4H-Chromenone Glycosides from Eranthis hyemalis (L.) SALISBURY

Investigation of the tubers of Eranthis hyemalis (Ranunculaceae) afforded six chromenone glycosides. Their structures have been elucidated mainly by spectroscopic (FAB-MS, 2D-NMR techniques) and chemical methods (acidic and enzymatic hydrolysis) as 9-{[(β-D -glucopyranosyl)oxy]methyl}-8,11-dihydro-5-hydroxy-2-methyl-4H-pyrano[2,3-g][1]benzoxepin-4-one ( 1 ), 9-{[(β-D -gentiobiosyl)oxy]methyl}-8,11-dihydro-5-hydroxy-2-methyl-4H-pyrano[2,3-g][1]benzoxepin-4-one( 2 ), 9-{[(β-D -glucopyranosvl)oxy]melhyl}-8,11-dihydro-5-hydroxy-2-(hydroxy-methyl)-4H-pyrano[2,3-g][1]benzoxepin-4-one( 3 ), 8-{(2E)-4-[(β-D -glucopyranosyl)oxy]-3-methylbut-2-enyl}-5,7-dihydroxy-2-methyl-4H-1-benzopyran-4-one ( 4 ), 8-{(2E)-4-[(β-D -glucopyranosyi)oxy]-3-methylbut-2-enyl}-5,7-dihydroxy-2-(hydroxymethyl)-4H-1-benzopyran-4-one ( 5 ), and 7-{[(β-D -glucopyranosy1)oxy]methyl}-2,3-dihydro-2-(l-hydroxy-1-methylethyl)-4-methoxy-5H-furo[3,2-g][1]benzopyran-5-one ( 6 ). Compound 2 exhibited negative inotropic activity.     

Synthesis via pummerer intermediates. III. Rearrangements of 3-(methylsulfinyl)quinolinones, 3-(methylsulfinyl)cinnolinones, 3-(methylsulfinyl)chromanones and 3-(methylsulfinyl)chromones with acetic anhydride and with thionyl chloride

The reaction of 1-methyl-3-(methylsulfinyl)-4(1H)quinolinone ( 1 ) with acetic anhydride and thionyl chloride gave 3-[[(acetyloxy)methyl]thio]]-1-methyl-4(1H)quinolinone ( 2 ) and 3-[(chloromethyl)thio]-1-methyl-4(1H)quinolinone ( 3 ) respectively. 3-(Methylsulfinyl)-4(1H)cinnolinone ( 4 ) gave the corresponding products when treated under similar conditions. Treatment of 8-methoxy-3-(methylsulfinyl)-4H-1-benzopyran-4-one ( 11 ) with acetic anhydride and thionyl chloride gave bis addition vinyl Pummerer products 2,3-bis(acetyloxy)-2,3-dihydro-8-methoxy-3-(methylthio)-4H-1-benzopyran-4-one ( 12 ) and 2,3-dichloro-2,3-dihydro-8-methoxy-3-(methylthio)-4H-1-benzopyran-4-one ( 13 ), respectively.     

Naturstoffchemie, 174. Mitt. [1]: Oxidation von Acronycin mit Kaliumpermanganat

Zusammenfassung Die Oxidation des Acridonalkaloids Acronycin (1) mit Kaliumpermanganat führt zu (1S-cis)-1,2,3,12-Tetrahydro-1,2-dihydroxy-6-methoxy-3,3,12-trimethyl-7-H-pyrano[2,3-c]acridin-7-on (2), 1-Hydroxy-6-methoxy-3,3,12-trimethyl-1H-pyrano[2,3-c]acridin-2,7(3H,12H)-dion (3) und 1-Hydroxy-6-methoxy-3,3,12-trimethyl-1-(2-oxopropyl)-1H-pyrano[2,3-c]acridin-2,7(3H,12H)-dion (4).

