67400-04-8Relevant academic research and scientific papers
Alkene synthesis by photocatalytic chemoenzymatically compatible dehydrodecarboxylation of carboxylic acids and biomass
Nguyen, Vu T.,Nguyen, Viet D.,Haug, Graham C.,Dang, Hang T.,Jin, Shengfei,Li, Zhiliang,Flores-Hansen, Carsten,Benavides, Brenda S.,Arman, Hadi D.,Larionov, Oleg V.
, p. 9485 - 9498 (2019/10/11)
Direct conversion of renewable biomass and bioderived chemicals to valuable synthetic intermediates for organic synthesis and materials science applications by means of mild and chemoselective catalytic methods has largely remained elusive. Development of artificial catalytic systems that are compatible with enzymatic reactions provides a synergistic solution to this enduring challenge by leveraging previously unachievable reactivity and selectivity modes. We report herein a dual catalytic dehydrodecarboxylation reaction that is enabled by a crossover of the photoinduced acridine-catalyzed O-H hydrogen atom transfer (HAT) and cobaloxime-catalyzed C-H-HAT processes. The reaction produces a variety of alkenes from readily available carboxylic acids. The reaction can be embedded in a scalable triple-catalytic cooperative chemoenzymatic lipase-acridine-cobaloxime process that allows for direct conversion of plant oils and biomass to long-chain terminal alkenes, precursors to bioderived polymers.
Chemoenzymatic macrocycle synthesis using resorcylic acid lactone thioesterase domains
Heberlig, Graham W.,Brown, Jesse T. C.,Simard, Ryan D.,Wirz, Monica,Zhang, Wei,Wang, Meng,Susser, Leah I.,Horsman, Mark E.,Boddy, Christopher N.
, p. 5771 - 5779 (2018/08/22)
A key missing tool in the chemist's toolbox is an effective biocatalyst for macrocyclization. Macrocycles limit the conformational flexibility of small molecules, often improving their ability to bind selectively and with high affinity to a target, making them a privileged structure in drug discovery. Macrocyclic natural product biosynthesis offers an obvious starting point for biocatalyst discovery via the native macrocycle forming biosynthetic mechanism. Herein we demonstrate that the thioesterase domains (TEs) responsible for macrocyclization of resorcylic acid lactones are promising catalysts for the chemoenzymatic synthesis of 12- to 18-member ring macrolactones and macrolactams. The TE domains responsible for zearalenone and radicicol biosynthesis successfully generate resorcylate-like 12- to 18-member macrolactones and a 14-member macrolactam. In addition these enzymes can also macrolactonize a non-resorcylate containing depsipeptide, suggesting they are versatile biocatalysts. Simple saturated omega-hydroxy acyl chains are not macrocyclized, nor are the alpha-beta unsaturated derivatives, clearly outlining the scope of the substrate tolerance. These data dramatically expand our understanding of substrate tolerance of these enzymes and are consistent with our understanding of the role of TEs in iterative polyketide biosynthesis. In addition this work shows these TEs to be the most substrate tolerant polyketide macrocyclizing enzymes known, accessing resorcylate lactone and lactams as well as cyclicdepsipeptides, which are highly biologically relevant frameworks.
Bio-based α,ω-Functionalized Hydrocarbons from Multi-step Reaction Sequences with Bio- and Metallo-catalysts Based on the Fatty Acid Decarboxylase OleTJE
Bojarra, Samiro,Reichert, Dennis,Grote, Marius,Baraibar, álvaro Gómez,Dennig, Alexander,Nidetzky, Bernd,Mügge, Carolin,Kourist, Robert
, p. 1192 - 1201 (2018/02/13)
OleT from Jeotgalicoccus sp. ATCC 8456 catalyzes the decarboxylation of ω-functionalized fatty acids to the corresponding alkenols, which can themselves serve as starting material for the synthesis of polymers and fine chemicals. To show the versatility of possible reactions, a series of in vitro reaction cascades was developed where an alkenol produced by the decarboxylation of ω-hydroxy fatty acids can be further converted into alkenylamines and diols. By coupling OleT with an alcohol dehydrogenase or alcohol oxidase as well as an amino-transaminase, an oxidative decarboxylation followed by the oxidation of the terminal alcohol and a subsequent reductive transamination could be carried out. By using different cofactors or electron sources, the reactions could be performed sequentially or simultaneously. The combination of enzymatic decarboxylation with a ruthenium catalyst in a chemo-enzymatic cascade provides a novel way to synthesize long-chain diols.
Fine-tuning latent fingerprint detection on paper using 1,2-indanedione bi-functional reagents
Lee, Jisun,Joullié, Madeleine M.
