- Stereoselective synthesis of natural (2E,4E)-dienamides and their synthetic analogs
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A procedure has been developed for stereoselective synthesis of a number of naturally occurring (2E,4E)-dienamides and their analogs via palladium-catalyzed reaction of (1E)-1-iodoalk-1-enes with acrylamides. Pleiades Publishing, Ltd., 2012.
- Shakhmaev,Ishbaeva,Zorin
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p. 908 - 913
(2012/11/06)
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- Conjugated dienamides, methods of production thereof, compositions containing same and uses thereof
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Described are mixtures of at least four of the alkadienamides defined according to the structure: wherein R represents C1 - C2 n-alkyl; R1 is 2-methyl-1-propyl and R2 is hydrogen, or R1 and R2 taken together is a moiety having the formula wherein n is 4 or 5, or compositions containing substantial concentrations of such mixtures, prepared according to novel processes: (a) extraction of a ground substantially dried fruit of one of the Piper species, Piper longum Linn orPiper peepuloides; (b) natural product-forming synthesis; or (c) synthetic product-forming synthesis. Also described are uses of the thus-formed products for augmenting, enhancing or imparting an aroma, taste, chemesthetic effect and/or antibacterial effect in or to a consumable material and/or in the oral cavity and/or on the mammalian epidermis.
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Page/Page column 14-15
(2010/02/11)
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- Stereoselective synthesis of naturally occurring unsaturated amide alkaloids by a modified Ramberg-Baecklund reaction
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A convenient and rapid approach for the synthesis of naturally occurring unsaturated amide alkaloids 1a-1n by the recently developed one-flask Ramberg-Baecklund reaction is described. The starting material was alcohol 3, which was transformed into thiolacetate 4 using the Mitsunobu reaction. In situ cleavage of acetyl moiety of 4, followed by alkylation of the resulting thiol with appropriate chloroacetamide 5, provided the sulfide 6. Oxidation of sulfide 6 gave the corresponding sulfone 2. Treatment of the sulfone 2 with the dibromodifluoromethane in the presence of alumina-supported potassium hydroxide in dichloromethane solution afforded unsaturated amide alkaloids 1a-1n. To the best of our knowledge, the synthesis of 1e and 1i was reported for the first time.
- Li, Yang,Zhang, Yu,Huang, Zhi,Cao, Xiaoping,Gao, Kun
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p. 622 - 630
(2007/10/03)
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- Stereoselective enzymatic synthesis of cis-pellitorine, a taste active alkamide naturally occurring in tarragon
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The alkamide cis-pellitorine [(2E,4Z)-N-isobutyldeca-2,4-dienamide] that occurs naturally in tarragon was prepared in yields up to 80% by lipase-catalyzed conversion of ethyl 2E,4Z-decadienoate, the so-called pear ester, and isobutylamine both with and without the use of cosolvents. Of 13 different commercial enzyme preparations tested (lipases, proteases, esterases), only the lipase type B from Candida antarctica has a suitable activity. The reaction of the different geometric isomers of ethyl 2,4-decadienoate to the appropriate pellitorines shows a remarkable selectivity: the 2E,4Z ester is converted between 1.4 and 3.9 times faster than the 2E,4E isomer, and the relative yield of cis-pellitorine compared with trans-pellitorine is 5.7 to 16.3 times higher. In contrast to the better known frans-pellitorine, which at 10 ppm is only slightly tingling and numbing, cis-pellitorine shows very interesting pungent and warming sensations after tasting trials already in low concentrations of 10 ppm. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004.
- Ley, Jakob P.,Hilmer, Jens-Michael,Weber, Berthold,Krammer, Gerhard,Gatfield, Ian L.,Bertram, Heinz-Juergen
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p. 5135 - 5140
(2007/10/03)
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- USE OF TRANS-PELLITORIN IN THE FORM OF AN AROMATIC SUBSTANCE
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The invention relates to the use of N-isobutylamide 2E, 4E-decadien acid (trans-pellitorin) in the form of an aromatic substance, in particular a saliva stimulating aromatic substance preferably for food, buccal hygiene or gustatory preparations. The preparations, semifinished products, compounds of odorant, aromatic and gustatory substances which contain trans-pellitorin and a method for the production of said trans-pellitorin are also disclosed.
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- PRODUCTION OF CIS-PELLITORIN AND USE AS A FLAVOURING
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The invention relates to a method for producing 2E,4Z-decadienoic acid-N-isobutylamide (cis-pellitorin) and the use thereof as a pungent agent and a flavouring that generates heat, preferably in foodstuffs, oral hygiene or gourmet preparations.