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Natural product chemistry, part. 174 [1]: Oxidation of acronycine by potassium permanganate

Summary Oxidation of the acridone alkaloid acronycine (1) by potassium permanganate results in oxidation of the cromenering to give (1S-cis)-1,2,3,12-tetrahydro-1,2-dihydroxy-6-methoxy-3,3,12-trimethyl-7H-pyrano[2,3-c]acridine-7-one (2), 1-hydroxy-6-methoxy-3,3,12-trimethyl-1H-pyrano-[2,3-c]acridine-2,7(3H,12H)-dione (3) and 1-hydroxy-6-methoxy-3,3,12-trimethyl-1-(2-oxopropyl)-1H-pyrano[2,3-c]acridine-2,7(3H,12H)-dione (4).

     

Synthesis of 1-methyl-7-(trifluoromethyl)-1H-pyrido[2,3-c][1,2]thiazin-4(3H)-one 2,2-dioxide

The reaction of methyl 2-bromo-6-(trifluoromethyl)-3-pyridinecarboxylate ( 1 ) with methanesulfonamide gave methyl 2-[(methylsulfonyl)amino]-6-(trifluoromethyl)-3-pyridine-carboxylate ( 2 ). Alkylation of compound 2 with methyl iodide followed by cyclization of the resulting methyl 2-[methyl(methylsulfonyl)amino]-6-(trifluoromethyl)-3-pyridinecarboxylate ( 3 ) yielded 1-methyl-7-(trifluoromethyl)-1H-pyrido[2,3-c][1,2]thiazin-4(3H)-one 2,2-dioxide ( 4 ). The reaction of compound 4 with α,2,4-trichlorotoluene, methyl bromopropionate, methyl iodide, 3-trifluoromethylphenyl isocyanate, phenyl isocyanate and 2,4-dichloro-5-(2-propynyloxy)phenyl isothiocyanate gave, respectively, 4-[(2,4-dichlorophenyl)methoxy]-1-methyl-7-(trifluoromethyl)-1H-pyrido[2,3-c][1,2]thiazine 2,2-dioxide ( 5 ), methyl 2-[[1-methyl-2,2-dioxido-7-(trifluoromethyl)-1H-pyrido[2,3-c][1,2]thiazin-4-yl]oxy]propanoate ( 6 ), 1,3,3-trimethyl-7-(trifluoromethyl)-1H-pyrido[2,3-c][1,2]thiazin-4(3H)-one 2,2-dioxide ( 7 ), 4-hydroxy-1-methyl-7-(trifluoromethyl)-N-[3-(trifluoromethyl)phenyl]-1H-pyrido[2,3-c][1,2]thiazine-3-carboxamide 2,2-dioxide ( 8 ), 4-hydroxy-1-methyl-7-(trifluoromethyl)-N-phenyl-1H-pyrido[2,3-c][1,2]thiazine-3-carboxamide 2,2-dioxide ( 9 ) and N-[2,4-dichloro-5-(2-propynyloxy)phenyl]-4-hydroxy-1-methyl-7-(trifluoromethyl)-1H-pyrido[2,3-c][1,2] thiazine-3-carboxamide 2,2-dioxide ( 10 ).     

Synthesis,structures, and photochromic properties of 3-[(<Emphasis Type="Italic">E</Emphasis>)-alk-1-enyl]-4-(1-alkyl-5-methoxy-2-methyl-1<Emphasis Type="Italic">H</Emphasis>-indol-3-yl)furan-2,5-diones

New hetarylethenes, viz., 3-[(E)-alk-1-enyl]-4-(1-alkyl-5-methoxy-2-methyl-1H-indol-3-yl)furan-2,5-diones, exhibiting photochromic properties in solution were synthesized. The molecular and crystal structure of 3-(5-methoxy-1,2-dimethyl-1H-indol-3-yl)-4-[(E)-prop-1-enyl]furan-2,5-dione was determined by X-ray diffraction. The initial and photoinduced forms of hetarylethenes are characterized by thermal stability. The open-ring isomers of furandiones exhibit fluorescence with quantum yields of up to 0.1.     

