Two Antioxidant Alkaloids from Portulaca oleracea L.

Two alkaloids, oleraceins F and G, were isolated from Portulaca oleracea L., and their structures were determined as methyl (2S)‐6‐[(β‐D ‐glucopyranosyl)oxy]‐2,3‐dihydro‐5‐hydroxy‐1‐[(2E)‐3‐(4‐hydroxy‐3‐methoxyphenyl)prop‐2‐enoyl]‐1H‐indole‐2‐carboxylate and methyl (2S)‐6‐[(β‐D ‐glucopyranosyl)oxy]‐2,3‐dihydro‐5‐hydroxy‐1‐[(2E)‐3‐(4‐hydroxyphenyl)prop‐2‐enoyl]‐1H‐indole‐2‐carboxylate, based on their spectroscopic data. Oleraceins F and G exhibited scavenging activity against 1,1‐diphenyl‐2‐picrylhydrazyl (DPPH) radical, with EC₅₀ values of 21.00 and 37.69 μM , respectively.     

Phenolic Derivatives from the Root Bark of Oplopanax horridus

Four new phenolic derivatives, including two phenylpropanoid glycosides, one benzoate glycoside, and one lignan glycoside, together with one known glyceride, were isolated from the root bark of Oplopanax horridus. The structures of the new compounds were elucidated as 3‐{4‐[(6‐O‐acetyl‐β‐D ‐glucopyranosyl)oxy]‐3,5‐dimethoxyphenyl}propanoic acid ( 1 ), (+)‐[5,6,7,8‐tetrahydro‐7‐(hydroxymethyl)‐10,11‐dimehoxydibenzo[a,c][8]annulen‐6‐yl]methyl β‐D ‐glucopyranoside ( 2 ), (+)‐methyl 4‐[6‐O‐{3‐hydroxy‐3‐methyl‐5‐(1‐methylpropyl)oxy]‐5‐oxopentanoyl}‐4‐O‐(β‐D ‐glucopyranosyl)‐β‐D ‐glucopyranosyl)oxy]‐3‐methoxybenzoate ( 3 ), and 2‐methoxy‐4‐[(1E)‐3‐methoxy‐3‐oxoprop‐1‐en‐1‐yl]phenyl 6‐O‐{3‐hydroxy‐3‐methyl‐5‐[(1‐methylpropyl)oxy]‐5‐oxopentanoyl‐4‐O‐β‐d‐ glucopyranosyl‐β‐d‐ glucopyranoside ( 4 ) on the basis of spectroscopic techniques including NMR and MS analyses. The known compound was identified as glycer‐2‐yl ferulate ( 5 ) by comparing its physical and spectral data with those reported in the literature.     

New Triterpenoidal Saponins Acylated with Monoterpenic Acid from Albizia adianthifolia

