Bisabolane Derivatives from Leontopodium alpinum

From the roots of Leontopodium alpinum, four new bisabolane sesquiterpenoids, (1R*,2S*,4R*,5S*)‐4‐(acetyloxy)‐2‐[3‐(acetyloxy)‐1,5‐dimethylhex‐4‐enyl]‐5‐methylcyclohexyl (2Z)‐2‐methylbut‐2‐enoate ( 1 ), (1R*,4S*,6R*)‐4‐(acetyloxy)‐6‐[3‐(acetyloxy)‐1,5‐dimethylhex‐4‐enyl]‐3‐methylcyclohex‐2‐en‐1‐yl (2Z)‐2‐methylbut‐2‐enoate ( 2 ), and 3‐methyl‐1‐{2‐[(1R*,2R*,5R*,6S*)‐2,5,6‐tris(acetyloxy)‐4‐methylcyclohex‐3‐en‐1‐yl]propyl}but‐2‐enyl (2Z)‐2‐methylbut‐2‐enoate ( 3 and 4 ) have been isolated. The latter constituents differ from each other by the relative configurations of the chiral centers of the hexenyl side chain.     

Neoclerodane Diterpenes from Amoora stellato‐squamosa

From the twigs of Amoora stellato‐squamosa, five new neoclerodane diterpenes have been isolated and characterized, methyl (13E)‐2‐oxoneocleroda‐3,13‐dien‐15‐oate (=methyl (2E)‐3‐methyl‐5‐[(1S,2R,4aR,8aR)‐1,2,3,4,4a,7,8,8a‐octahydro‐1,2,4a,5‐tetramethyl‐7‐oxo‐naphthalen‐1‐yl]pent‐2‐enoate; 1 ), (13E)‐2‐oxoneocleroda‐3,13‐dien‐15‐ol (=(4aR,7R,8S,8aR)‐1,2,4a,5,6,7,8,8a‐octahydro‐8‐[(E)‐5‐hydroxy‐3‐methylpent‐3‐enyl]‐4,4a,7,8‐tetramethylnaphthalen‐2(1H)‐one; 2 ), (3α,4β,13E)‐neoclerod‐13‐ene‐3,4,15‐triol (=(1R,2R,4aR, 5S,6R,8aR)‐decahydro‐5‐[(E)‐5‐hydroxy‐3‐methylpent‐3‐enyl]‐1,5,6,8a‐tetramethylnaphthalene‐1,2‐diol; 3 ), (3α,4β,13E)‐4‐ethoxyneoclerod‐13‐ene‐3,15‐diol (=(1R,2R,4aR,5S,6R,8aR)‐1‐ethoxydecahydro‐5‐[(E)‐5‐hydroxy‐3‐methylpent‐3‐enyl]‐1,5,6,8a‐tetramethylnaphthalen‐2‐ol; 4 ), and (3α,4β,14RS)‐neoclerod‐13(16)‐ ene‐3,4,14,15‐tetrol (=(1R,2R,4aR,5S,6R,8aR)‐decahydro‐5‐[3‐(1,2‐dihydroxyethyl)but‐3‐enyl]‐1,5,6,8a‐tetramethylnaphthalene‐1,2‐diol; 5 ), together with two known compounds, (13E)‐neocleroda‐3,13‐diene‐15,18‐diol ( 6 ) and (13S)‐2‐oxoneocleroda‐3,14‐dien‐13‐ol ( 7 ).     

A Novel Norlignan and a Novel Phenylpropanoid from Peperomia tetraphylla

A novel cyclobutane‐type norlignan, peperotetraphin (=methyl rel‐(1R,2S,3S)‐2,3‐bis(7‐methoxy‐1,3‐benzodioxol‐5‐yl)cyclobutanecarboxylate; 1 ), and a novel phenylpropanoid, i.e., methyl (2E)‐3‐(7‐methoxy‐1,3‐benzodioxol‐5‐yl)prop‐2‐enoate ( 2 ), along with three known compounds, α‐asarone (=1,2,4‐trimethoxy‐5‐[(1E)‐prop‐1‐en‐1‐yl]benzene), vanillic acid (=4‐hydroxy‐3‐methoxybenzoic acid), and veratric acid (=3,4‐dimethoxybenzoic acid), were isolated from the EtOH extract of the whole plant of Peperomia tetraphylla. Their structures were determined by spectroscopic methods, especially 1D‐ and 2D‐NMR techniques. This is the first report of naturally occurring cyclobutane‐type norlignans.     