Studies on quinones. XII. Cycloketalization of michael adducts from hydroxyquinones

The reaction of 2-hydroxy-3-(1-phenyl-3-oxobutyl)-1,4-naphthoquinone ( 1 ) with either acidic methanol or a mixture of trimethyl orthoformate, methanol and ammonium chloride resulted in the formation of the p-quinonic cycloketals: trans- and cis-4-phenyl-2-methyl-2-methoxy-3,4-dihydro-2H-naphtho[2,3-b]pyran-5,10-dione ( 2a,2b ). Cyclization of the Michael adducts 6, 10 and 11 , which are structurally related to 1 , with trimethyl orthoformate-methanol-ammonium chloride gave the corresponding p-quinonic cycloketals 7, 12 and 13 . The structures of the regioisomers 2a and 2b are proposed based on the spectral properties of compound 7 and by analysis of its proton nmr spectra.     

Reaction of Dimethyl Sulfoxide with 4-Acyloxycoumarins

Dimethyl sulfoxide converts 4-acetoxycoumarin (1) exclusively to 2-(2-hydroxybenzoyl)-2-[(methylthio)methyl]-2,3-dihydro-4 H-furo[3,2-c]chromen-4-one (3) at 180°C under a nitrogen atmosphere, but in the absence of nitrogen, the products obtained are dicoumarol and its dehydrative cyclization products 7 H-bis[1]benzopyrano[4,3-b: 3′,4′-c]pyran-6,8-dione (9) and (3). Under similar conditions, 4-benzoyloxycoumarin (1a) affords benzoic acid, 4-hydroxy-3-({2-[(methylthio)methyl]-3-oxo-2,3-dihydro-1-benzofuran-2-yl}methyl)-2H-chromen-2-one (7), and 3-(2-hydroxybenzoyl)-3,4-dihydro-2H,5H-pyrano[2,3-b] chromen-5-one (8).     

Transformations of isomeric naphthopyranones. The synthesis of substituted β-naphthyl-α,β-dehydro-α-amino acid derivatives

The opening of the pyranone ring in 2H-naphtho[1,2-b]pyran-2-one derivative (1) and 3H-naphtho[2,1-b]-pyran-3-one derivatives 8 and 20 with nucleophiles afforded 3-(naphthyl-1)- and 3-(naphthyl-2)propenoates (substituted β-naphthyl-α,β-dehydro-α-amino acid derivatives) 7, 13, 14, 15, 24 , and 35 .     

Novel heterocycles. Synthesis of 2,3-dihydro-6-methyl-2-phenyl-4H,6H-pyrano[3,2-c][2,1]benzothiazin-4-one 5,5-dioxide and related compounds

The reaction of 2-chloro-4-(methylsulfonyl)benzoyl chloride ( 5 ) with 1-methyl-1H-2,1-benzothiazin-4-(3H)-one 2,2-dioxide ( 4 ) gave the O-benzoyl compound, 1-methyl-2,2-dioxido-1H-2,1-benzothiazin-4-yl 2-chloro-4-(methylsulfonyl)benzoate ( 6 ), which rearranged to give the C-benzoyl isomer, [2-chloro-4-(methylsulfonyl)phenyl] (4-hydroxy-1-mefhyl-2,2-dioxido-1H-2,1-benzothiazin-3-yl)methanone ( 7 ). The O-cinnamoyl compound 13 that resulted from the addition of 2,4-dichlorocinnamoyl chloride ( 11 ) to compound 4 rearranged to give the C-cinnamoyl compound, 3-(2,4-dichlorophenyl)-1-(4-hydroxy-1-methyl-2,2-dioxido-1H-2,1-benzothiazin-3yl)-2-propen-1-one ( 15 ). On the other hand, 1-methyl-2,2-dioxido-1H-2,1-benzothiazin-4-yl 3-phenyl-2-propenoate ( 19 ) (from cinnamoyl chloride ( 17 ) and compound 4 ) rearranged to give 2,3-dihydro-6-methyl-2-phenyl-4H,6H-pyrano[3,2-c][2,1]benzothiazin-4-one 5,5-dioxide ( 21 ), an example of a hitherto unknown ring system. Additional examples of this novel heterocycle were prepared from 1-methyl-7-(trifluoromethyl)-1H-pyrido[2,3-c][1,2]thiazin-4(3H)-one 2,2-dioxide ( 23 ) and 1-methyl-1H-thieno[3,2-c][1,2]thiazin-4(3H)-one 2,2-dioxide ( 8 ).     