Four new triterpenoidal saponins acylated with monoterpenic acid, i.e., adianthifoliosides C, D, E, and F ( 1 – 4 ), besides the two known julibroside III and the monodesmonoterpenyl elliptoside A, were isolated from the roots of Albizia adianthifolia. Their structures were elucidated on the basis of extensive 1D‐ and 2D‐NMR studies and mass spectrometry as 3‐O‐{O‐α‐L ‐arabinopyranosyl‐(1→2)‐O‐β‐d‐ fucopyranosyl‐(1→6)‐O‐[β‐d‐ glucopyranosyl‐(1→2)]‐β‐d‐ glucopyranosyl}‐21‐O‐{(2E,6S)‐6‐{{4‐O‐[(2E,6S)‐2,6‐dimethyl‐6‐(β‐D ‐quinovopyranosyloxy)octa‐2,7‐dienoyl]‐β‐d‐ quinovopyranosyl}oxy}‐2‐(hydroxymethyl)‐6‐methylocta‐2,7‐dienoyl}acacic acid 28‐{O‐α‐L ‐arabinofuranosyl‐(1→4)‐O‐[β‐d‐ glucopyranosyl‐(1→3)]‐O‐α‐L ‐rhamnopyranosyl‐(1→2)‐β‐d‐ glucopyranosyl} ester ( 1 ), 21‐O‐{(2E,6S)‐6‐{{4‐O‐[(2E,6S)‐2,6‐dimethyl‐6‐(β‐d‐ quinovopyranosyloxy)octa‐2,7‐dienoyl]‐β‐d‐ quinovopyranosyl}oxy}‐2‐(hydroxymethyl)‐6‐methylocta‐2,7‐dienoyl}‐3‐O‐{O‐β‐D ‐xylopyranosyl‐(1→2)‐O‐β‐d‐ fucopyranosyl‐(1→6)‐2‐(acetylamino)‐2‐deoxy‐β‐d‐ glucopyranosyl}acacic acid 28‐{O‐α‐L ‐arabinofuranosyl‐(1→4)‐O‐[β‐d‐ glucopyranosyl‐(1→3)]‐O‐α‐L ‐rhamnopyranosyl‐(1→2)‐β‐d‐ glucopyranosyl} ester ( 2 ), 21‐O‐{(2E,6S)‐6‐{{3‐O‐[(2E,6S)‐2,6‐dimethyl‐6‐(β‐d‐ quinovopyranosyloxy)octa‐2,7‐dienoyl]‐β‐d‐ quinovopyranosyl}oxy}‐2,6‐dimethylocta‐2,7‐dienoyl}‐3‐O‐{O‐β‐D ‐xylopyranosyl‐(1→2)‐O‐β‐d‐ fucopyranosyl‐(1→6)‐2‐(acetylamino)‐2‐deoxy‐β‐d‐ glucopyranosyl}acacic acid 28‐{O‐α‐L ‐arabinofuranosyl‐(1→4)‐O‐[β‐d‐ glucopyranosyl‐(1→3)]‐O‐α‐L ‐rhamnopyranosyl‐(1→2)‐β‐d‐ glucopyranosyl} ester ( 3 ), and 3‐O‐{O‐α‐L ‐arabinopyranosyl‐(1→2)‐O‐β‐d‐ fucopyranosyl‐(1→6)‐O‐[β‐d‐ glucopyranosyl‐(1→2)]‐β‐d‐ glucopyranosyl}‐21‐O‐{(2E,6S)‐2,6‐dimethyl‐6‐(β‐d‐ quinovopyranosyloxy)octa‐2,7‐dienoyl}acacic acid 28‐{O‐α‐L ‐arabinofuranosyl‐(1→4)‐O‐[β‐d‐ glucopyranosyl‐(1→3)]‐O‐α‐L ‐rhamnopyranosyl‐(1→2)‐β‐d‐ glucopyranosyl} ester ( 4 ).     

Flavonoid Glycosides from Ranunculus chinensis Bge.

Four new flavonoid glycosides, 3‐O‐[α‐L ‐arabinopyranosyl‐(1→2)‐β‐D ‐galactopyranosyl]‐7‐O‐β‐D ‐glucopyranosylkaempferol ( 1 ), 3‐O‐(α‐L ‐arabinopyranosyl‐(1→2)‐{4‐O‐[(E)‐caffeoyl]‐β‐D ‐galactopyranosyl})‐7‐O‐β‐D ‐glucopyranosylquercetin ( 2 ), 3‐O‐{2‐O‐[(E)‐caffeoyl]‐α‐L ‐arabinopyranosyl‐(1→2)‐β‐D ‐galactopyranosyl}‐7‐O‐β‐D ‐glucopyranosylkaemperfol ( 3 ), and 3‐O‐{2‐O‐[(E)‐caffeoyl]‐α‐L ‐arabinopyranosyl‐(1→2)‐β‐D ‐galactopyranosyl}kaempferol ( 4 ), together with two known compounds were isolated from the aerial parts of Ranunculus chinensis Bge . The structures of the new glycosides were determined on the basis of spectroscopic analysis, including 1D‐ and 2D‐NMR, and ESI‐MS techniques, and chemical methods.     

Two New Kaempferol Glycosides from Androsace umbellata

Two new kaempferol glycosides, 5‐hydroxy‐2‐(4‐hydroxyphenyl)‐4‐oxo‐7‐(α‐L ‐rhamnopyranosyloxy)‐4H‐chromen‐3‐yl 2‐O‐acetyl‐3‐O‐β‐D ‐glucopyranosyl‐α‐L ‐rhamnopyranoside ( 1 ) and 5‐hydroxy‐2‐(4‐hydroxyphenyl)‐4‐oxo‐7‐(α‐L ‐rhamnopyranosyloxy)‐4H‐chromen‐3‐yl β‐D ‐glucopyranosyl‐(1→2)‐6‐O‐[(2E)‐3‐(4‐hydroxyphenyl)prop‐2‐enoyl]‐β‐D ‐glucopyranosyl‐(1→2)‐β‐D ‐glucopyranoside ( 2 ), along with ten known compounds, were isolated from the 95% EtOH extract of the whole plant of Androsace umbellata. The structures of the new glycosides were determined on the basis of detailed spectroscopic analyses, including 1D‐ and 2D‐NMR, MS, and chemical methods.     