Isolation of a New Carotenoid and Two New Carotenoid Glycosides from Curtobacterium flaccumfaciens pvar poinsettiae

An efficient method for the extraction of the carotenoids from Curtobacterium flaccumfaciens pvar poinsettiae was developed. The glucosides of C.p. 450 (=(all‐E,2R,2′R)‐2‐[4‐(β‐D ‐glucopyranosyloxy)‐3‐methylbut‐2‐enyl]‐2′‐(4‐hydroxy‐3‐methylbut‐2‐enyl)‐β, β‐carotene; 4 ) and of C.p. 473 (=(all‐E,2R,2′S)‐2‐[4‐(β‐D ‐glucopyranosyloxy)‐3‐methylbut‐2‐enyl]‐2′‐(3‐methylbut‐2‐enyl)‐3′,4′‐didehydro‐1′,2′‐dihydro‐β,ψ‐caroten‐1′‐ol; 5 ) were isolated for the first time. In addition, the hitherto unknown 3′,4′‐dihydro derivative of C.p. 450, called C.p. 460 (=(all‐E,2R,2′R)‐2‐(4‐hydroxy‐3‐methylbut‐2‐enyl)‐2′‐(3‐methylbut‐2‐enyl)‐1′,2′‐dihydro‐β,ψ‐caroten‐1′‐ol; 6 ), was identified. The structures were established by UV/VIS, CD, ¹H‐ and ¹³C‐NMR, and mass spectra.     

Further Prenylated Bi‐ and Tricyclic Phloroglucinol Derivatives from Hypericum papuanum

From the petroleum‐ether extract of the dried aerial parts of Hypericum papuanum, three new prenylated tricyclic and four new bicyclic acylphloroglucinol derivatives were isolated by bioactivity‐guided fractionation. The structures of the bicyclic compounds enaimeone A, B, and C ( 1 / 1a , 2 / 2a , and 3 / 3a , resp.) were elucidated as rel‐(1R,5R,6S)‐4‐hydroxy‐6‐(1‐hydroxy‐1‐methylethyl)‐5‐methyl‐1‐(3‐methylbut‐2‐enyl)‐3‐(2‐methylpropanoyl)‐bicyclo[3.2.1]oct‐3‐ene‐2,8‐dione ( 1 / 1a ), rel‐(1R,5R,6R)‐4‐hydroxy‐6‐(1‐hydroxy‐1‐methylethyl)‐5‐methyl‐1‐(3‐methylbut‐2‐enyl)‐3‐(2‐methylpropanoyl)bicyclo[3.2.1]oct‐3‐ene‐2,8‐dione ( 2 / 2a ), rel‐(1R,5R,6R)‐4‐hydroxy‐6‐(1‐hydroxy‐1‐methylethyl)‐5‐methyl‐3‐(2‐methylbutanoyl)‐1‐(3‐methylbut‐2‐enyl)bicyclo[3.2.1]oct‐3‐ene‐2,8‐dione ( 3 / 3a ). The tricyclic isolates 8‐hydroxy‐3β‐(1‐hydroxy‐1‐methylethyl)‐4,4,7‐trimethyl‐9‐(2‐methylpropanoyl)‐5βH‐tricyclo[5.3.1.0^1,5]undec‐8‐ene‐10,11‐dione ( 4 ), 8‐hydroxy‐3α‐(1‐hydroxy‐1‐methylethyl)‐4,4,7‐trimethyl‐9‐(2‐methylpropanoyl)‐5βH‐tricyclo[5.3.1.0^1,5]undec‐8‐ene‐10,11‐dione ( 5 ), and 8‐hydroxy‐3α‐(1‐hydroxy‐1‐methylethyl)‐4,4,7‐trimethyl‐9‐(2‐methylbutanoyl)‐5βH‐tricyclo[5.3.1.0^1,5]undec‐8‐ene‐10,11‐dione ( 6 ), and their corresponding tautomers 4a , 5a , and 6a , were named 1′‐hydroxyialibinones A, B, and D, respectively. Oxidative decomposition of furonewguinone A (=2,3,3a,5‐tetrahydro‐3a‐hydroxy‐2‐(1‐hydroxy‐1‐methylethyl)‐5‐methyl‐5‐(3‐methylbut‐2‐enyl)‐7‐(2‐methylpropanoyl)‐benzofuran‐4,6‐dione; 7 ) led to furonewguinone B (=3,3a,7,7a‐tetrahydro‐3a,6,7a‐trihydroxy‐2‐(1‐hydroxy‐1‐methylethyl)‐7‐methyl‐7‐(3‐methylbut‐2‐enyl)‐5‐(2‐methylpropanoyl)benzofuran‐4(2H)‐one; 8 / 8a ). Structure elucidation was based on extensive 1D and 2D NMR studies, as well as on data derived from mass spectrometry. Furthermore, the cytotoxicity towards KB nasopharyngeal carcinoma cells and the antibacterial activity were determined.     

