- 1 - - 1, 3 - Alkadiene acyloxy method (by machine translation)
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- 1, 3 - Alkadiene 1 - acyloxy [to] a production method of a industrially useful. (1) Represented by the formula [a] α, β - unsaturated aldehyde reaction to produce the metal alkoxide [...] process is performed, the following formula (3) is reacted with a carboxylic acid anhydride [...] step - 1, 3 - alkadiene represented by the preparation of 1 - acyloxy. (In formula (1), R1 - R3 The, each independently hydrogen, an alkyl group or the like. )[Drawing] no (by machine translation)
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Paragraph 0025-0029
(2019/05/08)
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- METHOD FOR PRODUCING 1-ACYLOXY-1,3-BUTADIENE
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PROBLEM TO BE SOLVED: To provide a method for producing a 1-acyloxy-1,3-butadiene that can be performed only with a base of an industrially advantageous catalytic amount. SOLUTION: A method for producing a 1-acyloxy-1,3-butadiene represented by formula (3) includes mixing α,β-unsaturated aldehyde, carboxylic acid anhydride, and a catalytic amount of carboxylate, to heat and agitate the mixture (R1 is derived from α-position of the unsaturated aldehyde and is H, an alkyl group or the like; R2 is derived from β-position of the unsaturated aldehyde and is H, an alkyl group or the like; R3 is H, an alkyl group or the like; R4 is derived from a carboxyl residue of the carboxylic acid anhydride and is a C1-20 alkyl group). SELECTED DRAWING: None COPYRIGHT: (C)2018,JPOandINPIT
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Paragraph 0023-0024
(2018/09/11)
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- METHOD FOR PRODUCING 1-ACYLOXY-1,3-BUTADIENE
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PROBLEM TO BE SOLVED: To provide a method for producing a 1-acyloxy-1,3-butadiene that can be performed only with a base of a catalytic amount even when a substrate has a boiling point less than 135°C. SOLUTION: A method for producing a 1-acyloxy-1,3-butadiene represented by formula (3) includes treating α,β-unsaturated aldehyde with carboxylic acid anhydride and a catalytic amount of 4-dialkylaminopyridine at a temperature less than 135°C, without requiring a base other than 4-dialkylaminopyridine (R1-R2 independently represent H, a C1-30 linear/branched alkyl; R3 is H, a C1-30 alkyl or a C2-30 alkenyl; R4 is a C1-20 alkyl; alkyl groups of R3 and R4 may be linear/branched, substituted/unsubstituted with halogen, and the alkenyl group may further contain one or more C=C bonds in the group and may be linear/branched, substituted/unsubstituted with halogen). SELECTED DRAWING: None COPYRIGHT: (C)2018,JPO&INPIT
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Paragraph 0023
(2018/09/11)
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- The 'Mikami'-Catalyst in Enantioselective Diels-Alder Reactions of Juglone-Based Dienophiles with Different 1-Oxygenated Dienes: An Investigation on the Substitution Pattern Dependent Regioselectivity
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A mechanistic study investigating the substitution pattern depending regioselectivity of enantioselective BINOL-Ti-catalyzed- Diels-Alder reactions of juglone-based dienophiles with 1-oxygenated dienes is reported. The different influences of residues both on the diene as well as on the dienophiles are investigated giving a detailed picture of their role on the regioselectivity.
- B?se, Dietrich,Frey, Wolfgang,Pietruszka, J?rg
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supporting information
p. 2524 - 2532
(2015/12/26)
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- The 'Mikami'-catalyst in enantioselective diels-alder reactions of juglone-based dienophiles with different 1-oxygenated dienes: An investigation on the substitution pattern dependent regioselectivity
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A mechanistic study investigating the substitution pattern depending regioselectivity of enantioselective BINOL-Ti-catalyzed Diels-Alder reactions of juglone-based dienophiles with 1-oxygenated dienes is reported. The different influences of residues both on the diene as well as on the dienophiles are investigated giving a detailed picture of their role on the regioselectivity.
- B?se, Dietrich,Frey, Wolfgang,Pietruszka, J?rg
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supporting information
p. 2524 - 2532
(2014/11/08)
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- Syntheses of structurally-simplified and fluorescently-labeled neovibsanin derivatives and analysis of their neurite outgrowth activity in PC12 cells
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The syntheses of several neovibsanin derivatives were carried out in order to elucidate the simple structure required for displaying neurite outgrowth activity. In addition, a fluorescent probe molecule was synthesized and the analysis of its behavior in the PC12 cell line showed that the neovibsanins accumulate on the outer edge of the cell at the site of formation of prominences.
