pyran-2Portlock, Oahu 169 Onchidium verruculatum yl)ethyl)-4,4-dimethyl-1,3-dioxetan-2-yl)ethyl)-4,4-dimethyl-1,3-dioxetan-2-yl)pent-3-en-2-yl)-3,5-dimethyl4H-pyran-4-one Pupukea, Oahu 170 Ulapualide A Hexabranchus sanguineus Hexabranchus sanguineus Pupukea, Oahu 171 Ulapualide B Unidentified nudibranch Oahu Island 172 Sphinxolide Philinopsis speciosa Pupukea, Oahu 173 Pulo'upone Philinopsis speciosa Pupukea, Oahu 174 Niuhinone A Philinopsis speciosa Pupukea, Oahu 175 Niuhinone B Philinopsis speciosa Shark's Cove, Pupukea, Oahu 176 Kulolide Philinopsis speciosa Shark's Cove, Pupukea, Oahu 177 Pupukeamide Philinopsis speciosa Shark's Cove, Pupukea, Oahu 178 Kulolide-2 Philinopsis speciosa Shark's Cove, Pupukea, Oahu 179 Kulolide-3 Philinopsis speciosa Shark's Cove, Pupukea, Oahu 180 Kulolainalide-1 Philinopsis speciosa Shark's Cove, Pupukea, Oahu 181 Kulomo'opunalide-1 Philinopsis speciosa Shark's Cove, Pupukea, Oahu 182 Kulomo'opunalide-2 Philinopsis speciosa Shark's Cove, Pupukea, Oahu 183 Tolytoxin 23-acetate Philinopsis speciosa Shark's Cove, Pupukea, Oahu 184 Kulokekahalide-1 Philinopsis speciosa Shark's Cove, Pupukea, Oahu 185 Kulokekahalide-2 Elysia rufescens Black Point, Oahu 186 Kahalalide C Elysia rufescens Black Point, Oahu 187 Kahalalide D Elysia rufescens Black Point, Oahu 188 Kahalalide E Elysia rufescens Black Point, Oahu 189 Kahalalide H Elysia rufescens Black Point, Oahu 190 Kahalalide J Elysia rufescens Black Point, Oahu 191 Kahalalide V © GeorgElysia Thieme Verlag KG · DOI 10.1055/s-0042-105876 · Planta Med · Hagiwara KA et al. rufescens Black Point, Oahu 192 Kahalalide W

Elysia rufescens Elysia rufescens Elysia ornata

Black Point, Oahu Black Point, Oahu Black Point, Oahu

193 194 80

Kahalalide X Kahalalide Y Kahalalide O

Peptide Peptide Peptide

195 196 197 198

Palytoxin 42S-Hydroxy-50S-palytoxin 42S-Hydroxy-50R-palytoxin Pukalide

Polyketide Polyketide Polyketide Diterpenoid

199

Waixenicin A

Diterpene

200

Waixenicin B

Diterpene

201 202 203 204 205 206 207 208 209 210 211 212 213 214 215 216 217 218

Punaglandin 1 Punaglandin 2 Punaglandin 3 Punaglandin 4 2-Amino-3,9-dimethyl-5-dimethylamino-3H-1,3,4,6-tetrazacyclopent[e]azulene 2-Amino-3,9-dimethyl-5-methylamino-3H-1,3,4,6-tetrazacyclopent[e]azulene Coraxenolide A Coraxenolide B Coraxenolide C Coraxenolide D Corabohcin Papakusterol 7-Dehydropapakusterol 3-Chloroguaiazulene 3-Bromoguaiazulene Ehuazulene N,N-Dimethylamino-3-guaiaulenylmethane 3,5,8-Trimethylazuleno[6,5-b]furan-2,7-dione CaTX-A

Eicosanoid Eicosanoid Eicosanoid Eicosanoid Alkaloid Alkaloid Diterpene Diterpene Diterpene Diterpene Diterpene Steroid Steroid Sesquiterpene Sesquiterpene Sesquiterpene Sesquiterpene Sesquiterpene

103 103 46

Miscellaneous Cnidarians Muolea, Maui Palythoa toxica Palythoa spp. Muolea, Maui Palythoa spp. Muolea, Maui Palythoa spp. Blowhole, Oahu Anthelia edmondsoni Waimea Bay. Oahu (Sarcothelia edmondsoni) Anthelia edmondsoni Waimea Bay, Oahu (Sarcothelia edmondsoni) Telesto riisei Oahu Island Telesto riisei Oahu Island Telesto riisei Oahu Island Telesto riisei Oahu Island Parazoanthus sp. (Gerardia sp.)Oahu Island Gerardia sp. Oahu Island Corallium sp. Makapuu, Oahu Corallium sp. Makapuu, Oahu Corallium sp. Makapuu, Oahu Corallium sp. Makapuu, Oahu Corallium sp. Makapuu, Oahu Acanthogorgia sp. Makapuu, Oahu Acanthogorgia sp. Makapuu, Oahu Family Paramuriceidae Oahu Island Family Paramuriceidae Oahu Island Family Paramuriceidae Oahu Island Family Paramuriceidae Oahu Island Placogorgia sp. Oahu Island Carybdea alata (Alatina alata) Oahu Island

104-107 108 108 109-110 111 111 112 112 112 112 114 113 115 115 115 115 115 116 116 117-118 117-118 117-118 119 120 121

Echinoderms Echinoderm Echinithrix sp. Echinithrix sp. Echinithrix sp. Echinithrix sp. Echinithrix sp. Echinithrix sp. Echinithrix sp. Echinithrix sp. Echinithrix sp. Echinithrix sp. Echinithrix sp. Echinithrix sp.