Synthesis of a rotenone-like benzopyranobenzopyranone

The synthesis of a novel rotenone-like molecule, 9-methoxy-8-methyl-6,6a,12,12a-tetrahydro[1]benzopyrano-[3,4-b][1]benzopyran-12-one ( 2 ) is described. Efficient syntheses of 3,4-dihydro-2H-[1]benzopyran-3-one ( 9 ) from ethyl 3-hydroxy-2H-[1]benzopyran-4-carboxylate ( 6 ), an intermediate in the synthesis of 2 , were developed. Thermolysis of 6 and 9 in decalin yielded 6,8-dihydro-14H-bis[1]benzopyrano[3,4-b:4′,3′-e]pyran-14-one ( 8 ), which has previously been described. Also produced in the thermolysis was the isomeric 1H-bis[1]-benzopyrano[3,4-b:3′,4′-á]pyran-7-(9H)one ( 10 ), the first member of a novel, pentacyclic ring system.     

Acetylenchemie, 33. Mitt.: Synthese von 2-substituierten Dihydrofuro[2,3-b]chinolinen

Summary The reaction of 3-iodo-4-methoxy-2(1H)-quinolinone (1) and 3-iodo-4,6,8-trimethoxy-2(1H)-quinolinone (2) with 2-methyl-3-butyn-2-ol under modified Heck-conditions gave the 2-substituted derivatives 2-(1-hydroxy-1-methylethyl)-4-methoxyfuro[2,3-b]-quinoline (3) and 2-(1-hydroxy-1-methylethyl-4,6,8-trimethoxyfuro[2,3-b]-quinoline (4). By a subsequent hydrogenation-reaction with a homogeneous catalyst (PtO₂/Rh₂O₃), the furoquinoline-derivatives yielded the dihydrofuro-[2,3-b]quinolines, identified as 2-(1-hydroxy-1-methylethyl-4-methoxy-2,3-dihydrofuro[2,3-b]quinoline (5) (racemic platydesmine) and 2-(1-hydroxy-1-methylethyl)-4,6,8-trimethoxy-2,3-dihydrofuro-[2,3-b]quinoline (6) (racemic precursor of O⁴-methylptelefolonium salt).

     

Solid-phase synthesis of 4H-2-(3-hydroxy-4-methoxyphenyl)-naphtho[1,2-b]pyran-1-one

An effective solid-phase preparation of the pharmaceutically interesting 4H-2-(3-hydroxy-4-methoxyphenyl)-naphtho[1,2-b]pyran-1-one system from an anchored bisarylacetylene is described.     

