Alcohol-Directed ortho-C–H Alkenylation

Li, Li; Liu, Qinglan; Chen, Jiean; Huang, Yong

doi:10.1055/s-0037-1611538

Cited by 12 publications

(11 citation statements)

References 7 publications

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“…Subjection of 1 to the cycloaddition cascade with 2-methoxyfuran afforded the bicyclic tetrasubstituted arene 8 ; reduction of both esters ( 9 ) followed by selective hydrogenolysis of the benzylic alcohol gave 10 . To introduce the required hydroxymethyl group onto the benzene ring, the remaining alcohol was then utilized in a hydroxyl-directed ortho C–H alkenylation; pleasingly, this afforded enoate 11 in a 58% yield, which was advanced to the natural product in a further four steps (65%).…”

Section: Resultsmentioning

confidence: 99%

Collective Synthesis of Illudalane Sesquiterpenes via Cascade Inverse Electron Demand (4 + 2) Cycloadditions of Thiophene S,S-Dioxides

et al. 2022

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Thiophene S,S-dioxides are underutilized tools for the de novo construction of benzene rings in organic synthesis. We report a collective synthesis of nine illudalane sesquiterpenes using bicyclic thiophene S,S-dioxides as generalized precursors to the indane core of the natural products. Exploiting furans as unusual dienophiles in this inverse electron demand Diels–Alder cascade, this concise and convergent approach enables the synthesis of these targets in as little as five steps. Theoretical studies rationalize the reactivity of thiophene S,S-dioxides with both electron-poor and electron-rich dienophiles and reveal reaction pathways involving either nonpolar pericyclic or bifurcating ambimodal cycloadditions. Overall, this work demonstrates the wider potential of thiophene S,S-dioxides as convenient and flexible precursors to polysubstituted arenes.

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Section: Resultsmentioning

confidence: 99%

Collective Synthesis of Illudalane Sesquiterpenes via Cascade Inverse Electron Demand (4 + 2) Cycloadditions of Thiophene S,S-Dioxides

et al. 2022

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“… XRD patterns for (a) Cu/SiO 2 [38] ((a) Cu/SiO 2 treated with Ca(OH) 2 solution at 473 K; (b) Cu/SiO 2 after a one run; (c) spent Cu/SiO 2 after three runs; (d) spent Cu/SiO 2 after four runs; (e) the sample in (d) was re‐calcined; (f) the sample in (e) was reduced. ), (b) Ni/Ce−TiO 2 [37] (a and f: 623 K, b: 673 K, c: 723 K, d: 773 K, e: 823 K), (c) Ni−Cu/SiO 2 [36] ((a) reduced Ni−Cu/SiO 2 , (b) used Ni−Cu/SiO 2 after 5 runs, (c) reduced Cu/SiO 2 , (d) used Cu/SiO 2 after 5 runs.…”

Section: Performance Of Hydrogenolysis Of Xylitol In the Presence Of H2mentioning

confidence: 99%

Catalytic Deoxygenation of Xylitol to Renewable Chemicals: Advances on Catalyst Design and Mechanistic Studies

Xia

Jin

Zhang

et al. 2020

The Chemical Record

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Xylitol is commonly known as one of the top platform intermediates for biomass conversion. Catalytic deoxygenation of xylitol provides an atomic and energetic efficient way to produce a variety of renewable chemicals including ethylene glycol, 1,2‐propanediol, lactic acid and 1,4‐anhydroxylitol. Despite a few initial attempts in converting xylitol into those products, improving catalyst selectivity towards C−O and C−C cleavage reactions remains a grand challenge in this area. To our best knowledge, there is lack of comprehensive review to summarize the most recent advances on catalyst design and mechanisms in deoxygenation of xylitol, offering important perspective into future development of xylitol transformation technologies. Therefore, in this mini‐review, we have critically discussed the conversion routes involved in xylitol deoxygenation over solid catalyst materials, the nanostructures of supported metal catalysts for C−H, C−C and C−O bond cleavage reactions, and mechanistic investigation for xylitol conversion. The outcome of this work provides new insights into rational design of effective deoxygenation catalyst materials for upgrading of xylitol and future process development in converting hemicellulosic biomass.

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“…However,when CDI/triphosgene was replaced by N,N'-disuccinimidyl carbonate (DSC) side-product formation was minimised and building block B2 (180) was obtained in almost quantitative yield. [124][125][126] Buildingb lock B3 was synthesised startingf rom protected cyclopropyla mino acid 160,w hich was also used in the synthesis of simeprevir. [113,114] Hydrolysis of the ethyl ester of 160 followed by coupling with cyclopropyl sulphonamide using CDIp rovided acyl sulfonamide 181.H ydrogenation of 181 over 5% Ru/C and subsequentB oc depro- tection of 182 completed the synthesis of amine building block B3 (183).…”

Section: Hcv Ns3/4aprotease Inhibitorsmentioning

confidence: 99%

“…RifamycinB(31)a nd its semi-synthetic derivatives are 24-membered macrocyclest hat originate from the class of ansamycin natural products (Figure 5). They have high MWs (823-877 Da), > 10 HBAs and 5-6 hydrogen bond donors (HBDs) and are among the most structurally complex bRo5 drugs approved in the last three decades (SMCM [123][124][125][126][127][128][129][130][131][132][133][134][135][136][137][138][139]. Rifamycins are antibacteriala gents that are used to treat tuberculosis,a ided by their accumulation in the lungs and macrophages.…”

Section: Rifamycinsmentioning

confidence: 99%

Drug Syntheses Beyond the Rule of 5

Tyagi

Begnini

Poongavanam

et al. 2019

Chemistry A European J

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Drugs in the chemical space beyond the rule of 5 (bRo5) can modulate targets with difficult binding sites while retaining cell permeability and oral absorption. Reviewing the syntheses of bRo5 drugs approved since 1990 highlights synthetic chemistry's contribution to drug discovery in this space. Initially, bRo5 drugs were mainly natural products and semi‐synthetic derivatives. Later, peptidomimetics and de novo designed compounds, that include up to seven chiral centres and macrocyclic rings became dominant. These drugs are prepared by total synthesis, sometimes by routes of more than 25 steps with stereocentres originating from the chiral pool, or being installed by chiral induction or enzymatic resolution. Interestingly, ring‐closing metathesis proved to be the method of choice for macrocyclisation in hepatitis C virus protease inhibitors. We conclude that structural simplification, planning of synthetic routes regarding incorporation of stereocentres and macrocyclisation, as well as incorporation of structural knowledge and consideration of chameleonic properties in design, should facilitate drug discovery in bRo5 space.

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Alcohol-Directed ortho-C–H Alkenylation

Cited by 12 publications

References 7 publications

Collective Synthesis of Illudalane Sesquiterpenes via Cascade Inverse Electron Demand (4 + 2) Cycloadditions of Thiophene S,S-Dioxides

Collective Synthesis of Illudalane Sesquiterpenes via Cascade Inverse Electron Demand (4 + 2) Cycloadditions of Thiophene S,S-Dioxides

Catalytic Deoxygenation of Xylitol to Renewable Chemicals: Advances on Catalyst Design and Mechanistic Studies

Drug Syntheses Beyond the Rule of 5

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