Kaneohe Bay, Oahu Kaneohe Bay, Oahu Kaneohe Bay, Oahu Kaneohe Bay, Oahu Kaneohe Bay, Oahu Kaneohe Bay, Oahu Kaneohe Bay, Oahu Kaneohe Bay, Oahu Kaneohe Bay, Oahu Kaneohe Bay, Oahu Kaneohe Bay, Oahu Kaneohe Bay, Oahu Kaneohe Bay, Oahu

219 220 221 222 223 224 225 226 227 228 229 230 231

Spinochrome M 2-Hydroxy-3-acetyl-naphthazarin 2-Hydroxy-6-ethyljuglone 2-Hydroxy-6-ethylnaphthazarin Naphthopurpurin 2,7-Dihydroxy-6-acetyljuglone 2,7-Dihydroxy-3-ethylnaphthazarin 2,7-Dihydroxynaphthazarin 2,5-Dihydroxy-3-ethylbenzoquinone 2-Hydroxy-6-acetylnaphthazarin 2,3,7-Trihydroxy-6-acetyljuglone 2,3,7-Trihydroxy-6-ethyljuglone 2-Methyl-8-hydroxy-2H-pyrano[3,2-g]naphthazarin

Quinone Quinone Quinone Quinone Quinone Quinone Quinone Quinone Quinone Quinone Quinone Quinone Quinone

122 123 123 123 123 123 123 123 123 123 123 123 124

Thelepus setosus Thelepus setosus Thelepus setosus Thelepus setosus Thelepus setosus

Kaneohe Bay, Oahu Kaneohe Bay, Oahu Kaneohe Bay, Oahu Kaneohe Bay, Oahu Kaneohe Bay, Oahu

232 233 234 235 236

3,5-Dibromo-4-hydroxybenzyl alcohol 3,5-Dibromo-4-hydroxybenzyl aldehyde bis(3,5-Dibromo-4-hydroxyphenyl)methane Thelepin Thelephenol

Brominated Phenol Brominated Phenol Brominated Phenol Brominated Phenol Brominated Phenol

125 125 125 125 125

Ptychodera sp. Ptychodera sp. Ptychodera sp. Ptychodera sp. Ptychodera sp. Ptychodera sp. Ptychodera sp. Ptychodera sp. Ptychodera sp. Ptychodera sp. Ptychodera sp.

Kinau Point, Maui Kinau Point, Maui Kinau Point, Maui Kinau Point, Maui Kinau Point, Maui Kinau Point, Maui Kinau Point, Maui Kinau Point, Maui Kinau Point, Maui Kinau Point, Maui Kinau Point, Maui

237 238 239 240 241 242 243 244 245 246 247

2,6-Dibromophenol 2,4,6-Tribromophenol 2,6-Dibromohydroquinone 2,4-Dibromophenol 2,4-Dibromoresorcinol 3,4,6-Tribromoindole (4S,5R,6S)-4-Acetoxy-2,6-dibromo-5-hydroxycyclohex-2-enone (4S,5R,6R)-4-Acetoxy-2,6-dibromo-5-hydroxycyclohex-2-enone (1R,4S,5R,6S)-4-Acetoxy-2,6-dibromo-1,5-dihydroxycyclohexene (4S,5R,6R)-4-Acetoxy-2-bromo-5,6-epoxycyclohex-2-enone (4S,5R,6R)-2-Bromo-5,6-epoxy-4-hydroxycyclohex-2-enone

Brominated Phenol Brominated Phenol Brominated Phenol Brominated Phenol Brominated Phenol Brominated Indole Brominated Phenol Brominated Phenol Brominated Phenol Brominated Phenol Brominated Phenol

126 126 126 126 126 126 126 126 126 126 126

Annelid

Acorn Worm

Cyanobacteria


Lyngbya majuscula (Moorea producens) Lyngbya majuscula (Moorea producens) Lyngbya majuscula (Moorea producens) Lyngbya majuscula (Moorea producens) Lyngbya majuscula (Moorea producens) Lyngbya majuscula (Moorea producens) Lyngbya majuscula (Moorea producens) Lyngbya majuscula (Moorea producens) Lyngbya majuscula (Moorea producens) Lyngbya majuscula (Moorea producens) Lyngbya majuscula (Moorea producens) Lyngbya majuscula (Moorea producens) Lyngbya majuscula (Moorea producens) Lyngbya majuscula (Moorea producens) Lyngbya majuscula (Moorea producens) Lyngbya majuscula (Moorea producens) Lyngbya majuscula (Moorea producens) Lyngbya majuscula (Moorea producens) Lyngbya aestuarii Symploca laete-viridis Symploca laete-viridis Symploca laete-viridis Symploca laete-viridis Symploca laete-viridis Symploca sp. VP452 Symploca sp. VP452 Leptolyngbya crossbyana Leptolyngbya crossbyana Leptolyngbya crossbyana Leptolyngbya crossbyana Leptolyngbya crossbyana Leptolyngbya crossbyana Leptolyngbya crossbyana