Chemical Constituents of the Flowers of Azadirachta indica

Studies on the chemical constituents of the flowers of Azadirachta indica have led to the isolation of two new flavanones, flowerine (=5‐hydroxy‐7,4′‐dimethoxy‐8‐(3‐methylbut‐2‐enyl)flavan‐4‐one; 1 ) and flowerone (=5,7,8,4′‐tetrahydroxy‐3′‐(3‐methylbut‐3‐enyl)flavan‐4‐one; 2 ), and two new triterpenoids, O‐methylazadironolide (=7α‐(acetoxy)‐23ξ‐methoxy‐21,23‐epoxy‐24,25,26,27‐tetranorapotirucalla‐1,14,20(22)‐trien‐3,21‐dione; 3 ) and diepoxyazadirol (=(20S,23S,24R)‐7‐α‐(acetoxy)‐25‐hydroxy‐21,24 : 23,24‐diepoxyapotirucalla‐1,14‐dien‐3‐one; 4 ) along with the known triterpenoid trichilenone acetate (=7α‐(acetoxy)‐14,15 : 21,23‐diepoxy‐24,25,26,27‐tetranorapotirucalla‐1,20,22‐trien‐3‐one; 5 ), two known flavanones, nimbaflavone (=5,7‐dihydroxy‐4′‐methoxy‐8,3′‐bis(3‐methylbut‐2‐enyl)‐flavan‐4‐one; 6 ) and 3′‐prenylnaringenin (=5,7,4′‐trihydroxy‐3′‐(3‐methylbut‐2‐enyl) flavan‐4‐one; 7 ), and 4‐(2‐hydroxyethyl)phenol ( 8 ). Their structures have been elucidated through spectral studies, including 2D‐NMR experiments, and chemical transformation. Compounds 5, 7 and 8 are heretofore unreported from any part of tree, while 6 has been isolated earlier from leaves.     

