88346-87-6Relevant academic research and scientific papers
A concise Diels–Alder strategy leading to congeners of the ABC ring system of the marine alkaloid ‘upenamide
Wenzler, Marta E.,Melancon, Bruce J.,Sulikowski, Gary A.
, p. 3252 - 3253 (2016)
A second-generation approach to the BC spirocycle of ‘upenamide is reported. Central to the synthesis is an endo selective Diels–Alder reaction between 1-(t-butyldimethylsiloxy)-1,3-butadiene and bromomaleic anhydride followed by a radical mediated allylation of the ring fusion bromide. Functional group manipulation provides three (9–11) advanced synthetic intermediates ready for coupling with the remaining half (DE bicycle) of ‘upenamide.
Nickel-Catalyzed Enantioselective Synthesis of Pre-Differentiated Homoallylic syn- or anti-1,2-Diols from Aldehydes and Dienol Ethers
Davies, Thomas Q.,Murphy, John J.,Dousset, Maxime,Fürstner, Alois
supporting information, p. 13489 - 13494 (2021/09/11)
Nickel catalysis allied with cyclodiphosphazane or VAPOL-derived phosphoramidite ligands provides selective access to monoprotected vicinal diols by reductive coupling of dienol ethers and aldehydes. The observed regioselectivity is unprecedented, in that the diene reacts at the least nucleophilic and most hindered C atom that is attached to the oxygen substituent rather than at the terminal position. Notably, both syn and anti diastereomers of the products can be accessed depending on the configuration of the diene partner with usually excellent diastereo- and enantioselectivity.
Enantioselective Synthesis of cis-Decalin Derivatives by the Inverse-Electron-Demand Diels–Alder Reaction of 2-Pyrones
Cai, Quan,Li, Zhan-Ting,Si, Xu-Ge,Zhang, Zhi-Mao,Zheng, Cheng-Gong
supporting information, p. 18412 - 18417 (2020/08/21)
A novel strategy for the synthesis of cis-decalins by an ytterbium-catalyzed asymmetric inverse-electron-demand Diels–Alder reaction of 2-pyrones and silyl cyclohexadienol ethers is reported here. A broad range of synthetically important cis-decalin derivatives with multiple contiguous stereogenic centers and functionalities are obtained in good yields and stereoselectivities. A full set of diastereomeric substituted cis-decalin motifs are readily accessible by tuning the absolute configurations of substituted silyl cyclohexadienol ethers (R or S) as well as the ligands (R or S). The synthetic potential is showcased by the enantioselective total synthesis of 4-amorphen-11-ol, and further demonstrated by the first total synthesis of cis-crotonin.
A Concise Synthesis of Forskolin
Hylse, Ond?ej,Maier, Luká?,Ku?era, Roman,Pere?ko, Tomá?,Svobodová, Aneta,Kubala, Luká?,Paruch, Kamil,?venda, Jakub
supporting information, p. 12586 - 12589 (2017/09/12)
A 24-step synthesis of (±)-forskolin is presented, which delivered hundred milligram quantities of this complex diterpene in one pass. Transformations key to our approach include: a) a strategic allylic transposition, b) stepwise assembly of a sterically encumbered isoxazole ring, and c) citric acid-modified Upjohn dihydroxylation of a resilient tetrasubstituted olefin. The developed route has exciting potential for the preparation of new forskolin analogues inaccessible by semisynthesis.
1-tetralone spiro-diene as well as synthetic method and application thereof
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Paragraph 0049; 0050, (2017/01/02)
The invention relates to 1-tetralone spiro-diene as well as a synthetic method and an application thereof. 1-tetralone spiro-diene is represented by formula (1), and the compound can be used for synthesizing more types of 1-tetralone spiro-framework compounds. 1-tetralone spiro-diene is prepared by the steps of adding 2-crotonaldehyde, tert-butyldimethylsilyl triflate and triethylamine into dichloromethane for reaction so as to obtain a reaction system containing tert-butyl dimethyl silicon protected diene, adding 2-methylene-1-tetralone and zinc trifluoromethanesulfonate into a reaction container, adding an aromatic hydrocarbon solvent under the protection of inert gas, and adding prepared tert-butyl dimethyl silicon protected diene for reaction, so as to finally obtain 1-tetralone spiro-diene. A preparation method of 1-tetralone spiro-diene is simple, the cost is low, and the consumption of catalysts is low.
Copper-Catalyzed Regiospecific and 1,2-Regioselective Cyclopropanation of (1 Z)-1-Amino- and (1 Z)-1-Oxy-1,3-butadienyl Derivatives
Tayama, Eiji,Saito, Shun
supporting information, p. 1880 - 1884 (2015/08/06)
The copper-catalyzed regiospecific and 1,2-regioselective cyclopropanation of (1Z)-1-amino- and (1Z)-1-oxy-1,3-butadienyl derivatives, which could be prepared by Z-stereoselective 1,4-elimination with α-aryl diazoesters was successfully demonstrated. This successful regiospecific protocol enabled the preparation of the corresponding 1-amino- and 1-oxy-2-vinylcyclopropane derivatives as almost single stereoisomers.
Stereocontrolled Synthesis of a Potential Transition-State Inhibitor of the Salicylate Synthase MbtI from Mycobacterium tuberculosis
Liu, Zheng,Liu, Feng,Aldrich, Courtney C.
, p. 6545 - 6552 (2015/10/06)
Mycobactins are small-molecule iron chelators (siderophores) produced by Mycobacterium tuberculosis (Mtb) for iron mobilization. The bifunctional salicylate synthase MbtI catalyzes the first step of mycobactin biosynthesis through the conversion of the primary metabolite chorismate into salicylic acid via isochorismate. We report the design, synthesis, and biochemical evaluation of an inhibitor based on the putative transition state (TS) for the isochorismatase partial reaction of MbtI. The inhibitor mimics the hypothesized charge buildup at C-4 of chorismate in the TS as well as C-O bond formation at C-6. Another important design element of the inhibitor is replacement of the labile pyruvate side chain in chorismate with a stable C-linked propionate isostere. We developed a stereocontrolled synthesis of the highly functionalized cyclohexene inhibitor that features an asymmetric aldol reaction using a titanium enolate, diastereoselective Grignard addition to a tert-butanesulfinyl aldimine, and ring closing olefin metathesis as key steps.
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
B?se, Dietrich,Frey, Wolfgang,Pietruszka, J?rg
supporting information, p. 2524 - 2532 (2014/11/08)
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.
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
B?se, Dietrich,Frey, Wolfgang,Pietruszka, J?rg
supporting information, p. 2524 - 2532 (2015/12/26)
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.
Total synthesis of(±)-neovibsanin b
Imagawa, Hiroshi,Saijo, Hayato,Kurisaki, Takahiro,Yamamoto, Hirofumi,Kubo, Miwa,Fukuyama, Yoshiyasu,Nishizawa, Mugio
supporting information; experimental part, p. 1253 - 1255 (2009/09/25)
(±)-Neovibsanin B was synthesized based on a DMI-accelerated intramolecular Diels-Alder reaction followed by oxy-Michael addition- lactonization. The synthetic (±)-neovibsanin B induced similar morphological changes in NGF-mediated PC12 cells compared wit