Laie Bay, Oahu

248

Lyngbyatoxin A

Alkaloid

127-129

Kahala Bay, Oahu

249

Majusculamide A

Peptide

130

Kahala Bay, Oahu

250

Majusculamide B

Peptide

130

Kahala Bay, Oahu

251

(R)-3-Methyl-3-(2-oxopentyl)dihydrofuran-2(3H)-one

Lactone

131

Kahala Bay, Oahu

252

(S,E)-7-Methoxytetradec-4-enoic acid

Lipid

132

Kahala Bay, Oahu

253

Malyngamide A

Amide

133

Kahala Bay, Oahu

254

Malyngolide

Lactone

134

Kahala Bay, Oahu

255

Pukeleimide C

Amide

135

Kahala Bay, Oahu

256

Pukelemide A

Amide

136

Kahala Bay, Oahu

257

Pukeleimide B

Amide

136

Kahala Bay, Oahu

258

Pukeleimide D

Amide

136

Kahala Bay, Oahu

259

Pukeleimide E

Amide

136

Kahala Bay, Oahu

260

Pukelelimide F

Amide

136

Kahala Bay, Oahu

261

Pukeleimide G

Amide

136

Kahala Bay, Oahu

262

Lyngbyatoxin B

Tryptamine

137

Kahala Bay, Oahu

263

Lyngbyatoxin C

Tryptamine

137

Kahala Bay, Oahu

264

Isomalyngamide A

Amide

138

Kahala Bay, Oahu

265

Isomalyngamide B

Amide

138

Kamalo Jetty, Molokai Ala Moana Beach, Oahu Ala Moana Beach, Oahu Ala Moana Beach, Oahu Oahu-South Shore Ala Moana Beach, Oahu Kaneohe Bay, Oahu Kaneohe Bay, Oahu Honaunau, Hawaii Honaunau, Hawaii Honaunau, Hawaii Honaunau, Hawaii Honaunau, Hawaii Honaunau, Hawaii Honaunau, Hawaii

266 267 268 269 270 271 272 273 274 275 276 277 278 279 280

2,5-Dimethyldodecanoic acid Malevamide A Malevamide B Malevamide C Malevamide D Malevamide E Symplostatin 3 Dolastatin 14 Crossbyanol A Crossbyanol B Crossbyanol C Crossbyanol D Honuacin A Honuacin B Honuacin C

Lipid Peptide Cyclic Peptide Cyclic Peptide Peptide Cyclic Peptide Peptide Cyclic Peptide Brominated Phenol Brominated Phenol Brominated Phenol Brominated Phenol Lactone Ester Ester

139 140 140 140 141 142 143 143 144 144 144 144 145 145 145

Pyrone Pyrone Pyrone Pyrone Quinone Quinone Quinone Quinone Tetrahydrofuran Tryptamine Tryptamine Phenol Benzofuran Brominated Phenol Peptide Peptide Peptide Peptide

146 146 146 146 147 147 147 147 148 149 149 150 151 151 152 152 152 152

Bacteria Streptomyces sp. Wailupe Beach, Oahu 281 Wailupemycin A Streptomyces sp. Wailupe Beach, Oahu 282 Wailupemycin B Streptomyces sp. Wailupe Beach, Oahu 283 Wailupemycin C Streptomyces sp. Wailupe Beach, Oahu 284 3-epi-5-Deoxyenterocin Streptomyces sp. Mouth of Halawa Stream, Oahu 285 Halawanone A Streptomyces sp. Mouth of Halawa Stream, Oahu 286 Halawanone B Streptomyces sp. Mouth of Halawa Stream, Oahu 287 Halawanone C Streptomyces sp. Mouth of Halawa Stream, Oahu 288 Halawanone D Streptomyces sp. Kailua Beach, Oahu 289 Bonactin Nocardiopsis dassonvillei Kahaka Beach, Oahu 290 Kahakamide A Nocardiopsis dassonvillei Kahaka Beach, Oahu 291 Kahakamide B Pseudoalteromonas rubra Oahu Island 292 2-(p-Hydroxybenzyl)prodigiosin Pseudoalteromonas sp. CMMED Kaneohe 290 Bay, Oahu 293 2,3,5,7-Tetrabromobenzofuro[3,2-b]pyrrole Pseudoalteromonas sp. CMMED Kaneohe 290 Bay, Oahu 294 4,4',6-Tribromo-2,2'-biphenol Halimonas sp. LOB-5 Loihi Seamount 295 Loihichelin A Halimonas sp. LOB-5 Loihi Seamount 296 Loihichelin B LOB-5KG · DOILoihi Seamount © GeorgHalimonas Thiemesp. Verlag 10.1055/s-0042-105876 · Planta297 Med · Loihichelin HagiwaraCKA et al. Halimonas sp. LOB-5 Loihi Seamount 298 Loihichelin D