Synthesis and characterization of bromo‐, arylazo‐, and heterocyclic‐fused troponoids containing a 1,3‐benzodioxole system

A facile synthesis of a series of novel bromo‐, arylazo‐, and heterocyclic fused troponoid compounds containing 1,3‐benzodioxole system is described. The 7‐bromo‐, 5,7‐dibromo‐, and 5‐arylazo‐substituted 3‐[(2E)‐3‐(1,3‐benzodioxol‐5‐yl)prop‐2‐enoyl]tropolones ( 2 , 3 , and 5 , 6 , 7 ) were obtained by direct bromination or azo‐coupling reactions of 3‐[(2E)‐3‐(1,3‐benzodioxol‐5‐yl)prop‐ 2‐enoyl]tropolone ( 1 ) with bromine, and diazonium salts of aniline derivatives, respectively. 3‐[(2E)‐3‐(1,3‐Benzodioxol‐5‐yl)prop‐2‐enoyl]‐5‐bromotropolone ( 4 ) was obtained from 3‐acetyl‐5‐bromotropolone via one‐pot aldol dehydration reaction with piperonal. Tropolones 2, 3 , and 4 were subjected to nucleophilic cyclization with bifunctional hydroxylamine hydrochloride and phenylhydrazine hydrochloride to give the corresponding isoxazolo‐ and pyrazolo‐fused tropones ( 8 , 9 , 10 , 11 , 12 , 13 ), respectively. J. Heterocyclic Chem., (2012).     

Structure elucidation of new acacic acid‐type saponins from Albizia coriaria

Three new acacic acid derivatives, named coriariosides C, D, and E ( 1–3 ) were isolated from the roots of Albizia coriaria. Their structures were elucidated on the basis of extensive 1D‐ and 2D‐NMR studies and mass spectrometry as 3‐O‐[β‐D ‐xylopyranosyl‐(1 → 2)‐β‐D ‐fucopyranosyl‐(1 → 6)‐2‐(acetamido)‐2‐deoxy‐β‐D ‐glucopyranosyl]‐21‐O‐{(2E,6S)‐6‐O‐{4‐O‐[(2E,6S)‐2,6‐dimethyl‐ 6‐O‐(β‐D ‐quinovopyranosyl)octa‐2,7‐dienoyl]‐4‐O‐[(2E,6S)‐2,6‐dimethyl‐6‐O‐(β‐D ‐quinovopyranosyl)octa‐2,7‐dienoyl]‐β‐D ‐quinovopyranosyl}‐2,6‐dimethylocta‐2,7‐dienoyl}acacic acid 28‐O‐β‐D ‐xylopyranosyl‐(1 → 4)‐α‐L ‐rhamnopyranosyl‐(1 → 2)‐β‐D ‐glucopyranosyl ester ( 1 ), 3‐O‐{β‐D ‐fucopyranosyl‐(1 → 6)‐[β‐D ‐glucopyranosyl‐(1 → 2)]‐β‐D ‐glucopyranosyl}‐21‐O‐{(2E,6S)‐6‐O‐{4‐O‐[(2E,6S)‐2,6‐dimethyl‐6‐O‐(β‐D ‐quinovopyranosyl)octa‐2,7‐dienoyl]‐4‐O‐[(2E,6S)‐2,6‐dimethyl‐6‐O‐(β‐D ‐quinovopyranosyl)octa‐2,7‐dienoyl]‐β‐D ‐quinovopyranosyl}‐2,6‐dimethylocta‐2,7‐dienoyl}acacic acid 28‐O‐α‐L ‐rhamno pyranosyl‐(1 → 2)‐β‐D ‐glucopyranosyl ester ( 2 ), and 3‐O‐[β‐D ‐fucopyranosyl‐(1 → 6)‐β‐D ‐glucopyranosyl]‐21‐O‐{(2E,6S)‐6‐O‐{4‐O‐[(2E,6S)‐2,6‐dimethyl‐6‐O‐(β‐D ‐quinovopyranosyl)octa‐2,7‐dienoyl)‐β‐D ‐quinovopyranosyl]octa‐2,7‐dienoyl}acacic acid 28‐O‐β‐D ‐glucopyranosyl ester ( 3 ). Copyright © 2010 John Wiley & Sons, Ltd.     