Stereo‐Inversion in the (4R)‐γ‐Decanolactone Synthesis by Saccharomyces cerevisiae: (2E,4S)‐4‐Hydroxydec‐2‐enoic Acid Acts as a Key Intermediate

Methyl (2E,4R)‐4‐hydroxydec‐2‐enoate, methyl (2E,4S)‐4‐hydroxydec‐2‐enoate, and ethyl (±)‐(2E)‐4‐hydroxy[4‐²H]dec‐2‐enoate were chemically synthesized and incubated in the yeast Saccharomyces cerevisiae. Initial C‐chain elongation of these substrates to C₁₂ and, to a lesser extent, C₁₄ fatty acids was observed, followed by γ‐decanolactone formation. Metabolic conversion of methyl (2E,4R)‐4‐hydroxydec‐2‐enoate and methyl (2E,4S)‐4‐hydroxydec‐2‐enoate both led to (4R)‐γ‐decanolactone with >99% ee and 80% ee, respectively. Biotransformation of ethyl (±)‐(2E)‐4‐hydroxy(4‐²H)dec‐2‐enoate yielded (4R)‐γ‐[²H]decanolactone with 61% of the ²H label maintained and in 90% ee indicating a stereoinversion pathway. Electron‐impact mass spectrometry analysis (Fig. 4) of 4‐hydroxydecanoic acid indicated a partial C(4)→C(2) ²H shift. The formation of erythro‐3,4‐dihydroxydecanoic acid and erythro‐3‐hydroxy‐γ‐decanolactone from methyl (2E,4S)‐4‐hydroxydec‐2‐enoate supports a net inversion to (4R)‐γ‐decanolactone via 4‐oxodecanoic acid. As postulated in a previous work, (2E,4S)‐4‐hydroxydec‐2‐enoic acid was shown to be a key intermediate during (4R)‐γ‐decanolactone formation via degradation of (3S,4S)‐dihydroxy fatty acids and precursors by Saccharomyces cerevisiae.     

Two New Ceramides from the Marine Sponge Ircinia fasciculata

A new 4‐sulfated ceramide, ircisulfamide (=N‐[(1S*,2S*,3R*)‐2‐hydroxy‐1‐(hydroxymethyl)‐3‐(sulfooxy)heptadecyl]hexadecanamide; 1 ), and a new glycosphingolipid, ircicerebroside (=(2R*)‐N‐{(1S*,2R*,3E,7E)‐1‐[(β‐D ‐glucopyranosyloxy)methyl]‐2‐hydroxy‐8‐methylheptadeca‐3,7‐dienyl}‐2‐hydroxyeicosanamide; 2 ), were isolated from the aqueous EtOH extract of the marine sponge Ircinia fasciculata (Pallas ). The structures of the new compounds were elucidated on the basis of spectroscopic analysis and by means of chemical methods.     

A Guaianolide Sesquiterpene,a Chromenone,and a Flavanone from Ligularia macrophylla

Three new compounds, (5β,9β)‐guaia‐6,10(14)‐dien‐9‐ol (=rel‐(1R,3aS,5R,8aR)‐1,2,3,3a,4,5,6,8a‐octahydro‐1‐methyl‐4‐methylene‐7‐(1‐methylethyl)azulen‐5‐ol; 1 ), 6‐acetyl‐8‐methoxy‐2,3‐dimethylchromen‐4‐one (=6‐acetyl‐8‐methoxy‐2,3‐dimethyl‐4H‐1‐benzopyran‐4‐one; 2 ), and (2S)‐3′‐hydroxy‐5′,7‐dimethoxyflavanone (=(2S)‐2,3‐dihydro‐2‐(3‐hydroxy‐5‐methoxyphenyl)‐7‐methoxy‐4H‐1‐benzopyran‐4‐one; 3 ) were isolated from the roots and rhizomes of Ligularia macrophylla, together with seven known compounds. Their structures and configurations were elucidated by spectroscopic methods, including 2D‐NMR techniques.     

Three New Neolignans from the Aril of Myristica fragrans

Three new neolignans, named 1‐deoxycarinatone ( 1 ), isodihydrocarinatidin ( 2 ), and isolicarin A ( 3 ), together with the known neolignan (+)‐dehydrodiisoeugenol ( 4 ), were isolated from mace (the aril of Myristica fragrans Houtt .). Their structures were elucidated as 2‐[(1S)‐2‐(4‐hydroxy‐3‐methoxyphenyl)‐1‐methylethyl]‐6‐methoxy‐4‐(prop‐2‐enyl)phenol ( 1 ), 4‐[(2R,3R)‐2,3‐dihydro‐7‐methoxy‐3‐methyl‐5‐(prop‐2‐enyl)benzofuran‐2‐yl]‐2‐methoxyphenol ( 2 ), and 4‐{(2S,3R)‐2,3‐dihydro‐7‐methoxy‐3‐methyl‐5‐[(1E)‐prop‐1‐enyl]benzofuran‐2‐yl}‐2‐methoxyphenol ( 3 ) on the basis of spectroscopic data.     