Halimonas sp. LOB-5 Halimonas sp. LOB-5

Loihi Seamount Loihi Seamount

299 300

Loihichelin E Loihichelin F

Peptide Peptide

152 152

Helicascus kanaloanus Helicascus kanaloanus Myrothecium verrucaria Myrothecium verrucaria Myrothecium verrucaria Exserohilum rostratum Exserohilum rostratum Exserohilum rostratum Exserohilum rostratum Zygosporium masonii Aspergillus sp. CNK-371 Aspergillus sp. CNK-371 Aspergillus sp. CNK-371 Aspergillus sp. CNK-371 Aspergillus insulicola Aspergillus insulicola Aspergillus insulicola Malbranchea graminicola Malbranchea graminicola Malbranchea graminicola Malbranchea graminicola

State of Hawaii State of Hawaii Maui Island Maui Island Maui Island Lanai Island Lanai Island Lanai Island Lanai Island Maui Island Manele Bay, Lanai Manele Bay, Lanai Manele Bay, Lanai Manele Bay, Lanai State of Hawaii State of Hawaii State of Hawaii Kona, Hawaii Kona, Hawaii Kona, Hawaii Kona, Hawaii

301 302 303 304 305 306 307 308 309 310 311 312 313 314 315 316 317 318 319 320 321

Helicasolide A Helicasolide B 3-Hydroxyoroidin E 13'-Acetyltrichoverrin B Miophytocen C Rostratin A Rostratin B Rostratin C Rostratin D Zygosporamide Tropolactone A Tropolactone B Tropolactone C Tropolactone D Azonazine Pre-sclerotiotide F Sclerotiotide F (-)-Spiromalbramide (+)-Isomalbrancheamide B (+)-Malbrancheamide C (+)-Isomalbrancheamide C

Lactone Lactone Lactone Lactone Lactone Quinone Quinone Quinone Quinone Cyclic Peptide Meroterpene Meroterpene Meroterpene Meroterpene Cyclic Peptide Cyclic Peptide Cyclic Peptide Amide Amide Amide Amide

153 153 154 154 154 155 155 155 155 156 157 157 157 157 158 159 159 160 160 160 160

Fungi


1

2

3

6

7

5

4 O

8 O

O

S

S

S 9

O

10 O

O

O

S 12 O

O

S S

S

S

11

S

13 O S

S

S

S O

14

O

O

O

O S

O

S

S O

15

16 O

O

O O 17

18

H

H

O H HO

Acutilol A acetate (22)

OH

Dictyolene (20)

O H AcO

Acutilol A (21)

H

OH

Dictyoxepin (19)

O H HO

H

OHC OHC

H

H

Acutilol B (23)

Dictyodial (24)

CHO H

OH

H H

OHC H OHC

H3COH2C H OHC

OH

OH

H β-Crenulal (25)

4β-Hydroxydictyodial A (26)

18,O-Dihydro-4β-hydroxydictyodial (27)

Fig. 1S Compounds 1-27 © Georg Thieme Verlag KG · DOI 10.1055/s-0042-105876 · Planta Med · Hagiwara KA et al.

OH

Br

Br

BrCl

BrCl

BrCl OH Laurinterol (30)

Nidifidiene (29)

Nidificene (28)

OH

OH

Nidifidienol (31)

O

O Br

33

32 Cl

O

Cl Nidifocene (34)

Cl

O

O

35

Cl O

O O

O

Br

Br

O

Br

Br

Br Br

O

O

Br

cis-Maneonene A (36) cis-Maneonene B (37) trans-Maneonene B (38) iso-Maneonene A (39) iso-Maneonene B (40) OAc

O

Cl

O

OH NHAc OH

43 42

Br Br

OH

Br

cis-Maneonene C (41)

O

R= COCH2(CH2)nCH3 where n = 12, 14, 16, 20, 21, 22

O 44

49

OH Br

O

NHR

HO

OH Br

Br

HO

Cl

O Br

Kahukuene A (45) O

Kahukuene B (46) O

N H

N

O

HO

O OH O O

O

Martensine B (52)

OCH3

O Manauealide A (53)

O

O OH O O

Cl OH

O

N H

Martensine A (51)

OH

H N N

N H

Fragilamide (50)

OH

H N

Br allo-Isoobtusol (48)

N

NH

O

Br Ma'ilione (47)

OAc


O

OCH3

O Manauealide B (54)

OH

OH O OH O O

O

O

OCH3 O Br

O OH

O OH O O

OH

Manauealide C (55)

O

OCH3 61

O Debromoaplysiatoxin (56) OH

OH

OCH3 O O

O

O

O O

HO

O

OCH3 Malyngamide M (58)

O

Chondrocolactone (65)

Cl

O

OCH3

OH

OCH3

N O

O N

Br

Br Chondrocole A (62) O

Br

H

H Cl

HO 4S O

HO 4S O

-O

-O

Chondrocole B (63)

O HO

O Cl O

HO

O Cl

Cl

Malyngamide N (59)

OAc

O Cl

Malyngamide I Acetate (60) O

O

O

OH

Anhydrodebromoaplysiatoxin (57)

