- Methods and compositions for terpenoid tricycloalkane synthesis
-
In one aspect, the disclosure relates to methods for preparation of intermediates useful for the preparation of terpenoid cores. In a further aspect, the disclosed methods pertain to the preparation of compounds comprising a terpenoid core or scaffold, su
- -
-
Page/Page column 55; 88
(2019/05/26)
-
- Synthesis method of laspeyresia pomonella sex pheromone
-
The invention relates to a synthesis method of laspeyresi pomonella sex pheromone. The method comprises the steps as follows: (1) methanol is added to methyl sorbate as a raw material, and an intermediate A sorbic alcohol is obtained through 5% palladium-carbon catalytic hydrogenation reduction; (2) the intermediate A sorbitol obtained in (1) and acetic anhydride are subjected to a reaction in ethyl acetate, triethylamine and water to obtain an intermediate B sorbic acetate; (3) 6-chlorohexanol is subjected to a reaction with trimethylchlorosilane in toluene in the presence of ethyl acetate and triethylamine, after the reaction, water is added, stirring and layering are performed, and an intermediate C6-chlorohexanol trimethylsilyl ester is obtained; (4) the intermediate B sorbic acetate and the intermediate C6-chlorohexanol trimethylsilyl ester are subjected to a reaction with sodium sand in a toluene solution, then, water and sulfuric acid are dropwise added, layering and rectification are performed, and a target product E8,E10-dodecadiene-1-ol is obtained. The synthesis method has the advantages as follows: the laspeyresi pomonella sex pheromone is synthesized from available rawmaterials, the reaction route is short, and the selectivity and product yield can be increased.
- -
-
Paragraph 0030; 0033; 0034; 0039; 0042; 0043
(2019/09/17)
-
- An Enyne Cope Rearrangement Enables Polycycloalkane Synthesis from Readily Available Starting Materials
-
Cyclohexanone-derived Knoevenagel adducts (cyclohexylidenemalononitriles) and two different propargyl electrophiles serve as carbon sources for assembling diverse 6/7/5 tricycloalkanes, a common terpenoid framework. The sequence involves three unique reac
- Scott, Sarah K.,Grenning, Alexander J.
-
supporting information
p. 8125 - 8129
(2017/06/30)
-
- Eleuthesides and their analogs: VII. Synthesis of menthane derivatives by the Diels-Alder reaction of levoglucosenone with (2E,4E)-hexa-2,4-dien-1-yl acetate
-
The Diels-Alder reaction of levoglucosenone with (2E,4E)-hexa-2,4-dien-1-yl acetate was used to synthesize chiral functionalized derivatives of isopropyl(methyl)cyclohexene fused to a carbohydrate fragment.
- Pilipenko,Sharipov,Valeev
-
p. 1504 - 1510
(2015/02/19)
-
- Chiral gold complex-catalyzed hetero-diels-alder reaction of diazenes: Highly enantioselective and general for dienes
-
A chiral gold(I) complex-catalyzed highly regio- and enantioselective azo hetero-Diels-Alder reaction has been developed. The chiral gold(I) complex acting as a Lewis acid exhibits high efficiency in the activation of urea-based diazene dienophiles. Moreover, this chiral gold catalyst also rendered a cascade intramolecular enyne cycloisomerization/asymmetric azo-HDA reaction.
- Liu, Bin,Li, Kang-Nan,Luo, Shi-Wei,Huang, Jian-Zhou,Pang, Huan,Gong, Liu-Zhu
-
supporting information
p. 3323 - 3326
(2013/04/23)
-
- Cobalt-catalyzed reductive allylation of alkyl halides with allylic acetates or carbonates
-
An efficient method for the direct allylation of alkyl halides catalyzed by simple cobalt(II) bromide has been developed. This reaction, using a variety of substituted allylic acetates or carbonates, provides the linear product as the major product. It displays broad substrate scope and good functional group tolerance. Copyright
- Qian, Xin,Auffrant, Audrey,Felouat, Abdellah,Gosmini, Corinne
-
supporting information; experimental part
p. 10402 - 10405
(2011/12/03)
-
- Sequential catalytic isomerization and allylic substitution. Conversion of racemic branched allylic carbonates to enantioenriched allylic substitution products
-
A catalytic protocol for the conversion of readily accessible racemic, branched aromatic allylic esters to branched allylic amines, ethers, and alkyls has been developed. Palladium-catalyzed isomerization of branched allylic esters to terminal allylic esters, followed by sequential iridium-catalyzed allylic substitution, gave the branched allylic products in good yield with high regioisomeric and enantiomeric selectivity. Both electron-rich and electron-poor branched allylic esters gave products in >90% ee. High enantiomeric excesses were also observed for the products from the reactions of 2-thienyl acetates and dienyl carbonates. Copyright
- Shekhar, Shashank,Trantow, Brian,Leitner, Andreas,Hartwig, John F.