New α‐Glucosidase Inhibitors from the Mongolian Medicinal Plant Ferula mongolica

The four new and four known sesquiterpenoid derivatives 1 – 4 and 5 – 8 , respectively, were isolated from the air‐dried roots of Ferula mongolica. The structures of these compounds were determined by spectroscopic methods and found to be rel‐(2R,3R)‐2‐[(3E)‐4,8‐dimethylnona‐3,7‐dienyl]‐3,4‐dihydro‐3,8‐dihydroxy‐2‐methyl‐2H,5H‐pyrano[2,3‐b][1]benzopyran‐5‐one ( 1 ), rel‐(2R,3R)‐2‐[(3E)‐4,8‐dimethylnona‐3,7‐dienyl]‐2,3‐dihydro‐7‐hydroxy‐2,3‐dimethyl‐4H‐furo[2,3‐b][1]benzopyran‐4‐one ( 2 ), rel‐(2R,3R)‐2‐[(3E)‐4,8‐dimethylnona‐3,7‐dienyl]‐2,3‐dihydro‐7‐hydroxy‐2,3‐dimethyl‐4H‐furo[3,2‐c][1]benzopyran‐4‐one ( 3 ), rel‐(2R,3R)‐2‐[(3E)‐4,8‐dimethylnona‐3,7‐dienyl]‐2,3‐dihydro‐7‐methoxy‐2,3‐dimethyl‐4H‐furo[3,2‐c][1]benzopyran‐4‐one ( 4 ), (4E,8E)‐1‐(2‐hydroxy‐4‐methoxyphenyl)‐5,9,13‐trimethyltetradeca‐4,8,12‐trien‐1‐one ( 5 ), the rel‐(2R,3S) diastereoisomer 6 of 2 , the rel‐(2R,3S) diastereoisomer 7 of 4 , and (4E,8E)‐1‐(2,4‐dihydroxyphenyl)‐5,9,13‐trimethyltetradeca‐4,8,12‐trien‐1‐one ( 8 ). These compounds were tested as inhibitors against the enzyme α‐glucosidase. The compounds 1 – 6 and 8 exhibited significant inhibitory activity and, therefore, represent a new class of α‐glucosidase inhibitors.     

New Cholinesterase‐Inhibiting Steroidal Alkaloids from Sarcococca saligna

Seven new steroidal alkaloids, 2‐hydroxysalignarine‐E (=(2′E,20S)‐20‐(dimethylamino)‐2β‐hydroxy‐3β‐(tigloylamino)pregn‐4‐ene; 1 ), 5,6‐dihydrosarconidine (=(20S)‐20‐(dimethylamino)‐3β‐(methylamino)‐5α‐pregn‐16‐ene; 2 ), salignamine (=(20S)‐20‐(methylamino)‐3β‐methoxypregna‐5,16‐diene; 3 ), 2‐hydroxysalignamine (=(20S)‐20‐(dimethylamino)‐2β‐hydroxy‐3β‐methoxypregna‐5,16‐diene; 4 ), salignarine‐F (=(2′E, 20S)‐20‐(dimethylamino)‐4β‐hydroxy‐3β‐(tigloylamino)pregn‐5‐ene; 5 ), salonine‐C (=(2′E,20S)‐20‐(dimethylamino)‐3β‐(tigloylamino)pregna‐4,14‐diene; 6 ), and N‐[formyl(methyl)amino]salonine‐B (=(20S)‐20‐[formyl(methyl)amino]‐3β‐methoxypregna‐5,16‐diene; 7 ) have been isolated from the MeOH extract of Sarcococca saligna, along with the six known alkaloids dictyophlebine ( 8 ), epipachysamine‐D ( 9 ), saracosine ( 10 ), iso‐N‐formylchonemorphine ( 11 ), sarcodinine ( 12 ), and alkaloid‐C ( 13 ). The structures of 1 – 7 were deduced from spectral data. Compounds 1 – 13 demonstrated significant activity against acetyl‐ and butyrylcholinesterase.     