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- Ene reaction with pummerer-type reaction intermediate of α-(methylthio)isobutyl acetamide: A new synthesis of pellitorine
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Pummerer-type reaction intermediate 2 of α-(methylthio)isobutyl acetamide (1) has been found to react with 1-alkenes to afford ene adducts 3. Pellitorine 4 was synthesized from the adduct 3d.
- Chen, Ling-Ching,Kang, Iou-Jiun,Wang, Huey-Min
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p. 963 - 966
(2007/10/03)
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- A synthetic approach to natural dienamides of insecticidal interest
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An efficient synthesis of dienamides of insecticidal interest has been stereoselectively achieved featuring a Stille cross-coupling reaction as the key step.
- Abarbri, Mohamed,Parrain, Jean-Luc,Duchene, Alain
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p. 239 - 249
(2007/10/03)
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- Ene Reaction of Pummerer-Type Reaction Intermediate and Synthesis of Pellitorine
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Pummerer-type reaction intermediate 2 of α-(methylthio)acetic acid (1) has been found to react with 1-alkenes to afford ene adducts 3. Pellitorine S was synthesized from the adduct 3d.
- Lin, Wei-Shing,Wang, Huey-Min,Chen, Ling-Ching
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p. 159 - 161
(2007/10/03)
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- Expedient synthesis of unsaturated amide alkaloids from Piper spp: Exploring the scope of recent methodology
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The Sakai aryl aldehyde - cyclic ketone aldol - Grob fragmentation sequence was extended to cinnamaldehyde and cyclohexanone, and the product was elaborated to analogues of the alkaloid piperstachine. The effects of substituents on the reaction involving cinnamaldehyde were studied. The aldol-fragmentation sequence failed with benzaldehyde when cyclooctanone or cyclobutanone was substituted for cyclohexanone or cyclopentanone, and the reasons for this failure were examined. Four-carbon Wittig homologation of the piperonal-cyclobutanone aldol-fragmentation product, a hypothetical route to alkaloids such as retrofractamide A, was thus not viable. Instead, three-carbon homologation of the readily available piperonal-cyclopentanone product, using alkyne chemistry recently disclosed by Lu and Trost, afforded these alkaloids in excellent overall yield. The alkyne isomerization was also used to effect efficient syntheses of pellitorine and several other non-aromatic 2E,4E-dienoic Piper amide alkaloids. The Sakai aryl aldehyde - cyclic ketone aldol - Grob fragmentation sequence was extended to cinnamaldehyde and cyclohexanone, and the product was elaborated to analogues of the alkaloid piperstachine. The effects of substitutents on the reaction involving cinnamaldehyde were studied. The aldol-fragmentation sequence failed with benzaldehyde when cyclooctanone or cyclobutanone was substituted for cyclohexanone or cyclopentanone, and the reasons for this failure were examined. Four-carbon Wittig homologation of the piperonal-cyclobutanone aldol-fragmentation product, a hypothetical route to alkaloids such as retrofractamide A, was thus not viable. Instead, three-carbon homologation of the readily available piperonal-cyclopentanone product, using alkyne chemistry recently disclosed by Lu and Trost, afforded these alkaloids in excellent overall yield. The alkyne isomerization was also used to effect efficient syntheses of pellitorine and several other non-aromatic 2E,4E-dienoic Piper amide alkaloids.
- Strunz, George M.,Finlay, Heather J.
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p. 419 - 432
(2007/10/03)
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- Efficient Synthesis of Conjugated (2E)- or (2Z)-En-4-ynoic Acids and (2E,4E)- or (2Z,4E)-Dienoic Acids via Palladium-Catalysed Cross Coupling
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(E)- or (Z)-Enynoic acids and (2E,4E)- or (2Z,4E)-dienoic acids can be obtained in good yields under mild conditions through palladium-catalysed cross coupling of (E)- or (2)-3-iodoprop-2-enoic acid with alkynylzinc or vinyltin reagents.
- Abarbri, Mohamed,Parrain, Jean-Luc,Cintrat, Jean-Christophe,Duchene, Alain
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- Dilithiated (E)-N-isobutyl-4-tosyl-2-butenamide: An allyl sulfone dianion for the regiospecific γ-functionalization of crotonamide dianion
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(E)-N-Isobutyl-4-tosyl-2-butenamide (5b) (prepared from vinylacetic acid by stereoselective iodosulfonylation-dehydroiodination and further amidation) has been lithiated with two equiv of n-butyllithium at -78°C in the presence of DMPU leading to the corresponding allyl dianion 6. This intermediate reacts with electrophiles (alkyl bromides, aldehydes and electrophilic olefins) regiospecific and stereoselectively at the γ-position to afford γ-substituted (E)-N-isobutyl-4-tosyl-2-butenamides 7. Desulfonylation of compounds 7 occurs stereoselectively to provide (E)-β,γ-unsaturated amides 9. This methodology has been applied to the synthesis of dienamides such as naturally occurring N-isobutyl-(2E,4E)-decadienamide (pellitorine).