2,2′-Bifurylidene-5,5′-diones,Coumarins, 3a, 7a-dihydro-1H-inden-1-ones,and 5H-furo[3,2-b]pyran-5-ones from propyne and carbon monoxide

The [Co₂ (CO)₈]-catalyzed reaction between propyne and CO in acetone at 110° and 170 bar was re-investigated. There are five major products: (E)-3,4′-dimethyl-2,2′-bifurylidene-5,5′-dione ( 4 ), 3,5,8-trimethylcoumarin ( 8 ), 3a, 7a-dihydro-2,4,7,7a-tetramethyl-1H-inden-1-one ( 9 ), 2,6-dimethyl-5H-furo [3,2, -b]- pyran-5-one ( 11 ), and 2,7-dimethyl-5H-furo 3,2-b-pyran-5-one ( 12 ); of these, only one, 4 . had previously been recognized. In parallel experiments were obtained 2,6-dipentyl-5 H-furo[3,2-b]pyran-5-one ( 13 ), 2,7-dipentyl–5H-furo[3,2-b]pyran-5-one ( 14 ), 3a, 7a-dihydro-2,4,7,7a-tetrapentyl-1H-inden-1-one ( 15 ). And 3a, 7a-dihydro-2,4,6,7a-tetrapentyl-1H-inden-1-one ( 16 ) from hept-1-yne, and two further types of products from two atypical 1-alkynes: 3,6,9-tri(tert-butyl)-1-oxaspiro[4.4]nona-3,6,8-trien-2-one ( 20 ) from (tert-butyl)acetylene and the exo-dimer 21 of 2,5-bis(trimethylsilyl)cyclopenta-2,4-dien-1-one ( 22 ) from (trimethylsilyl)acetylene. Compounds 11,12 , and 20 were identified by X-ray analysis.     

Syntheses of 6-Amino-1-(β-D-ribofuranosyl)-1H-pyrazolo[3,4-d]-1,3-oxazin-4-one,an isostere of oxanosine,and the guanosine analog 6-amino-1-(β-d-ribofuranosyl)-1H-pyrazolo[3,4-d]pyrimidin-4(5H)-one via ring closure of pyrazole-5-thioureido intermediates

6-Amino-1-(β-D-ribofuranosyl)-1H-pyrazolo[3,4-d]-1,3-oxazin-4-one ( 4 ), an isostere of the nucleoside antibiotic oxanosine has been synthesized from ethyl 5-amino-1-(2,3-O-isopropylidene-β-D-ribofuranosyl)pyrazole-4-carboxylate ( 6 ). Treatment of 6 with ethoxycarbonyl isothiocyanate in acetone gave the 5-thioureido derivative 7 , which on methylation with methyl iodide afforded ethyl 1-(2,3-O-isopropylidene-β-D-ribofuranosyl)-5-[(N'-ethoxycarbonyl-S-methylisothiocarbamoyl)amino]pyrazole-4-carboxylate ( 8 ). Ring closure of 8 under alkaline media furnished 6-amino-1-(2,3-O-isopropylidene-β-D-ribofuranosyl)-1H-pyrazolo[3,4-d]-1,3-oxazin-4-one ( 10 ), which on deisopropylidenation afforded 4 in good yield. 6-Amino-1-(β-D-ribofuranosyl)-1H-pyrazolo[3,4-d]pyrimidin-4(5H)-one ( 5 ) has also been synthesized from the AICA riboside congener 5-amino-1-(2,3-O-isopropylidene-β-D-ribofuranosyl)pyrazole-4-carboxamide ( 12 ). Treatment of 12 with benzoyl isothiocyanate, and subsequent methylation of the reaction product with methyl iodide gave 1-(2,3-O-isopropylidene-β-D-ribofuranosyl)-5-[(N'-benzoyl-S-methylisothiocarbamoyl)amino]pyrazole-4-carboxamide ( 15 ). Base mediated cyclization of 15 gave 6-amino-1-(2,3-O-isopropylidene-β-D-ribofuranosyl)-1H-pyrazolo[3,4-d]pyrimidin-4(5H)-one ( 14 ). Deisopropylidenation of 14 with aqueous trifluoroacetic acid afforded 5 in good yield. Compound 4 was devoid of any significant antiviral or antitumor activity in culture.     