-
p. 11770 - 11771
(2007/10/03)
-
- Reactivity of Lysine Moieties toward γ-Hydroxy-α,β-unsaturated Epoxides: A Model Study on Protein-Lipid Oxidation Product Interaction
-
Epoxyols are generally accepted as crucial intermediates in lipid oxidation. The reactivity of γ-hydroxy-α,β-unsaturated epoxides toward lysine moieties is investigated, employing trans-4,5-epoxytrans-2-hexen-1-ol (EH) as a model substrate and propylamine or N2-acetyl-L-lysine 4-methylcoumar-7-ylamide (AcLys-MCA) as model reagents for protein-bound lysine. Independent syntheses are reported for EH and AcLys-MCA. Reaction of the amine components with EH in THF yields 4-(propylamino)-trans-2-hexene-1,5-diol and N2-acetyl-N6-(1,5-dihydroxy-trans-2-hexen-4-yl)-L-lysine 4-methylcoumaryl-7-amide, respectively. Unequivocal structural characterization of the products prove the epoxy ring cleavage to proceed by a true SN2 mechanism. Incubation of EH with propylamine and AcLys-MCA in aqueous medium at 37 °C shows the turnover to decrease with lower pHs. From reaction of EH (100 mM) with AcLys-MCA (50 mM) under physiological conditions (pH 7.4), 3% of the lysine moieties can be identified in the form of N2-acetyl-N6-(1,5-dihydroxy-trans-2-hexen-4-yl)-L-lysine 4-methylcoumar-7-ylamide after 24 h.
- Lederer, Markus O.
-
p. 2531 - 2537
(2007/10/03)
-
- Synthesis of dodeca-8E,10E-dien-1-ol - The sex pheromone of Laspeyresia pomonella via the acetolysis of 4-propenyl-1,3-dioxane
-
A new scheme has been developed for the synthesis of dodeca-8E,10E-dien-1-ol (the sex pheromone of the codling moth) from sorbyl acetate, available from 4-propenyl-1,3-dioxane through the intermediate diacetate of 3-propenyl-2-oxapentane-1,5-diol.
- Shakova,Zorin,Musavirov,Safarov,Muslukhov,Kharisov,Ishmuratov,Rakhmankulov
-
p. 582 - 584
(2007/10/03)
-
- Novel Synthesis of Phenol Derivatives by Palladium-Catalyzed Cyclocarbonylation of 2,4-Pentadienyl Acetates
-
Phenyl acetates were selectively obtained in good yields by cyclocarbonylation of 2,4-pentadienyl acetates in the presence of NEt3, Ac2O, and a catalytic amount of palladium complexes such as PdCl2(PPh3)2 at 120-140 deg C under 50 atm of CO.No five-membered ring products were observed.A platinum complex PtCl2(PPh3)2 was also effective as a catalyst.The reaction of 5-phenyl-2,4-pentadienyl bromide with M(CO)(PPh3)3 (M = Pd or Pt) under CO gave the corresponding 6-phenyl-3,5-hexadienoyl complexes in a high yield, which in turn afforded 2-acetoxybiphenyl in 41-51percent yield on heating to 160 deg C under 50 atm of CO in the presence of NEt3 and Ac2O.Similar 3,5-hexadienoyl complexes are proposed to be intermediates in the catalytic cyclocarbonylation of 2,4-pentadienyl acetates.On the other hand, PdCl2(PPh3)2-catalyzed carbonylation of o-(bromomethyl)(1-alkenyl)benzenes in the presence of NEt3 and Ac2O gave 2-naphthyl acetates in moderate yields, while the reaction in the absence of Ac2O gave five-membered ring products such as 2-indanones or a tricyclic lactone by incorporation of one or two CO, respectively.