New Acylated Presenegenin Saponins from Two Species of Muraltia

Six new acylated bisdesmosidic triterpene glycosides 1 – 6 were isolated from the roots of Muraltia heisteria (L.) DC., as three inseparable mixtures 1 / 2, 3 / 4 , and 5 / 6 of the (E)‐ and (Z)‐3,4,5‐trimethoxycinnamoyl derivatives. The compound pair 1 / 2 along with four known saponins were also isolated from the roots of Muraltia satureioides DC. Their structures were elucidated mainly by spectroscopic experiments including 2D‐NMR techniques as 3‐O‐(β‐D ‐glucopyranosyl)presenegenin 28‐{O‐β‐D ‐apiofuranosyl‐(1→3)‐O‐[β‐D ‐xylopyranosyl‐(1→4)]‐O‐α‐L ‐rhamnopyranosyl‐(1→2)‐O‐[6‐O‐acetyl‐β‐D ‐galactopyranosyl‐(1→3)]‐4‐O‐[(E)‐3,4,5‐trimethoxycinnamoyl]‐β‐D ‐fucopyranosyl} ester ( 1 ) and its (Z)‐isomer 2 , 3‐O‐(β‐D ‐glucopyranosyl)presenegenin 28‐{O‐6‐O‐acetyl‐β‐D ‐galactopyranosyl‐(1→3)‐O‐[3‐O‐acetyl‐α‐L ‐rhamnopyranosyl‐(1→2)]‐4‐O‐[(E)‐3,4,5‐trimethoxycinnamoyl]‐β‐D ‐fucopyranosyl} ester ( 3 ) and its (Z)‐isomer 4 , and 3‐O‐(β‐D ‐glucopyranosyl)presenegenin 28‐{O‐3‐O‐acetyl‐α‐L ‐rhamnopyranosyl‐(1→2)‐O‐[β‐D ‐xylopyranosyl‐(1→3)]‐4‐O‐[(E)‐3,4,5‐trimethoxycinnamoyl]‐β‐D ‐fucopyranosyl} ester ( 5 ) and its (Z)‐isomer 6 , respectively.     

Asymmetric Syntheses of the Macrocyclic Spermine Alkaloids (−)‐(S)‐Protoverbine, (−)‐(S)‐Buchnerine,and Their Naturally Occurring Congenial Alkaloids

Asymmetric syntheses of the following 17‐membered macrocyclic spermine alkaloids are presented: (−)‐(S)‐protoverbine (=(8S)‐8‐phenyl‐1,5,9,13‐tetraazacycloheptadecane‐6‐one; 1 ), (+)‐(S)‐protomethine (=(2S)‐2‐phenyl‐1,5,9,14‐tetraazabicyclo[12.3.1]octadecan‐4‐one; 2 ), (−)‐(S)‐buchnerine (=(8S)‐8‐(4‐methoxyphenyl)‐1,5,9,13‐tetraazacycloheptadecane‐6‐one; 8 ), (+)‐(S)‐verbamethine (=(+)‐(2S)‐9‐[(E)‐phenylprop‐2‐enoyl]‐2‐phenyl‐1,5,9,14‐tetraazabicyclo[12.3.1]octadecan‐4‐one; 4 ), (−)‐(S)‐verbacine (=(−)‐(8S)‐1‐[(E)‐phenylprop‐2‐enoyl]‐8‐phenyl‐1,5,9,13‐tetraazacycloheptadecan‐6‐one; 3 ), (−)‐(S)‐verbasikrine (=(−)‐(8S)‐1‐[(E)‐3‐(4‐methoxyphenyl)prop‐2‐enoyl]‐8‐phenyl‐1,5,9,13‐tetraazacycloheptadecan‐6‐one; 26 ), (−)‐(S)‐isoverbasikrine (=(−)‐(8S)‐1‐[(Z)‐3‐(4‐methoxyphenyl)prop‐2‐enoyl]‐8‐phenyl‐1,5,9,13‐tetraazacycloheptadecan‐6‐one; 25 ), (+)‐(S)‐verbamekrine (=(+)‐(2S)‐9‐[(E)‐3‐(4‐methoxyphenyl)prop‐2‐enoyl]‐2‐phenyl‐1,5,9,14‐tetraazabicyclo[12.3.1]octadecan‐4‐one; 23 ), and (+)‐(S)‐isoverbamekrine (=(+)‐(2S)‐9‐[(Z)‐3‐(4‐methoxyphenyl)prop‐2‐enoyl]‐2‐phenyl‐1,5,9,14‐tetraazabicyclo[12.3.1]octadecan‐4‐one; 24 ). Effective methods for ¹H‐NMR determination of the enantiomeric purity in which (S)‐2‐hydroxy‐2‐phenylacetic acid and (S)‐2‐acetoxy‐2‐phenylacetic acid are used as shift reagents for 1, 8 , and related macrocyclic alkaloids are described.     