Synthesis of analogues of the 2,3,6,-triazaphenothiazine ring system

Treatment of 2,3-dichloroquinoxalines with 2-amino-6-picoline-3-thiol gave a mixture of 2,3-bis(2-amino-6-picolinyl-3-thio)quinoxalines ( 16 , R = H, CI) and 2,3-bis (N,N-dimethylamino)quinoxalines ( 15 , R = H, CI) separated by fractional crystallization. A similar reaction of 3-amino-6-methoxypyridine-2(1H)-thione ( 9 ) with 4,5-dichloropyridazin-3(2H)-one ( 21 ) gave 4-chloro-5-(3-amino-6-methoxypyridyl-2-thio)pyridazin-3(2H)-one ( 22 ). Concentrated hydrochloric acid-catalysed cyclization of 22 gave the non-rearranged 7-methoxy-2,3,6-triazaphenothiazin-1(2H)-one. The action of compound 22 in refluxing glacial acetic acid gave, on the other hand, 7-methoxy-2,3,6-triazaphenothiazin-4(3H)-one via a Smiles rearrangement. These cyclized compounds are the first known derivatives of the new 2,3,6-triazaphenothiazine ring system.     

Reactions of Elemental Phosphorus and Phosphine with Electrophiles in Superbasic Systems: XV. Phosphorylation of Allyl Halides with Elemental Phosphorus

Elemental phosphorus (red or white) reacts with allyl chloride and allyl bromide in a two-phase system aqueous KOH-organic solvent to form tertiary symmetrical and mixed phosphine oxides among which tris(prop-2-enyl)-, bis(prop-2-enyl)[(E)-prop-1-enyl]-, bis(prop-2-enyl)[(Z)-prop-1-enyl]-, (prop-2-enyl)[(E)-prop-1-enyl][(Z)-prop-1-enyl]-, bis[(E)-prop-1-enyl](prop-2-enyl)-, bis[(Z)-prop-1-enyl](prop-2-enyl)-, tris-[(E)-prop-1-enyl]-, and bis[(E)-prop-1-enyl][(Z)-prop-1-enyl]phosphine oxides were identified. The conditions (room temperature, 60% aqueous KOH-dioxane) allowing preparation from white phosphorus and allyl bromide of tris(prop-2-enyl)- and bis(prop-2-enyl)[(E)-prop-1-enyl]phosphine oxides as major products in the total yield of up to 96% were found.     

A study of the Claisen rearrangement of 7-(3-phenyl-2-propenyloxy)-3-phenyl-(4H)-1-benzopyran-4-one derivatives

Summary The Claisen rearrangement of 7-(3-phenyl-2-propenyloxy)-3-phenyl-(4H)-1-benzopyran-4-one (2 a) gave 7-hydroxy-8-(1-phenyl-2-propenyl)-3-phenyl-(4H)-1-benzopyran-4-one (3 a) and 2,3-dihydro-2,6-diphenyl-3-methyl-(7H)furo[2,3-h]-1-benzopyran-7-one (7 a). 2-Methyl-7-(3-phenyl-2-propenyloxy)-3-phenyl-(4H)-1-benzopyran-4-one (2 b) afforded4 b and7 b. 8-Methyl-7-(3-phenyl-2-propenyloxy)-3-phenyl-(4H)-1-benzopyran-4-one (12) gave only the alkali soluble product 7-hydroxy-8-methyl-6-(1-phenyl-2-propenyl)-3-phenyl-(4H)-1-benzopyran-4-one (13).3 a,4 b, and13 were further cyclized in acidic medium to9 a,10 b, and14 followed by dehydrogenation.This paper is dedicated to Dr. F. M. Dean, Department of Organic Chemistry, Robert Robinson Laboratories, University of Liverpool, Liverpool, U. K., on his retirement     

Regioselective Heterocyclization of 3-(Cyclohex-2′-enyl)-4-hydroxy-6-methylpyran-2-one