- Ishii, Youichi,Gao, Chao,Xu, Wen-Xiang,Iwasaki, Masakazu,Hidai, Masanobu
-
p. 6818 - 6825
(2007/10/02)
-
- SYNTHESIS OF SORBIC ALCOHOL (2E,4E-HEXADIEN-1-OL)
-
The decomposition of 1-acetoxy-3-acetoxymethoxy-4-hexene by the action of acids leads to a 1:2 mixture of 1-acetoxy-2,4-hexadiene and 1-acetoxy-3,5-hexadiene.The same compounds are formed in a ratio of 1:1 during the pyrolysis of 1,3-diacetoxy-4-hexene.
- Vasil'ev, A. A.,Poddubnaya, S. S.,Cherkaev, G. V.,Cherkaev, V. G.
-
p. 1457 - 1460
(2007/10/02)
-
- Stereoselective Synthesis of (2E,4E)- and (2Z,4E)-2,4-Alkadienoates by the Ester Enolate Claisen Rearrangement of (E)-1-Alkyl-3-trimethylsilyl-2-propenyl Glycolates Followed by the Peterson Reaction
-
The ester enolate Claisen rearrangement of (E)-1-alkyl-3-trimethylsilyl-2-propenyl glycolates gave (E)-erythro-2-hydroxy-3-trimethylsilyl-4-alkenoates with high diastereoselectivity, which were stereoselectively converted into (2E,4E)- and (2Z,4E)-2,4-alkadienoates by the Peterson reaction.
- Sato, Toshio,Tsunekawa, Hiroshi,Kohama, Hiromasa,Fujisawa, Tamotsu
-
p. 1553 - 1556
(2007/10/02)
-
- Preparation of (E)-1,3,5-Hexatriene and (3E,5E)-1,3,5,7-Octatetraene by the Palladium Catalyzed Elimination of Acetic Acid form Allylic Acetates
-
Palladium complex-catalyzed elimination of acetic acid from (2E,4E)-2,4-hexadienyl acetate and (2E,4E,6E)-2,4,6-octatrienyl acetate afforded, respectively, the title conjugated polyenes stereoselectively.
- Yamamoto, Keiji,Suzuki, Shigeaki,Tsuji, Jiro
-
p. 2541 - 2542
(2007/10/02)
-
- SYNTHESIS OF CONJUGATED AND UNCONJUGATED 1-ALKADIENOLS AS CANDIDATES FOR INSECT ATTRACTANTS
-
Six 1-alkadienols, which are potential insect sex attractants or their precursors, have been stereoselectively or stereospecifically synthesized in high stereoisomeric purity starting from commercially available materials.The synthesized alcohols include (4Z,6Z)-4,6-nonadien-1-ol (1), (3Z,5Z)-3,5-nonadien-1-ol (2), (3Z,5Z)-3,5-tetradecadien-1-ol (3), (5E,7E)-nonadien-1-ol (4), (4Z,7Z)-4,7-nonadien-1-ol (5), and (E)-4,8-nonadien-1-ol (6).Compounds 1-5 were not previously described in the literature.
- Rossi, Renzo,Carpita, Adriano,Quirici, Maria Grazia
-
p. 173 - 180
(2007/10/02)
-
- PdII-catalysed Isomerisations of 3-Acetoxy-1,4-dienes to 1-Acetoxy-2,4-dienes: Stereochemical and Preparative Aspects
-
The rapid PdII-catalysed rearrangement of 3-acetoxy-1,4-dienes to 1-acetoxy-2,4-dienes (3E,5Z)-2-acetoxydeca-3,5-diene (ca. 80percent)> occurs in a stereoselective and regioselective manner.
- Golding, Bernard T.,Pierpoint, Colin,Aneja, Rajindra
-
p. 1030 - 1031
(2007/10/02)
-