- Caturla, Francisco,Najera, Carmen
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p. 4787 - 4790
(2007/10/03)
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- A New Straightforward, and General Approach to Dienamide Natural Products
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A new synthetic approach to various conjugated (E,E) dienamides has been developed, starting from an easily accessible bifunctional dienyl compound and based upon a double selective electrophilic substitution, followed by coupling reactions.
- Babudri, Francesco,Fiandanese, Vito,Naso, Francesco,Punzi, Angela
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p. 2067 - 2070
(2007/10/02)
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- Synthesis of 2(E),4(E)-Dienamides and 2(E),4(E)-Dienoates from 1,3-Dienes via 2-Phenylsulfonyl 1,3-Dienes
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A procedure for the preparation of 2E,4E unsaturated carboxylic acid derivatives from dienes was developed.Transformation of terminal 1,3-dienes to (E)-2-phenylsulfonyl 1,3-dienes and subsequent addition of a carboxy anion equivalent and elimination of benzenesulfinic acid led to 2,4-dienoic amides and esters.In this way the natural products N-isobutyl-2(E),4(E)-undecadienamide (1a), N-isobutyl-2(E),4(E)-decadienamide (pellitorine, 1b), and methyl 2(E),4(E)-decadienoate (1c) were obtained in high isomeric purity.
- Plobeck, Niklas A.,Baeckvall, Jan-E.
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p. 4508 - 4512
(2007/10/02)
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- A CONVENIENT STEREOSELECTIVE SYNTHESIS OF CONJUGATED DIENOIC ESTERS AND AMIDE
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(2E,4E)-Dienoic esters and amides could be synthesized via the stereoselective isomerization of the corresponding 2-ynoic esters and amides, respectively, under the catalysis of ruthenium or iridium complexes.
- Ma, Dawei,Lu, Xiyan
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p. 3189 - 3198
(2007/10/02)
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- A SHORT, HIGHLY STEREOSELECTIVE PALLADIUM AND PHASE TRANSFER CATALYZED SYNTHESIS OF PELLITORINE.
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Pellitorine has been synthesized from a vinylic iodide by a short, or even one-pot stereocontrolled palladium and phase transfer catalyzed procedure.
- Jeffery, Tuyet
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- A GENERAL AND HIGHLY STEREOSELECTIVE APPROACH TO UNSATURATED ISOBUTYLAMIDES VIA ARSONIUM SALT. NEW SYNTHESIS OF PELLITORINE
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The highly stereoselective synthesis of conjugated unsaturated isobutylamides in good yields via the arsonium salt is described, and the new synthesis of pellitorine is also reported.
- Shi, Lilan,Yang,, Jianhua,Wen, Xueging,Huang, Yao-Zeng
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p. 3949 - 3950
(2007/10/02)
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- HYDROZIRCONATION METHODS FOR NATURAL ISOBUTYLAMIDES (ANACYCLIN, PELLITORINE AND ITS VINYLOGUE) AND SYNTHONS.
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Hydrometallation of α,ο-diynes is used to make ο-acetylenic isobutylamide synthons: new syntheses of anacyclin, pellitorine and its vinylogous triene are described.
- Crombie, Leslie,Hobbs, Andrew J. W.,Horsham, Mark A.,Blade, Robert J.
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p. 4875 - 4878
(2007/10/02)
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- TOTAL SYNTHESIS OF SYLVAMIDE, A PIPER ALKAMIDE
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Key Word Index - Piper sylvaticum; Piperaceae; alkamide; sylvamide; N-isobutyl-4,5-dihydroxy-2(E)-decenamide. The structure, N-isobutyl-4,5-dihydroxy-2(E)-decenamide, for sylvamide is confirmed by its total synthesis.The erythro stereochemistry is also established by comparison of the properties of the natural and synthetic samples.
- Banerji, Avijit,Pal, Sudhir C.