Summary.  Regioselective heterocyclization of 3-(cyclohex-2′-enyl)-4-hydroxy-6-methyl pyran-2-one with various reagents afforded different heterocycles. With N-iodosuccinimide in acetonitrile at 0–5°C it gave 6-methyl-9′-iodo-2′-oxabicyclo[3.3.1]nonano[3,2-c]pyran-2-one, with C₅H₅NHBr₃ or C₆H₁₂N₄HBr₃ in CHCl₃ at 0–5°C it furnished 6-methyl-9′-bromo-2′-oxabicyclo[3.3.1]nonano[3,2-c]pyran-2-one. Cold concentrated H₂SO₄ lead to 6-methyl-2′-oxabicyclo[3.3.1]nonano[3,2-c]pyran-2-one, whereas PdCl₂(PhCN)₂ in C₆H₆ at 80°C afforded 9-methyl benzofuro[3,2-c]pyran-2-one. Corresponding author. E-mail: kcm@klyuniv.ernet.in Received December 27, 2001. Accepted (revised) March 1, 2002     

Bioactive metabolites from <Emphasis Type="Italic">Penicillium</Emphasis> sp. P-1, a fungal endophyte in <Emphasis Type="Italic">Huperzia serrata</Emphasis>

A chemical study of metabolites of the strain Penicillium sp. P-1, an endophyte from the stems of Huperzia serrata, furnished a new chromone derivative, (2S)-2,3-dihydro-7-hydroxy-6,8-dimethyl-2-[(E)-prop-1-enyl]- chroman-4-one (1), an enantiomer of a known compound, and seven known compounds 2–8. The structure and absolute configuration of 1 were established using spectroscopic methods, including extensive 2D NMR and CD analyses. Cytotoxic activity of compounds 1–3 against HeLa and HepG2 cell lines were evaluated, in which compounds 2 and 3 exhibited marked cytotoxic activity against HeLa cells.     

New Monoterpene-Substituted Dihydrochalcones from Piper aduncum

Five New unusual monoterpene-substituted dihydrochalcones, the adunctins A–E (1″S)-1-{2′-hydroxy-4′-methoxy-6′-[4″-methyl-1″-(1?-methylethyl)cyclohex-3″ -en-1″ -yloxy]phenyl}-3-phenylpropan-1-one ( 1 ), (5aR*,8R*,9aR*)-3-phenyl-1-[5′,8′,9′,9′a-tetrahydro-3′-hydroxy-1′-methoxy-8′-(1″-methylethyl)-5′-a-methyldibenzo-[b,d]furan-4′-yl]propan-1-one ( 2 ), (2′R*,4″S*)-1-{6′-hydroxy-4′-methoxy-4″-(1?-methylethyl)spiro[benzo[b]-furan-2′(3′H),1″ -cyclohex-2″ -en]-7′-yl}-3-phenylpropan-1-one ( 3 ), (2′R*,4″R*)-1-{6′-hydroxy-4′-methylethyl-4″-(1?-methylethyl)spiro[benzo[b]furan-2′(3′H),1″-cyclohex-2″-en]-7′-yl}-3-phenypropan-1-one ( 4 ), and (5′aR*,6′S*, 9′R*,9′aS*)-1-[5′a,6′,7′,8′,9′a-hexahydro-3′,6′-methoxy-6′-methyl-9′-(1″-methylethyl)dibenzo[b,d]-furan-4′-yl]-3-phenylpropan-1-one ( 5 ) were isolated from the leaves of Piper aduncum (Piperaceae) by preparative liquid chromatography. In addition, (?)-methyllindaretin ( 6 ), trans-phytol, and α-tocopherol ( = vitamin E) were also isolated and identified. The structures were elucidated by spectroscopic methods, including 1D- and 2D-NMR spectroscopy as well as single-crystal X-ray diffraction analysis. The antibacterial and cytotoxic potentials of the isolates were also investigated.