, p. 7620 - 7629 (2015/09/07)
In order to address the need for consistency and generality in chemical methods developed for detection of latent fingerprints on paper substrates, a practical protocol was developed using 1,2-indanedione-based bi-functional reagents. A series of novel bi
The first convergent total synthesis of penarolide sulfate A2, a novel α-glucosidase inhibitor
Gao, Yangguang,Shan, Qiuli,Liu, Jun,Wang, Linlin,Du, Yuguo
, p. 2071 - 2079 (2014/03/21)
Penarolide sulfate A2, a 31-membered macrolide encompassing a proline residue and three sulfate groups, was firstly synthesized in 16 linear steps with 4.8% overall yield. Three consecutive stereogenic centers in penarolide sulfate A2 were efficiently derived from natural chiral template l-arabinose. The crucial assembly reactions included Brown asymmetric allylation, olefin cross-metathesis, alkyne-epoxide coupling, and macrolactamization. The anti-yeast α-glucosidase activities of penarolide sulfate A2 and its fully desulfated derivative were examined showing IC50 values of 4.87 and 10.74 μg mL-1, respectively.
Zirconium-catalyzed chemoselective methylalumination of ethers, amines, and sulfides bearing two terminal alkenyl groups
Takagi, Ryukichi,Igata, Nao,Yamamoto, Kazuhiro,Kojima, Satoshi
, p. 1556 - 1564 (2011/06/17)
Chemoselectivity in the methylalumination reaction of unsymmetrical ethers, amines, and sulfides bearing two different terminal alkenyl groups, a 13-tetradecenyl group and an allyl, 4-pentenyl or 6-heptenyl group was examined. The methylalumination of the allyl derivatives proceeded with complete chemoselectivity to afford only the 13-tetradecenyl-monomethylated products. In the methylalumination reactions of the 4-pentenyl and the 6-heptenyl derivatives, in addition to the 13-tetradecenyl-monomethylated products, and dimethylated products were also obtained. However, as in the case of the allyl derivatives, monomethylation to the shorter 4-pentenyl or 6-heptenyl group was not observed, except in the case of 6-heptenyl 13-tetradecenyl amine. The unique selectivity was rationalized upon how readily the intramolecular ligand exchange reaction between intermediate zirconocenium-alkene and zirconocenium-heteroatom complexes could occur.
Tishchenko reactions of aldehydes promoted by diisobutylaluminum hydride and its application to the macrocyclic lactone formation
Hon, Yung-Son,Wong, Ying-Chieh,Chang, Chun-Ping,Hsieh, Cheng-Han
, p. 11325 - 11340 (2008/03/12)
Aliphatic aldehydes react with catalytic amount of Dibal-H in n-pentane to give the corresponding Tishchenko products in good to excellent yields. On contrary, α-silyloxy aldehydes give α-silyloxy ketones via Oppenauer oxidation under similar condition. Tishchenko reaction of ω-alkene aldehydes followed by RCM and hydrogenation affords a convenient method to prepare the 11-37 membered macrocyclic lactones.
Synthesis of γ,δ-unsaturated-β-keto lactones via sequential cross metathesis-lactonization: A facile entry to macrolide antibiotic (-)-A26771B
Gebauer, Julian,Blechert, Siegfried
, p. 2021 - 2025 (2007/10/03)
A simple access to γ,δ-unsaturated-β-keto lactones is presented, allowing a rapid total synthesis of the naturally occurring 16-membered macrolide antibiotic (-)-A26771B via cross metathesis, asymmetric dihydroxylation, and lactonization as the key steps.
Catalytic asymmetric synthesis of macrocyclic (E)-allylic alcohols from ω-alkynals via intramolecular 1-alkenylzinc/aldehyde additions
Oppolzer,Radinov,El-Sayed
, p. 4766 - 4770 (2007/10/03)
The ω-alkynals yielded macrocyclic (S)-allylic alcohols in a one-pot reaction sequence involving alkyne monohydroboration, boron to zinc transmetalation, and ((+)-DAIB)-catalyzed enantioselective intramolecular ring closure to the aldehyde function. A general study of this macrocyclization methodology is presented with respect to ligand type, size, and nature of the formed rings.
A Selective Monodehydration of C4-14-α,ω-Alkanediols with Stearic and/or Palmitic Acids
Yamanaka, Tohr,Imai, Takashi
, p. 1585 - 1586 (2007/10/02)
The formation of monoesters of the C4-14-α,ω-alkanediol (1) with stearic and/or palmitic acids and the consecutive pyrolysis of the monoesters to an ω-alken-1-ol (2) were effected at 320-350 deg C under 260-760 mmHg in a backmix flow reactor of a constant volume equipped with a fractionating column, through which the unchanged 1 was partially recycled.The selectivity in the preparations of 2(C6, C10, C14) was greater than 79percent.