Two New Phenolic Compounds from Artemisia iwayomogi

Two new phenolic compounds, (Z)‐5′‐hydroxyjasmone 5′‐O‐{6″‐O‐[(E)‐caffeoyl]‐β‐D ‐glucopyranoside} ( 1 ) and quercetin‐7‐O‐β‐D ‐glucuronide methyl ester ( 2 ), along with ten known phenolic compounds, 3 – 12 , were isolated from the aerial parts of Artemisia iwayomogi. Their structures were elucidated by spectroscopic methods, including 1D‐ and 2D‐NMR, and HR‐ESI‐TOF‐MS techniques. The inhibitory effects of compounds 1 – 12 on the LPS‐stimulated production of IL‐12 p40, IL‐6, and TNF‐α in bone marrow‐derived dendritic cells were evaluated.     

Five Aromatics Bearing a 4‐O‐Methylglucose Unit from Cordyceps cicadae

Five new aromatics bearing a 4‐O‐methylglucose unit, namely 3‐methoxy‐1,4‐hydroquinone 1‐(4′‐O‐methyl‐β‐glucopyranoside) (=4‐hydroxy‐3‐methoxyphenyl 4‐O‐methyl‐β‐glucopyranoside; 1 ), 3‐methoxy‐1,4‐hydroquinone 4‐(4′‐O‐methyl‐β‐glucopyranoside) (=4‐hydroxy‐2‐methoxyphenyl 4‐O‐methyl‐β‐glucopyranoside; 2 ), vanillic acid 4‐(4′‐O‐methyl‐β‐glucopyranoside) (=3‐methoxy‐4‐[(O‐methyl‐β‐glucopyranosyl)oxy]benzoic acid; 3 ), 5‐methoxycinnamic acid 3‐O‐(4′‐O‐methyl‐β‐glucopyranoside) (=(2E)‐3‐{3‐methoxy‐5‐[(4‐O‐methyl‐β‐glucopyranosyl)oxy]phenyl}prop‐2‐enoic acid; 4 ), and naphthalene‐1,8‐diol 1,8‐bis(4′‐O‐methyl‐β‐glucopyranoside) (=naphthalene‐1,8‐diyl bis(4‐O‐methyl‐β‐glucopyranoside; 5 ), were isolated from the cultivated Cordyceps cicadae mycelia, together with thirteen known compounds. Their structures were determined by spectroscopic methods. The absolute configurations of the sugar units were not determined.     

Synthesis of a C‐Iminoribofuranoside Analog of the Nicotinamide Phosphoribosyltransferase (NAMPT) Inhibitor FK866

FK866 (also named APO866 or WK175) is a potent NAMPT inhibitor being evaluated (Phase II) as a potential anticancer drug. The preparation of the C‐iminoribofuranoside analog (2E)‐N‐[4‐(1‐benzoylpiperidin‐4‐yl)butyl]‐3‐{3‐[(2S,3S,4R,5R)‐3,4‐dihydroxy‐5‐(hydroxymethyl)pyrrolidin‐2‐yl]phenyl}prop‐2‐enamide ((?)‐ 1 ) is reported.     