Br

Cl

N

O

66

O

67

HO

O

Chondrocole A (Revised) (64) H HO -O

H

H

HO

4S

-O

HO 4S

HO 4S

O

72

71 HO

O

H -O

-O

O

4S

70 O

H HO 4S

-O

69

OH HO

-O

HO

-O

4S

68

OH

H

O

O

73

4S

-O

O

O

74


4S

O

O

75

H2N

O O

O

N OH

NH

O

HN

O HN

HN

O

O

O

O

O NH

O

H N

O

O O

HN

HO H N

NH

NH

H N

N H

O

O

N

O

H N

N H

O

OH

O

Kahalalide A (77)

O

HN O HO

Kahalalide F (76)

NH O

HN

NH

O O

O

O

N OH

NH

N

H2N O

O HN

NH

NH O

O

HO

O HO

NH

OH

O OH H N

HO

HN

O O

H N

HN HO O

O

O

HN

HN

O O

O

O

O

O

O N

N H OH

O O

O

NH

O N

H N

HN

O

O HN Kahalalide O (81)

Kahalalide K (80)

N

Kahalalide G (79)

HN

O

HN

O

H N

O O

NH

O NH O

OH

O

O

H N

HN

Kahalalide B (78)

H N

N H

O NH

O

O

O HN

HN

O

N N H

O

HO OH

O

O

HO H N

O

H2N

H N

N H

O

O

O

O

O

H N

O

N H

O

H2N Kahalalide P (82)


O

NH

HN O

OH

H N

HO

HN

O

O O

HN

O

H N

HO

HN N

N H OH

O

O

O

O

H N

N

NH

O

O

O

O O

OH

HN

O O

NH

HN O

N H

O

O

O

O O

H N

HN

NH

norKA (85)

O

H2N Kahalalide Q (83)

H N O O

HN HO

H2N OH O

H N

H

H N N H

O

O

O N H

O

N

O

H N N H

NH O

O O

O O HN O

N H

O

NH

OH OH

5-OHKF (84) OH

H N

HO O

OH OH OH

OH

OH OH

OH OH

OH

O O

OH

HO OH

OH

OH

HO OH OH HO3SO

OH

OH OH OH

OH

O

HO OH

O

OH OH

OH HO

OH O

HO OH

Zooxanthellamide A (86) O OH HO3SO


OH OH

NH

OH OH OH

H N

HO O

OH

OH

OH OH

OH OH

O

OH

O O

OH

HO OH

OH

OH

HO OH OH

OH OH

OH

HO3SO

OH

OH

O

HO OH

O

OH OH

OH HO

OH O

HO

Zooxanthellamide B (87)

OH NH

O OH HO3SO

OH OH

OH OH OH

H N

HO OH OH O

OH HO

OH OH

O

OH

O O

OH

HO OH

OH

OH

HO OH OH HO3SO

OH

OH OH OH

OH

O

HO OH

O

OH OH

OH HO

OH O

HO OH Zooxanthellamide C-1 (88)

O OH HO3SO


OH OH

NH

OH OH OH

H N

HO OH OH

OH O

O

OH OH

OH

HO

OH

O O

OH

HO OH

OH

OH

HO OH

OH OH

OH

HO3SO

OH

OH

O

HO OH

O

OH OH

OH HO

OH O

HO OH Zooxanthellamide C-2 (89)

NH

O OH HO3SO

OH OH OH OH

OH

H N

HO OH OH

OH O

O

OH OH

OH

OH

O O

OH

HO OH

OH

OH

HO OH OH HO3SO

OH

OH OH OH

OH

O

HO OH

O

OH OH

OH HO

OH O

HO

Zooxanthellamide C-3 (90)

OH O OH HO3SO

OH OH


NH

OH OH OH

H N

HO OH OH

OH

OH OH

OH OH

OH

O O

OH

HO OH

OH

OH

HO O O HO3SO

OH OH

OH OH OH

OH

O

HO OH

O

OH OH

OH HO

OH O

HO Zooxanthellamide C-4 (91)

OH NH

O OH HO3SO

OH OH

OH OH OH

H N

HO OH OH O

OH

OH OH

OH OH

OH

O O

OH

HO OH

OH

OH

O OH OH HO3SO

OH

OH OH OH

OH

O

HO OH

O

OH OH

OH HO

OH O

HO OH

Zooxanthellamide C-5 (92) O OH HO3SO

OH OH


NH

O

OH O

O

OH OH

HO O

H

H

O

O H

O

HO

OCH3

O H

H

H Puupehenone (93)

H 94

Puupehenol (96)

Ilimaquinone (95)

OH Cl

OH

OH OH

O

O

OH OH

OCH3 H3CO

OH

O

CHO

O Upial (98)

O OH

Cl

O O

N

OH Poipuol (105)

H Molokinenone (104)

H

O O O

O

O

OH OH Cl

H

O H

H

H

H 107

H Auauamine (106) C

HO

H HO

O O OH

N H

H

O P

O H

O

O

NH2-+O3S

O Cl

O

H 15-Oxopuupehenol (103)

Nakafuran-9 (101) N

Cl

OH H 21-Chloropuupehenol (102)

O

Nakafuran-8 (100)

97

OH

O Upiol (99)

O

O

O

O Pokepola ester (108)