- Imagawa, Hiroshi,Saijo, Hayato,Yamaguchi, Hitomi,Maekawa, Ken,Kurisaki, Takahiro,Yamamoto, Hirofumi,Nishizawa, Mugio,Oda, Masataka,Kabura, Michiko,Nagahama, Masahiro,Sakurai, Jun,Kubo, Miwa,Nakai, Megumi,Makino, Kosho,Ogata, Mitsuko,Takahashi, Hironobu,Fukuyama, Yoshiyasu
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supporting information; experimental part
p. 2089 - 2093
(2012/04/17)
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- The high stereoselectivity of the tandem sequence Diels-Alder reaction/Ireland-Claisen rearrangement starting from substituted O-(E)-buta-1,3-dienyl ketene acetals and cyclic dienophiles
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A new tandem reaction leads to bicyclic cyclohexene derivatives with complete control of the relative configuration of the four chiral centers formed. The high diastereoselectivity is the consequence of an endo-selective Diels-Alder reaction followed by an Ireland-Claisen rearrangement that proceeds via a boat-like transition state. Georg Thieme Verlag Stuttgart.
- Soldermann, Nicolas,Velker, Joerg,Neels, Antonia,Stoeckli-Evans, Helen,Neier, Reinhard
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p. 2379 - 2387
(2008/02/13)
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- Competition between hetero-Diels-Alder and cheletropic addition of sulfur dioxide. Theoretical and experimental substituent effects on the relative stability of 3,6-dihydro-1,2-oxathiin-2-oxides (sultines) and 2,5- dihydrothiophene-1,1-dioxides (sulfolenes). Anomeric effects in sultine and 6-substituted derivatives
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At low temperature and in the presence of CF3COOH, SO2 undergoes Diels-Alder additions with (E)-1-acetoxybutadiene (8d) giving a 1:10 mixture of diastereomeric 6-acetoxysultines (9d + 10d). The Van't Hoff plot for equilibria 8d + SO2 ? 9d + 10d led to ΔH(r) = -7.0 ± 0.3 kcal/mol, ΔS(r) = -42 ± 3 cal·mol-1·K -1. At 20 °C, 8d underwent a slow cheletropic addition with SO2 giving 2-acetoxysulfolene (11d, ΔH(r) ? -11.5 kcal/mol), the structure of which was established by single-crystal X-ray diffraction studies. (E)-Chloro (8e) and (E)-bromobutadiene (8f) did not undergo Diels- Alder additions with SO2, even in the presence of protic or Lewis acid promoters. Low yields of 2-chloro- (11e) and 2-bromosulfolene (11f) were obtained at 20 °C. The structure of 11e was confirmed by single-crystal X- ray diffraction. The potential energy hypersurfaces of the Diels-Alder and cheletropic additions of SO2 to butadiene (8a), (E)-piperilene (8b), (E)-1- methoxy- (8c), (E)-1-acetoxy- (8d), and (E)-1-chlorobutadiene (8e) were studied by ab initio quantum calculations at the MP2/631G* level. In agreement with the experiment, 6-substituted sultines 9X and 10X were less stable than the corresponding 2-substituted sulfolenes 11X for X = Me, OAc, Cl. With X = OMe, the two diastereomeric 6-methoxysultines (9c, 10c) and 2- methoxysulfolene (11c) were calculated to have similar stabilities. This is attributed to a stabilizing thermodynamic anomeric effect or gem- sulfinate/methoxy disubstitution effect in 9c, 10c. Such effects were not detected for sulfinate/acetoxy (9d, 10d) and sulfinate/chloro (9e, 10e) disubstitutions. The relative instability of 2-acetoxy- (11d) and 2- chlorosulfolene (11e) compared with their cycloaddents is attributed to repulsive interactions between the SO2 moieties and the 2-substituents. The Alder endo mode of [4 + 2] cycloaddition of SO2 is predicted to be faster than the 'anti-Alder mode' of additions for dienes 8X, X = Me, OMe, OAc, Cl. The resulting diastereomeric sultines 9X and 10X, respectively, exist as equilibria (energy barrier: ca. 5-6 kcal/mol) of two conformers 9X ? 9'X, 10X ? 10'X. In general, the conformers 9X, 10X with pseudoaxial S=O group are preferred (conformational anomeric effect of the sulfinate moiety). Repulsive interactions between pseudoaxial S=O and polar cis-6-substituents (e.g.: X = OMe, OAc) in 9X may render conformers 9'X (with the S=O and 6-X groups in pseudoequatorial positions) as stable as conformers 9X. The calculations predict the existence of conformational anomeric effects of 2-3 kcal/mol for the gem-sulfinate/methoxy (9c, 10'c) and gem-sulfinate/acetoxy disubstitution (9d, 10'd).