Scyphiphorins A and B,Two New Iridoid Glycosides from the Stem Bark of a Chinese Mangrove Scyphiphora hydrophyllacea

Two new iridoid glycosides, named scyphiphorins A ( 1 ) and B ( 2 ), together with four known compounds, geniposidic acid (=(1S,4aS,7aS)‐1‐(β‐D ‐glucopyranosyloxy)‐1,4a,5,7a‐tetrahydro‐7‐(hydroxymethyl)cyclopenta[c]pyran‐4‐carboxylic acid; 3 ), 4‐(4‐hydroxy‐3‐methoxybenzyl)butan‐2‐one, oleanolic acid (=(3β)‐3‐hydroxyolean‐12‐en‐28‐oic acid), and stigmasterol β‐D ‐glucoside (=(3β,22E)‐stigmasta‐5,22‐dien‐3‐yl β‐D ‐glucopyranoside), were isolated for the first time from the stem bark of a Chinese mangrove, Scyphiphora hydrophyllacea Gaertn . f. The structures of compounds 1 and 2 were determined as 10‐O‐benzoylgeniposidic acid and 10‐O‐[(2E,6R)‐8‐hydroxy‐2,6‐dimethyl‐1‐oxooct‐2‐en‐1‐yl]geniposidic acid, respectively, on the basis of spectroscopic data and chemical methods, including 2D NMR techniques.     

Reduction of Capsorubin and Cryptocapsin

(6′S)‐ and (6′R)‐‘Capsorubol‐6‐one' (=(3S,3′S,5R,5′R,6′S)‐ and (3S,3′S,5R,5′R,6′R)‐3,3′,6′‐trihydroxy‐κ,κ‐caroten‐6‐one; 8 and 9 , resp.), (6S,6′R)‐ and (6R,6′R)‐capsorubol (=3S,3′S,5R,5′R,6S,6′R)‐ and (3S,3′S,5R,5′R,6R,6′R)‐κ,κ‐carotene‐3,3′,6,6′‐tetrol; 11 and 12 , resp.) and (6′S)‐ and (6′R)‐cryptocapsol (=(3′S,5′R,6′S)‐ and (3′S,5′R,6′R)‐β,κ‐carotene‐3′,6′‐diol; 5 and 6 , resp.) were prepared in crystalline from by the reduction of capsorubin (=(3S,3′S,5R,5′R)‐3,3′‐dihydroxy‐κ,κ‐carotene‐6,6′‐dione; 7 ) and cryptocapsin (=(3′S,5′R)‐3′‐hydroxy‐β,κ‐caroten‐6′‐one; 4 ) and characterized by their UV/VIS, CD, ¹H‐NMR, and mass spectra.     

Iridoids from Viburnum cylindricum

Two new iridoids, methyl (+)‐rel‐(1R,3S,4R,5R,8R,9R)‐1,3,4,5,8,9‐hexahydro‐8‐hydroxy‐3‐methoxy‐2H‐1a,2‐dioxacyclopent[cd]indene‐4‐carboxylate ( 1 ) and methyl (+)‐rel‐(1R,3S,4S,5R,8R,9R)‐1,3,4,5,8,9‐hexahydro‐8‐hydroxy‐3‐methoxy‐2H‐1a,2‐dioxacyclopent[cd]indene‐4‐carboxylate ( 2 ), were isolated from Viburnum cylindricum along with 14 known compounds. Their structures were determined by spectroscopic analyses. This type of iridoids bearing a MeO group at C(3) was discovered for the first time.     