O

109

O O

O H

O H

O H

O H

H

H

HO

HO OH

110

H

O H HO

OH

111


OH

112

H

O

OCH3

Lehualide A (113) O

O

O

O

S

OCH3

O

O O

HS

OCH3

Lehualide C (115)

OCH3

Lehualide B (114)

OH

OCH3 O

O

O

O H HO

H Kiheisterone A (117)

HO

Cl Kiheisterone C (119)

O

H

O

O

H

H

H

122

123

O

NC Cl Kiheisterone E (121)

125

NHCHO 126

127

124

CN

NCS 9-Isocyanopupukeanane (128)

H

OH

CN

HO

H

H 129

OH

NC

130

H H

OH

NH3+Cl-

131

NHCHO

H

H

H

NCS

NCO

H

NC

HO

H Cl Kiheisterone D (120) H

H

O

H Kiheisterone B (118)

HO

H

H

H

O

O

H

O

H

H

H

HO

HO O

H

O

O

HO

HO

OCH3

Lehualide D (116)

O

H

OCH3

OH Isocyanoneopupukeanane (133)

+H

3N

Br

O H

H 15-Cyanopuupehenol (134)

OCH3 H 136

NC O H

O

Fig. 10S Compounds 11

O

Br

NC

132

OH

O

NH3+

Br Moloka'iamine (135)

3-137


H 15-Cyanopuupehenone (137)

H O

OH Cl

NCOC

O

O

O

O

H

H

H

H

O

NH2

H

Puupehedione (139)

Chloropuupehenone (138)

H Br

Dipuupehetriol (140) Cl

O

Br

O

NH

Br N-Methylceratinamine (141)

OH

HO

O

Br O

OH O

H N

Br

O

NH2

O O N NH

H3CO HO

Br N

Br

O

O

Psammaplysin A (144) Br

O

O Wai'anaeamine A (142)

O

H N

Br

Cl

Cl H2N

O

O Br

Br

Wai'anaeamine B (143)

OH

H3CO

N

H N

Br

O

R1HN NH3+

O

Aplysamine 3 (146)

Br NHR2

Br

Br O

Br OH

H3CO

N

R1, R2 = H N

Br

Br R1, R2 =

O

(CH2)7 (CH2)7

NH3+

O

Aplysamine 4 (147)

Br

R1, R2 = 11-17

Br H3CO

(CH2)12-13

Mololipids (145)

OH N

H N

Br

O

O Br

O N H

Aplysamine 5 (148)


OH O

OH O

O

OH O

O

OH O

O

OH

O

OCH3Br O

O

OH

O

O

O

OCH3Br O

OH

O

O

OCH3

O OAc Debromoaplysiatoxin acetate (151)

OAc Aplysiatoxin (149)

O

Aplysiatoxin acetate (150)

Cl N O

O

OCH3

C7H15

O

O

OCH3

N

O Malyngamide O (155)

Stylocheilamide (152) OAc

Cl

OCH3

Cl

OCH3

Cl

O

O

OCH3

N O

Malyngamide P (156) O O

Br

O N

O

O

N

O

O

HN

O Makalika ester (153)

Cl

Br O

N

(E)-Ocellenyne (158)

O

Makalikone ester (154)

Br OH

CHO

CN

CHO

H 2-Isocyanopupukeanane (160) OH

H

(Z)-Ocellenyne (159)

161

CHO

Lyngbyatoxin A acetate (157)

O

H

H H

162

H 163

O OH

O O O

OAc H Olepupuane (164)

O O

O

O

O

165

O

167

O O

O O O O

OH O

O

OH O

O

O

H

O OH

166

O

AcO

O

OCH3

O OH OH

OH

AcO

CHO CHO

H

O Br O

H

CHO

H

N H

O

168


O 169

O O

O

O

N

O

N

N

H

N

O

N

O

O

OAc

O

O

O O

Pulo'upone (173) O O O OCH3 O

H CO OCH3 3 OH

N+

O

O O Niuhinone B (175)

OCH3 OSphinxolide (172) O

O O

O

Niuhinone A (174)

HO

OCH3

H N

N

O O

N

H N

O

N

O

HN

Pupukeamide (177)

O O

O N

N

H N

O

O

O

O O

Kulolide (176) N H N

HN

O O O H N

N O

O O

O

O

N

O

O O

O

O

N

N H

O O

O

O

N O

Kulolide-2 (178)

N

O N

O O

O

H N

Kulomo'opunalide-1 (181) O

O

H N

N H

O O

O O

N

O

O O

O

O

O

N O

OAc OCH3

H3CO

H N

O

Ulapualide B (171) OCH3

O

O

Ulapualide A (170) N

N

O

OH O H3CO

O

H

OCH3

N

O OH O H3CO

HN

OCH3

N

HN

O O O H N

O

N

Kulolide-3 (179)

N N

O

O O N O

O Kulolainalide-1 (180)

Kulomo'opunalide-2 (182)


O O

O OCH3 OCH3 OCH3 O OH

N OAc

O

O

O

OH

NH

HO

O

O

N

N

HN

O

N H

O

O

O

Kulokekahalide-2 (185) H N

O

O

O

H N

NH2

NH

O

O

HN

HN O

N

NH

HN NH O

O

OH

O

O

Kahalalide D (187)