Electrospray ionization mass spectrometry of tributyltin(IV) complexes and their larvicidal activity on mosquito larvae: crystal and molecular structure of polymeric (Bu3Sn[O2CC6H4{NN(C6H3‐4‐OH(C(H)NC6H4OCH3‐4))}‐o])n

A series of tributyltin(IV) complexes of 2‐[(E)‐2‐(3‐formyl‐4‐hydroxyphenyl)‐1‐diazenyl]benzoic acid and 4‐[((E)‐1‐{2‐hydroxy‐5‐[(E)‐2‐(2‐carboxyphenyl)‐1‐diazenyl]phenyl}methylidene)amino]aryls have been investigated by electrospray mass spectrometry (ESI‐MS) and tandem mass spectrometry (MSⁿ) techniques. The assignments are facilitated by agreement between observed and calculated isotopic patterns and MSⁿ studies. Single‐crystal X‐ray crystallography of (Bu₃Sn[O₂CC₆H₄{N?N(C₆H₃‐4‐OH(C(H)?NC₆H₄OCH₃‐4))}‐o])_n reveals a polymeric structure. Toxicity studies of the tributyltin(IV) complexes of the 4‐[((E)‐1‐{2‐hydroxy‐5‐[(E)‐2‐(2‐carboxyphenyl)‐1‐diazenyl]phenyl}methylidene)amino]aryls on the second larval instar of the Aedes aegypti and Anopheles stephensi mosquito larvae are also reported. The LC₅₀ values indicate that the complexes are effective larvicides, which range from a low of 0.36 ppm to a high of 0.69 ppm against the Ae. aegypti larvae and between 0.82 and 1.17 ppm against the An. stephensi larvae. Copyright © 2005 John Wiley & Sons, Ltd.     

Phenyl and Phenylethyl Glycosides from Picrorhiza scrophulariiflora

Three new phenyl glycosides, scrophenoside A ( 1 ), B ( 2 ), and C ( 3 ), and two new phenylethyl glycosides, scroside D ( 4 ) and scroside E ( 5 ), were isolated from the stem of Picrorhiza scrophulariiflora Pennell (Scrophularlaceae), besides five known compounds. On the basis of spectroscopic evidence, the structures of the new compounds were elucidated as 4‐acetyl‐2‐methoxyphenyl 6‐O‐[4‐(β‐D ‐glucopyranosyloxy)vanilloyl]‐β‐D ‐glucopyranoside ( 1 ), 4‐acetylphenyl 6‐O‐[(E)‐p‐coumaroyl]‐β‐D ‐glucopyranoside ( 2 ), 4‐[(1R)‐ and (1S)‐1‐hydroxyethyl]‐2‐methoxyphenyl β‐D ‐glucopyranoside ( 3a and 3b , resp.), 2‐(3,4‐dihydroxyphenyl)ethyl O‐β‐D ‐glucopyranosyl‐(1→3)‐4‐O‐[(E)‐feruloyl]‐β‐D ‐glucopyranoside ( 4 ), and 2‐(3,4‐dihydroxyphenyl)ethyl O‐β‐D ‐glucopyranosyl‐(1→3)‐6‐O‐[(E)‐feruloyl]‐β‐D ‐glucopyranoside ( 5 ).     