Paecilomycines A and B,Novel Diterpenoids,Isolated from Insect‐Pathogenic Fungi Paecilomyces sp. ACCC 37762

Two new diterpenoids, named paecilomycine A ( 1 ) and paecilomycine B ( 2 ), including a novel skeleton with a five‐membered lactone ring, together with three known labdane diterpenoids, rel‐(1R,3S,4aS,5R,8aS)‐5‐[(3E)‐4‐carboxy‐3‐methylbut‐3‐en‐1‐yl]decahydro‐3‐hydroxy‐1,4a‐dimethyl‐6‐methylidenenaphthalene‐1‐carboxylic acid ( 3 ), botryosphaerin E ( 4 ), and agathic acid ( 5 ), were isolated from solid culture of the insect pathogenic fungi strain Paecilomyces sp. The structures of all compounds were established on the basis of comprehensive spectroscopic studies. The relative configurations of 1 and 2 were determined by single‐crystal X‐ray diffraction analyses.     

New Nonhydrolyzable Mimetics of Sialyl Lewis X and Their Binding Affinity to P‐Selectin

Wittig olefination of (2S,3R,5S,6R)‐5‐(acetyloxy)‐tetrahydro‐6‐[(methoxymethoxy)methyl]‐3‐(phenylthio)‐ 2H‐pyran‐2‐acetaldehyde ((+)‐ 10 ) with {2‐[(2S,3R,4R,5R,6S)‐tetrahydro‐3,4,5‐tris(methoxymethoxy)‐6‐methyl‐ 2H‐pyran‐2‐yl]ethyl}triphenylphosphonium iodide ((?)‐ 11 ) gave a (Z)‐alkene derivative (+)‐ 12 that was converted into (αR,2R,3S,4R,5R,6S)‐tetrahydro‐α,3‐dihydroxy‐2‐(hydroxymethyl)‐5‐(phenylthio)‐6‐{(2Z)‐4‐[(2S,3S,4R,5S,6S)‐tetrahydro‐3,4,5‐trihydroxy‐6‐methyl‐2H‐pyran‐2‐yl]but‐2‐enyl}2H‐pyran‐4‐acetic acid ( 8 ), (αR,2R,3S,4R,6S)‐tetrahydro‐α,3‐dihydroxy‐2‐(hydroxymethyl)‐6‐{4‐[(2S,3S,4R,5S,6S)‐tetrahydro‐3,4,5‐trihydroxy‐6‐methyl‐2H‐pyran‐2‐yl]butyl}‐2H‐pyran‐4‐acetic acid ( 9 ), and simpler analogues without the hydroxyacetic side chain such as (2S,3S,4R,5S,6S)‐tetrahydro‐6‐methyl‐2‐{(2Z)‐4‐[(2S,3R,5S,6R)‐tetrahydro‐5‐hydroxy‐6‐(hydroxymethyl)‐3‐(phenylthio)‐2H‐pyran‐2‐yl]but‐2‐enyl}‐2H‐pyran‐3,4,5‐triol ( 30 ), (2S,3S,4R,5S,6S)‐tetrahydro‐6‐methyl‐2‐{[(2S,5S,6R)‐tetrahydro‐5‐hydroxy‐6‐(hydroxymethyl)‐2H‐pyran‐2‐yl]butyl}‐2H‐pyran‐3,4,5‐ triol ((?)‐ 41 ) and (2S,3S,4R,5S,6S)‐tetrahydro‐6‐methyl‐2‐{(2Z/E))‐4‐[(2R,5S,6R)‐tetrahydro‐5‐hydroxy‐6‐(hydroxymethyl)‐2H‐pyran‐2‐yl]but‐2‐enyl}‐2H‐pyran‐3,4,5‐triol ( 43 ). The key intermediates (+)‐ 10 and (?)‐ 11 were derived from isolevoglucosenone and from L ‐fucose, respectively. The following IC₅₀ values were measured in a ELISA test for the affinities of sialyl Lewis x tetrasaccharide, 8, 9, 30 , (?)‐ 41 , and 43 toward P‐selectin: 0.7, 2.5–2.8, 7.3–8.0, 5.3–5.9, 5.0–5.2, and 3.4–4.1 mM , respectively.     