OH

O H N

HN HO OH

HN

NH

Kahalalide C (186)

Kahalalide E (188)

O

N

O

O

HN

O

HN

O O

O

O N

N H OH

O

O

HN N

N H OH

O

NH

O HO

O

H N O O

N H

H N

N H

HO

O

N

O

HN

O

O O

O

H N

N H

O

HN

O

O

O

HN O

O

H N

O

Kulokekahalide-1 (184)

H2N

NH

O O

O O

N

N

Tolytoxin 23-acetate (183)

O

H N

HN

H

OCH3

O O

N

O

O

NH

O

HN

OH Kahalalide H (189)

O

HO

O OH O

HN NH2 HN

OH Kahalalide J (190)

H N

OH O H N

NH2 O

N

O HN

O

HO

O H N

NH2 O

HN

NH

HN O O

O HN

NH

NH O

N

O

Kahalalide W (192)


HO

O

HO Kahalalide V (191)

NH

O

OH

OH

O O

OH O

NH2 HO

OH

OH

HO

OH OH

OH OH

OH

OH OH OH

OH O HO

N H

O

HO

N H

HO

OH

OH OH

OH

O OH

O

OH

HO

OH

O

HO

OH H OH O OH HO

Palytoxin (195)

OH

O

OH

O

OH OH

OH OH

OH

OH O

OH

OH

O O

OH O

NH2 HO

OH

OH

HO

OH OH

OH OH

OH

OH OH OH

OH O HO

N H

O N H

HO

HO

O

OH O

OH OH

OH

Ac

OH

HO

OH

O

OH

O O

42S-Hydroxy-50S-palytoxin (196)

HO

OH OH H OH O OH HO

OH OH OH


OH OH

OH

OH

O

OH

O

OH

HO

OH

HO

OH O

NH2

O

O

OH

O

CO2CH3

OH OH

OH OH

OH

O O Pukalide (198)

OH OH OH

OH O

O

N H

HO

HO

N H

HO

OH OH

O

O

O

OH HO

HO OAc

O

OAc OAc

OH

O

HO

OAc

O

202

OCH3

Cl

OAc HO

N

NH2 N

205

N

N

O

Coraxenolide A (207)

OAc OH Waixenicin B (200)

OAc

NH2 N Corabohcin (211)

206

O

O

O

OAc Waixenicin A (199)

204

HN N

OAc

OAc

O

N

OAc

OAc

203

OAc

N

OH

OAc

O OCH3

N

OH OH

OH OH

HO

Cl

OH

OCH3

Cl O

HO

OH OH H OH O

OAc 201

O

OH

OCH3

Cl

HO

OH O

OAc OAc

OH OH

Ac

OH

42S-Hydroxy-50R-palytoxin (197)

O

O

O

Coraxenolide B (208)

O O

Coraxenolide C (209)


O

Coraxenolide D (210)

Cl

Br

H H

H

H

H

HO

HO

214

Papakusterol (212)

215

7-Dehydropapakusterol (213) O

OH O

OH

O

N

OH

Br

O

COCH3 O OH Spinochrome M (219)

O Ehuazulene (216)

217

O

218

OH O

O

OH O

OH

OH O 220

OH

OH O

HO

OH

OH HO

OH

H3COC OH O 221

OH O 222 O

OH O HO

OH O OH

HO

H3COC O 227

OH O 226

Br

Br

Br

Br

HO

OH Br

OH

Br O O

Br

Br

234

Br 235

233

OH

OH OH

Br Br

Br

OH

OH Br

Br

OH Br

Br

Br

Br

OH

OH

OH

Br

Br

OH OH O 230

Br

OH

OH 232

OH

OH OH O 229

O

Br

231

OH HO

H3COC

OH

OH O

O

HO

OH O 228 OH

OH O

OH O 225

O

OH

OH

O

OH O 224

OH O 223

236

Br 238

237

Br

Br

OH

O

O

Br

Br

Br

Br 240

OH 239

Br 241

O

Br Br

Br Br

OH

OH

O Br O

N H

Br 242

OH OAc 243

OAc 244

OAc 245


OAc 246

O OH 247

H N

HO

OCH3

O N

N

O

O

N

O

H3CO

O

O Lyngbyatoxin A (248)

NH2

N

O

O

Majusculamide B (250) H3CO

O

O

OCH3

O

N

N

O

O N

Malyngamide A (253)

Cl

OCH3

OH

OCH3

N

N

O O

N

O

O

N

H3CO Pukeleimide F (260)

O O

O

N O

O Pukeleimide E (259)

OCH3

OCH3

OCH3

O

O

OH 252

N

O

O Pukeleimide D (258)

HO Pukeleimide B (257)

OCH3

N

OH HO

O

251

O Pukeleimide A (256)

OCH3 O

O

N

O

N HO

OCH3 N

O

O

N

O Pukeleimide C (255)

O

N

O

OCH3 HO

N

N

O

O

Majusculamide A (249) N H

OCH3

NH2

H3CO

O Pukeleimide G (261) OCH3

Malyngolide (254)

OCH3

Isomalyngamide A (264)

HN

N O

N

HO

HO HN

O

O

OCH3

Cl

OH

N

N

O

O

OCH3 N H

N H

N O

N Isomalyngamide B (265)