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p. 1028 - 1030
(2007/10/02)
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- New Synthesis of α-Benzoyloxy Aldehydes. Application to the Stereoselective Synthesis of Conjugated (E,E)-Dienoic Esters
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A new synthetic method for the preparation of secondary α-benzoyloxy aldehydes (5a-d) and its use in the stereoselective synthesis of conjugated (E,E)-dienone (14) and dienoic esters (9b, 9c, 11, 15b, and 15c) were studied.Two-phase (benzene-H2O) reaction of RCH2CHXCHO (R=CH3, C3H7, C5H11, C7H15; X=Cl, Br) with sodium benzoate (4) in the presence of a catalytic amount of tetrabutylammonium bromide gave the corresponding α-benzoyloxy aldehydes (5a-d) in moderate yields.Compounds 5a-d were converted to γ-benzoyloxy-α,β-unsaturated carbonyl compounds or esters (7b, 7c, 10, 12, 13b, and 13c) either by the TiCl4/py-catalyzed condensation with malonate or acetoacetate or by the Wittig reaction with Ph3P=CHC(O)CH3 and Ph3P=CHCO2Et.Treatment of these compounds with 5 mol percent of (Ph3P)4Pd in refluxing THF afforded the corresponding conjugated (E,E)-dienones and dienoic esters stereoselectively.The reaction sequence was further extended to the stereoselective synthesis of ethyl (2E,4E,6E)-2,4,6-dodecatrienoate (18) and pellitorine (21).
- Sakai, Takashi,Seko, Katsuhiko,Tsuji, Akihiro,Utaka, Masanori,Takeda, Akira
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p. 1101 - 1106
(2007/10/02)
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- SYNTHETIC UTILITY OF A FLUORINE-FACILITATED CLAISEN REARRANGEMENT: A NOVEL SYNTHETIC METHOD FOR 2,4-ALKANEDIENOIC ACIDS USING 2,2,2-TRIFLUOROETHYL PHENYL SULFOXIDE
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A novel synthetic method for 2,4-alkadienoic acids from allylic alcohols and 2,2,2-trifluoroethyl phenyl sulfoxide is described which involves the in situ Claisen rearrangement facilitated by the fluorine.This method was applied to the stereocontrolled synthesis of pellitorine, a natural insecticide.
- Nakai, Takeshi,Tanaka, Kiyoshi,Ogasawara, Kyo,Ishikawa, Nobuo
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p. 1289 - 1292
(2007/10/02)
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- A NOVEL FIVE-CARBON HOMOLOGATION LEADING TO 3,4-ALKADIENOIC ACIDS BY SN2' REACTION OF β-ETHYNYL-β-PROPIOLACTONE WITH GRIGNARD REAGENTS IN THE PRESENCE OF COPPER(I) CATALYST
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β-Ethynyl-β-propiolactone reacts regioselectively with Grignard reagents in the presence of copper(I) catalyst to afford 3,4-alkadienoic acids in high yields.Synthetic utility of this reaction is demonstrated in the simple synthesis of pellitorine.
- Sato, Toshio,Kawashima, Masatoshi,Fujisawa, Tamotsu
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p. 2375 - 2378
(2007/10/02)
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- (ALLYLTHIO)ACETATE DIANION AS A MEW AND CONVENIENT REAGENT FOR THE STEREOSELECTIVE SYNTHESIS OF (2E,4E)DIENOATES FROM ALKYL HALIDES
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Treatment of (allylthio)acetate with lithium diisopropylamide followed by the addition of s-butyllithium produced a new dianion which could react with a variety of alkyl halides exclusively at the allylic position.The high regioselectivity of the allylic alkylation could be realized in the case of methyl (allylthio)acetate dianion.A convenient and general method for the stereoselective synthesis of (2E,4E)dienoates from alkyl halides has been developed.
- Tanaka, Kazuhiko,Terauchi, Makoto,Kaji, Aritsune
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p. 315 - 318
(2007/10/02)
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- A NEW SYNTHETIC METHOD FOR PELLITORINE
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A stereoselective synthesis of N-isobutyl-E,E-2,4-decadienamide, so called pellitorine is described in which the elimination reaction of acetic acid from 2-acetoxy-E-3-decenenitrile providing 2,4-decadienenitrile in a high yield was used as a key reaction.
- Mandai, Tadakatsu,Gotoh, Jiso,Otera, Junzo,Kawada, Mikio
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p. 313 - 314
(2007/10/02)
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- PYROLYSIS OF SULFOXIDE. III. CONVERSION OF 2-(PHENYLSULFINYL)ENOATE TO 2,4-DIENOATE AND SYNTHESIS OF PELLITORINE
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2,4-Dienoate was prepared by pyrolysis of 2-(phenylsulfinyl)enoate.N-Isobutyl-E,E-2,4-decadieneamide (pellitorine) was synthesized from decanoic acid in a satisfactory yield.
- Nokami, Junzo,Nishiuchi, Kotaro,Wakabayashi, Shoji,Okawara, Rokuro
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p. 4455 - 4456
(2007/10/02)
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