Two New Sesquiterpenes from the Roots of Valeriana fauriei Briq.

A phytochemical investigation of the MeOH extract of Valeriana fauriei Briq . roots resulted in the isolation of two new sesquiterpenes, isovalerianin A (=(1β,4Z,6β,8α)‐8‐(acetyloxy)‐1,10‐dihydroxy‐6,11‐cyclogermacr‐4‐en‐15‐al=rel‐(1R,2Z,6S,7R,9R,10S)‐9‐(acetyloxy)‐6,7‐dihydroxy‐7,11,11‐trimethylbicyclo[8.1.0]undec‐2‐ene‐3‐carboxaldehyde; 1 ) and valerianin C (=(2α,3α,6α,8α)‐3‐(acetyloxy)‐2,4,8‐trihydroxyguai‐1(10)‐ene‐12,6‐lactone=rel‐(3R,3aS,4R,7S,8S,9R,9aR,9bR)‐8‐(acetyloxy)‐3a,4,5,7,8,9,9a,9b‐ octahydro‐4,7,9‐trihydroxy‐3,6,9‐trimethylazuleno[4,5‐b]furan‐2(3H)‐one; 2 ), together with six known compounds, i.e., camphor, methyl 4‐hydroxybenzoate, 2‐methoxybenzoic acid, benzoic acid, quercetin, and kaempferol. The structures of the compounds were established by detailed spectral analysis and comparison with previously reported data.     

Lycopodine‐Type Lycopodium Alkaloids from Huperzia serrata

Eleven Lycopodium alkaloids with a lycopodine‐type skeleton were isolated from the basic material of the whole plant of Huperzia serrata (Thunb .) Trev. (Huperziaceae). Among them, 12‐epilycodoline N‐oxide (=(12α,15R)‐12‐hydroxy‐15‐methyllycopodan‐5‐one N‐oxide; 1 ), 7‐hydroxylycopodine (=(15S)‐7‐hydroxy‐15‐methyllycopodan‐5‐one; 2 ), and 4,6α‐dihydroxylycopodine (=(6α,15R)‐4,6‐dihydroxy‐15‐methyllycopodan‐5‐one; 3 ) are new compounds. Their structures were identified spectroscopically, especially by means of 1D‐ and 2D‐NMR.     

Partial Synthesis and Characterization of Karpoxanthins and Cucurbitaxanthin A Epimers

Karpoxanthin (=(all-E,3S,5R,6R,3′R)-5,6-dihydro-β,β-carotene-3,5,6,3′-tetrol; 7 ), 6-epikarpoxanthin (=(all-E,3S,5R,6S,3′R)-5,6-dihydro-β,β-carotene-3,5,6,3′-tetrol; 4 ), 5-epikarpoxanthin (=(all-E,3S,5S,6R,3′-R)-5,6-dihydro-β,β-carotene-3,5,6,3′-tetrol; 11 ), cucurbitaxanthin A (=(all-E,3S,5R,6R,3′R)-3,6-epoxy-5,6-dihydro-β,β-carotene-5,3′-diol; 10 ), epicucurbitaxanthin A (=(all-E-3S,5S,6R,3′R)-3,6-epoxy-5,6-dihydro-β,β-carotene-5,3′-diol; 14 ), and the corresponding mutatoxanthin epimers 8 , 9 , 12 , and 13 were prepared in crystalline state by the acid-catalyzed hydrolysis of (3S,5R,6S,3′R)- and (3S,5S,6R,3′R)-antheraxanthin ( 5 and 6 , resp.) and characterized by their UV/VIS, CD, ¹H- and ¹³C-NMR, and mass spectra.