HO

Lyngbyatoxin B (262)

O

O

HO Lyngbyatoxin C (263)


Cl

OCH3

COOH 266

O O

N N

H N

O

O NH O

O N

O

N

N H

O

O

N

N

N

N

O O NH

O

O

N

O

Malevamide A (267)

O

N

NH O

N O N

N O

O

O O

N

N O

NH O

O

O

NH

O

O

Malevamide B (268)

NH

O O

N O

O

N O

H N

N

O

O

N

N

H N

N O

Malevamide C (269)

O

O

O N

N

O O

N

N

O

O

O

Malevamide E (271)

NH O

H N

N

N

O

O

N

O

O

O

O

O HO

Malevamide D (270)

H N O

H N

N O

O

N

O N

N

O

N

NH

N

O

O

O

O

O

O

O

O N

N O

O

O O

Symplostatin 3 (272)

CO2H

N

O N

N

N

O

O

O O

N O

Dolastatin 14 (273) NH2


N O

O

Br

O O

OH Br

Br

Br

OH

Crossbyanol A (274)

O

O

HO

Br

O

OH

OH

Cl

O Honuacin C (280)

O

Cl O

O

Br

O

Honuacin B (279)

Honuacin A (278) O

OH

O

Cl

O

Br

Br

O O

O

O

HO

O

OH

O

O

O H3CO

O

O O

Wailupemycin A (281)

HO OCH3

OCH3

O

O

Br

Br

Br

Br

Wailupemycin B (282) OSO3H O Br Br O Crossbyanol B (275) OSO3H O

Wailupemycin C (283)

O H

284 O O

H

OSO3H

OH O

Br

Br

Br

OH

O

O

Halawanone B (286)

O O

O

O

OH O

O

Halawanone D (288)

Bonactin (289) NH2

OCH3

Br

NH2

OCH3

O

O N

OSO3H Br

Br

OH

Br Crossbyanol D (277)

N

OH

OH

O

O O

OH O

OH

O

OH

OCH3 Kahakamide A (290)


OH

OH O Halawanone C (287)

Crossbyanol C (276)

Br

Br

OH O

OH

Br

O

O

O

Br

O

HO

OH

O

O

Br

Br

HO

O

Halawanone A (285)

O

O

OH

OH O

Br

O O OH

OH

O NH2

Kahakamide B (291)

OH

OCH3

HO N H H N

Br

Br

O 293

N H

N

292

O

Br

H2N

O HO O

Br

OH O H N

N H

O HO

Loihichelin A (295)

O

N H

O

Br

HO 294

N H

O

Br

OH H N

O

H N

N H

O HO

OH

N

HO

H N

Br

O

O

O H2N

O HO OH O

OH O H N

N H

O HO

Loihichelin B (296)

HO N H

O HO

Loihichelin C (297)

OH H N

O

H N

N H

N H

O

O

O

HO

N

O

OH H N

O

H N

N H

O HO

N OH

O

O

H N

N H

N

O

O HO H2N

OH O H N

HO

H N

N H

O O

O

N H

O

O

N OH

O

O H2N

O HO O

OH O H N

N H

O HO

Loihichelin D (298)

O

N

HO O

H N

N H

N H

O HO

OH H N

O

H N

N H

O

O

O

O H2N

O HO O N H Loihichelin E (299)

OH O H N O HO

H2N

O HO O N H Loihichelin F (300)

N H

OH O H N O HO

N H

O H N

HO

H N O HO

N

O N H

O HO O

N OH

H N

O N H

O

OH H N O

O HO

O

N OH

N

O N H


H N O

O N H

OH H N O

O

N OH

N OH

O

H

H

O

O

H

OH

H

O

O

HO

O

O

OH OH

O

O

O

O

Helicasolide A (301)

H

O

O O

O

H

OH

OH

O

O

O

O

O O

O

HO HO AcO 304

HO

HO

303 Helicasolide A (302) OH H

O

O O N

H OH

S

SN

H

Rostratin A (306)

H

OH

N

S

SN

H

H3CO

H

O

NH

H N

O

S S N

HS

H OH

H

O

N

S S N

O

O

H

O

O

O

O

H O

H

O O

H

Tropolactone B (312)

H

Tropolactone C (313)

N

O

O N H

NH N

O

HN HN

CHO

OH

N O

N

N

CO2CH3 O

N

O

O

NH

O

O

H

O

Azonazine (315)

O

CHO

H

Tropolactone D (314) Sclerotiotide F (317)

Pre-sclerotiotide F (316) O

H N

OH N

317

H OH N N

H

H N

H N

OH N N

Br

NH 318

Cl

O

O

O

H

H

Rostratin D (309)

CO2CH3

H

O

OH

CO2CH3

Tropolactone A (311)

Zygosporamide (310)

H

CO2CH3

H

O

O

O

OH

H

O

O O

H

OH

O HN

N

Rostratin C (308)

OH

O

NH

H OH

O

Rostratin B (307)

O

OH

O O

Miophytocen C (305)

O

O H OH

O

H

H

OH

O

O

Cl

319

Cl

H

H

H N

OH N N

H 320


Br