Triterpene Saponins from Four Species of the Polygalaceae Family

Twelve triterpene saponins were isolated by successive MPLC over silica gel from four species of Polygalaceae: From Polygala ruwenzoriensis, five new saponins 1 – 5 of which 1 – 4 as two pairs of (E)/(Z)‐isomers, together with the four known compounds tenuifoline, (E)‐ and (Z)‐senegasaponin b, (E)‐ and (Z)‐senegin II, and polygalasaponin XXVIII, from the genus Carpolobia, one new saponin 6 from C. alba and the known arilloside ( 11 ) from C. lutea, and another new triterpene glycoside 7 from Polygala arenaria. Their structures were established mainly by 600‐MHz 2D‐NMR techniques (¹H,¹H‐COSY, TOCSY, NOESY, HSQC, HMBC) as 3‐O‐(β‐D ‐glucopyranosyl)presenegenin 28‐{O‐α‐L ‐arabinopyranosyl‐(1 → 4)‐O‐β‐D ‐xylopyranosyl‐(1 → 4)‐O‐α‐L ‐rhamnopyranosyl‐(1 → 2)‐4‐O‐[(E)‐4‐methoxycinnamoyl]‐β‐D ‐fucopyranosyl} ester ( 1 ) and its (Z)‐isomer 2 , 3‐O‐(β‐D ‐glucopyranosyl)presenegenin 28‐{O‐α‐L ‐arabinopyranosyl‐(1 → 4)‐O‐β‐D ‐xylopyranosyl‐(1 → 4)‐O‐α‐L ‐rhamnopyranosyl‐(1 → 2)‐4‐O‐[(E)‐3,4‐dimethoxycinnamoyl]‐β‐D ‐fucopyranosyl} ester ( 3 ) and its (Z)‐isomer 4 , 3‐O‐(β‐D ‐glucopyranosyl)presenegenin 28‐[O‐β‐D ‐galactopyranosyl‐(1 → 4)‐O‐β‐D ‐xylopyranosyl‐(1 → 4)‐O‐α‐L ‐rhamnopyranosyl‐(1 → 2)‐β‐D ‐fucopyranosyl] ester ( 5 ), 3‐O‐(β‐D ‐glucopyranosyl)presenegenin 28‐{O‐α‐L ‐arabinopyranosyl‐(1 → 3)‐O‐[β‐D ‐galactopyranosyl‐(1 → 4)]‐O‐β‐D ‐xylopyranosyl‐(1 → 4)‐O‐α‐L ‐rhamnopyranosyl‐(1 → 2)‐O‐[β‐D ‐apiofuranosyl‐(1 → 3)]‐4‐O‐acetyl‐β‐D ‐fucopyranosyl} ester ( 6 ), and 3‐O‐(β‐D ‐glucopyranosyl)presenegenin 28‐{O‐β‐D ‐galactopyranosyl‐(1 → 4)‐O‐[β‐D ‐glucopyranosyl‐(1 → 3)]‐O‐β‐D ‐xylopyranosyl‐(1 → 4)‐O‐α‐L ‐rhamnopyranosyl‐(1 → 2)‐β‐D ‐fucopyranosyl} ester ( 7 ) (presenegenin = (2β,3β,4α)‐2,3,27‐trihydroxyolean‐12‐ene‐23,28‐dioic acid).     

Two New 7‐Dehydrobrefeldin A Acids from Cylindrocarpon obtusisporum,an Endophytic Fungus of Trewia nudiflora

Two new 7‐dehydrobrefeldin A acids, (2E,4R*)‐4‐hydroxy‐4‐{(1R*,2S*)‐4‐oxo‐2‐[(1E)‐6‐oxohept‐1‐en‐1‐yl]cyclopentyl}but‐2‐enoic acid ( 3 ) and (2E,4R*)‐4‐hydroxy‐4‐{(1R*,2S*)‐2‐[(1E,6S*)‐6‐hydroxyhept‐1‐en‐1‐yl]‐4‐oxocyclopentyl}but‐2‐enoic acid ( 4 ), were isolated from the endophytic fungal strain Cylindrocarpon obtusisporum (Cooke & Harkness ) Wollenw . of Trewia nudiflora, together with two known compounds, 7‐dehydrobrefeldin A ( 2 ) and brefeldin A ( 1 ). Their structures were determined on the basis of extensive 1D‐ and 2D‐NMR‐spectral analysis.     

One‐Pot,Asymmetric and Diastereoselective Four‐Component Synthesis of Polyfunctional (Z)‐Alkenyl Methyl Sulfones with Three Stereogenic Centers