- Fernandez, Tino,Suarez, Dimas,Sordo, Jose A.,Monnat, Frederic,Roversi, Elena,De Castro, Antonio Estrella,Schenk, Kurt,Vogel, Pierre
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p. 9490 - 9499
(2007/10/03)
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- Synthetic routes to a constrained ring analog of didemnin B
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The didemnin class of biologically active cyclodepsipeptides, isolated from a marine tunicate, has shown antitumor, antiviral, and immunosuppressive activities. Synthetic studies were undertaken to prepare a modified analog of one of the most potent congeners, didemnin B (1). The side chain of the isostatine unit was tethered into the macrocycle via a cyclohexane ring in order to provide a more rigid conformation and determine the importance of this unit in bioactive compounds. This modification created a new macrocycle core and generated a diastereomeric mixture of a constrained analog of didemnin B (2).
- Mayer, Scott C.,Pfizenmayer, Amy J.,Joullie, Madeleine M.
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p. 1655 - 1664
(2007/10/03)
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- Practical enantiospecific synthesis of RPR 111905: A novel Non-peptide substance P antagonist
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The synthesis of enantiomerically pure RPR 111905 was achieved in twelve steps with an overall yield of 6.9%. The synthetic strategy was based on a Diels-Alder reaction to generate the bicyclio framework and the asymmetry was introduced by resolution.
- Mutti, Stephane,Daubie, Christophe,Malpart, Joel,Radisson, Xavier
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p. 8743 - 8746
(2007/10/03)
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- Synthetic studies of a constrained ring didemnin analog
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An asymmetric Diels-Alder reaction in the presence of 3.0 M lithium perchlorate-diethyl ether was used to generate the initial stereochemistry for a cyclohexane amino acid (3), a key intermediate in the preparation of a fused ring didemnin analog. This constrained ring macrocycle should provide insight into the binding site conformation of the bioactive species.
- Mayer,Pfizenmayer,Cordova,Li,Joullie
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p. 519 - 522
(2007/10/02)
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- Stereoselectivity in the Synthesis of Enol Esters from Chloromercurio Aldehydes and Acyl Chlorides
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Reactions of chloromercurio aldehydes with acyl chlorides gave a variety of (Z)- and (E)-enol esters.The Z/E ratio of the enol esters is dependent on the structure of chloromercurio aldehydes but independent of that of acyl chlorides.Z-Rich enol esters were prepared by acylation of 2-chloromercurio aldehydes derived from propanal, butanal, and 2-phenylethanal, while E-rich 1-acyloxy-1,3-butadiene was obtained by acylation of (E)-4-chloromercurio-2-butenal.Reaction mechanisms for the stereoselective formation of these enol esters are discussed together with the isomer composition of starting enol acetates from which the chloromercurio aldehydes were prepared.
- Fukuda, Wakichi,Sato, Hozumi,Kakiuchi, Hiroshi
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p. 751 - 756
(2007/10/02)
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- Diels-Alder Route to Potential Trichothecene Precursors
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2-Methyl-3-yn-2-ol (9) is efficiently converted into 6-formyl-3,6-dimethylcyclohex-2-enyl acetate (4b) and into 6-acetyl-3,6-dimethylcyclohex-2-enyl acetate (4c) via highly regio- and stereo-selective Diels-Alder cycloadditions of 3-methylbuta-1,3-dienyl acetate (2b).The cycloadduct (4b) is converted by base into 4a,5,6,8a-tetrahydro-4a,7-dimethylcoumarin (13b), whilst the cycloadduct (4c) yields 2,3,4a,5,6,8a-hexahydro-2-hydroxy-2,4a,7-trimethylchroman-4-one (15), the structure of which was confirmed by X-ray analysis.Both (13b) and (15) possess a number of structural features of the trichothecenes and may be of value in their total synthesis.
- Banks, Robert E.,Miller, Allen J.,Nunn, John M.,Stanley, Philip,Weakley, Timothy J. R.,Ullah, Zakir
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p. 1096 - 1102
(2007/10/02)
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- STEREOSELECTIVE SYNTHESIS OF (+/-)-PALITANTIN
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Stereoselective synthesis of (+/-)-palitantin has been completed.
- Ichihara, A.,Ubukata, M.,Sakamura, S.
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p. 1547 - 1550
(2007/10/02)
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