The reaction of 1‐(trimethylsilyloxy)cyclopentene ( 9 ) with (±)‐1,3,5‐triisopropyl‐2‐(1‐(RS)‐{[(1E)‐2‐methylpenta‐1,3‐dienyl]oxy}ethyl)benzene ((±)‐ 4a ) in SO₂/CH₂Cl₂ containing (CF₃SO₂)₂NH, followed by treatment with Bu₄NF and MeI gave a 3.0 : 1 mixture of (±)‐(2RS)‐2{(1RS,2Z,4SR)‐2‐methyl‐4‐(methylsulfonyl)‐1‐[(RS)‐1‐(2,4,6‐triisopropylphenyl)ethoxy]pent‐2‐en‐1‐yl}cyclopentanone ((±)‐ 10 ) and (±)‐(2RS)‐2‐{(1RS,2Z)‐2‐methyl‐4‐[(SR)‐methylsulfonyl]‐1‐[(SR)‐1‐(2,4,6‐triisopropylphenyl)ethoxy]pent‐2‐en‐1‐yl}cyclopentanone ((±)‐ 11 ). Similarly, enantiomerically pure dienyl ether (−)‐(1S)‐ 4a reacted with 1‐(trimethylsilyloxy)cyclohexene ( 12 ) to give a 14.1 : 1 mixture of (−)‐(2S)‐2‐{(1S,2Z,4R)‐2‐methyl‐4‐(methylsulfonyl)‐1‐[(S)‐1‐(2,4,6‐triisopropylphenyl)ethoxy]pent‐2‐enyl}cyclohexanone ((−)‐ 13a ) and its diastereoisomer 14a with (1S,2R,4R) or (1R,2S,4S) configuration. Structures of (±)‐ 10 , (±)‐ 11 , and (−)‐ 13a were established by single‐crystal X‐ray crystallography. Poor diastereoselectivities were observed with the (E,E)‐2‐methylpenta‐1,3‐diene‐1‐ylethers (+)‐ 4b and (−)‐ 4c bearing ( 1 S )‐1‐phenylethyl and (1S)‐1‐(pentafluorophenyl)ethyl groups instead of the Greene's auxiliary ((1S)‐(2,4,6‐triisopropylphenyl)ethyl group). The results demonstrate that high α/β‐syn and asymmetric induction (due to the chiral auxiliary) can be obtained in the four‐component syntheses of the β‐alkoxy ketones. The method generates enantiomerically pure polyfunctional methyl sulfones bearing three chiral centers on C‐atoms and one (Z)‐alkene moiety.     

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.     

An additional methylene group driving the conformation and assembly of two arylsulfonamide para‐alkoxychalcone hybrids

The structures of two arylsulfonamide para‐alkoxychalcones, namely, N‐{4‐[(E)‐3‐(4‐methoxyphenyl)prop‐2‐enoyl]phenyl}benzenesulfonamide, C₂₂H₁₉NO₄S, (I), and N‐{4‐[(E)‐3‐(4‐ethoxyphenyl)prop‐2‐enoyl]phenyl}benzenesulfonamide, C₂₃H₂₁NO₄S, (II), reveal the effect of the inclusion of one –CH₂– group between the CH₃ branch and the alkoxy O atom on the conformation and crystal structure. Although the molecular conformations and one‐dimensional chain motifs are the same in both structures, their crystallographic symmetry, number of independent molecules and crystal packing are different. The crystal packing of (I) is stabilized by weak C—H...π and π–π interactions, while only C—H...π contacts occur in the structure of (II). The role of the additional methylene group in the crystal packing can also be seen in the fact that the alkoxy O atom is an acceptor in nonclassical hydrogen bonds only in the para‐ethoxy analogue, (II). The remarkable similarity between the crystal packing features of (I) and (II) lies in the formation of N—H...O hydrogen‐bonded ribbons, a synthon commonly found in related compounds.     

Phenylethanoid Glycosides from the Roots of Digitalis ciliata Trautv.

Three new phenylethanoid glycosides, named digicilisides A – C ( 1  –  3 , resp.), have been isolated from the roots of Digitalis ciliata, along with five known phenylethanoid glycosides. The structures of 1  –  3 were identified as 2‐(4‐hydroxy‐3‐methoxyphenyl)ethyl β‐d ‐glucopyranosyl‐(1→3)‐[α‐l ‐rhamnopyranosyl‐(1→6)]‐4‐O‐[(E)‐feruloyl]‐β‐d ‐glucopyranoside ( 1 ), 2‐(3,4‐dihydroxyphenyl)ethyl α‐l ‐arabinopyranosyl‐(1→2)‐[β‐d ‐glucopyranosyl‐(1→3)]‐[α‐l ‐rhamnopyranosyl‐(1→6)]‐4‐O‐[(E)‐feruloyl]‐β‐d ‐glucopyranoside ( 2 ), and 2‐(3,4‐dihydroxyphenyl)ethyl β‐d ‐glucopyranosyl‐(1→3)‐{6‐O‐[(E)‐feruloyl]‐β‐d ‐glucopyranosyl‐(1→6)}‐4‐O‐[(E)‐caffeoyl]‐β‐d ‐glucopyranoside ( 3 ).