A5005153343- Traditional and Medicinal Uses of Annonaceae
- Crystallization and Solubility Studies
- X-ray Diffraction in Crystallography
- Cocoa and Sweet Potato Agronomy
- Crystallography and molecular interactions
- Asymmetric Synthesis and Catalysis
- Alkaloids: synthesis and pharmacology
- Phytochemical compounds biological activities
- Synthetic Organic Chemistry Methods
- Carbohydrate Chemistry and Synthesis
- Plant and Fungal Species Descriptions
- Marine Sponges and Natural Products
- Chemical synthesis and alkaloids
- Catalytic C–H Functionalization Methods
- Oxidative Organic Chemistry Reactions
- Cyclopropane Reaction Mechanisms
- Microbial Natural Products and Biosynthesis
- Axial and Atropisomeric Chirality Synthesis
- Asymmetric Hydrogenation and Catalysis
- Chemical Synthesis and Analysis
- Catalytic Alkyne Reactions
- Radical Photochemical Reactions
- Molecular spectroscopy and chirality
- Bioactive Compounds and Antitumor Agents
- Natural product bioactivities and synthesis
Nagasaki International University
2024-2025
Kyoto Pharmaceutical University
2014-2024
Cambridge Crystallographic Data Centre
2020
Kyoto College of Medical Science
2014
Osaka University
2003-2012
Osaka Ohtani University
2007
Kitasato University
2005-2006
Japan Science and Technology Agency
2006
Kitasato Institute Hospital
2005
Osaka University of Pharmaceutical Sciences
2000
The enantioselective total synthesis of (+)-hexachlorosulfolipid, a cytotoxin found in the Adriatic mussel Mytilus galloprovincialis, is described. unique chlorinated hydrocarbon motif lipid successfully furnished by series dichlorination reactions chiral epoxides with chlorophosphonium reagent generated situ from Ph3P/NCS. present has allowed confirmation absolute configuration natural cytotoxic (+)-hexachlorosulfolipid originally proposed Fattorusso, Ciminiello, and co-workers.
Building on our previously reported techniques, we developed a concise and highly stereoselective synthesis method for β,β-disubstituted α,β-unsaturated esters. This comprises 3 reactions: the aldol reaction of acetic ester derivatives with ketones, acetylation tert-alcohols, an elimination utilizing 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU). During process, anhydride 4-dimethylaminopyridine (DMAP) facilitated smooth bulky tert-alcohols; however, employing DBU as base reduced yields....
Palladium-catalyzed cascade C-H alkenylation and arylation provides convenient access to polycyclic aromatic compounds. Treatment of 3-bromoaniline derivatives bearing a bromocinnamyl group on the nitrogen atom with catalytic amount [Pd(OAc)(2)] PCy(3)·HBF(4) in presence Cs(2)CO(3) dioxane affords naphthalene-fused indole good yields. This double cyclization reaction is also applicable heterocyclic substrates, giving fused indoles containing heteroaromatic ring such as dibenzofuran,...
Abstract Previously we synthesized JCI ‐20679, a novel thiophene‐3‐carboxamide analog of annonaceous acetogenins which have shown potent antitumor activity, with no serious side effects, in mouse xenograft models. In this study, investigated the mechanism ‐20679. The growth inhibition profile (termed “fingerprint”) agent across panel 39 human cancer cell lines “ JFCR 39”) was measured; fingerprint analyzed by COMPARE algorithm utilizing entire drug sensitivity database for panel....
All eight diastereoisomers of the monotetrahydrofuran-ring cores annonaceous acetogenins have been synthesized through utilization asymmetric alkynylation and stereodivergent one-pot tetrahydrofuran-ring formation. In all cases, proceeded with very high diastereoselectivity to give kinds optically pure tetrahydrofuran core from a common alpha-oxyaldehyde. We also describe comparison (1)H NMR, (13)C CD spectral data isomers full details construction including model study alkynylation.
Four stereoisomers of the THF cores, synthetic intermediates acetogenins, have been synthesized with high diastereoselectivity by asymmetric alkynylation and subsequent stereodivergent ring formation. The α-oxyaldehyde (S)-3-butyne-1,2-diol derivatives (C4-unit) gave good yields syn anti adducts >97:3 dr 94:6 dr, respectively. These were converted into four types compounds via one-pot formation or intramolecular Williamson synthesis.
A total synthesis of the threo/trans/erythro-type acetogenin mosin B and one its diastereomers has been achieved. The carbon skeleton is assembled in a convergent fashion from two segments (a THF ring segment gamma-lactone segment) through Nozaki-Hiyama-Kishi reaction. was stereoselectively constructed by stereodivergent starting common intermediate (4-cyclohexene-1,2-diol) based on desymmetrization strategy. synthesized coupling triflate chiral alpha-sulfenyl gamma-lactone. By virtue these...
A new heterocyclic compound, C(2)-symmetric bis-sulfoxide 1, has been found to be an efficient chiral auxiliary for asymmetric desymmetrization of cyclic meso-1,2-diols via diastereoselective acetal fission. Both (R,R)- and (S,S)-1 are readily synthesized with high optical purity oxidation 5-benzodithiepan-3-one (2). After acetalization 6a-e a mono-TMS ether 6f this the resulting acetals 7a-f were subjected base-promoted fission upon treatment potassium hexamethyldisilazide (KHMDS) followed...
The first and concise total synthesis of murisolin (1) was accomplished using asymmetric alkynylation Sonogashira coupling as the key steps. threo/trans/threo-type THF ring moiety constructed with excellent stereoselectivity by 1,6-heptadiyne to α-tetrahydrofuranic aldehyde, which also prepared via alkynylation.
Convergent total syntheses of murisolin (1), natural 16,19-cis-murisolin 2, and unnatural 3 were accomplished by asymmetric alkynylation alpha-tetrahydrofuranic aldehyde with a diyne Sonogashira coupling gamma-lactone segment as the key steps. Stereoisomers synthesized high optical purity these 1,6-heptadiyne proceeded in good yield diastereoselectivity. The cell-growth inhibition profile COMPARE analysis synthetic compounds 1-3 also investigated.
Systematic synthesis of bis-THF ring cores, synthetic intermediates adjacent annonaceous acetogenins, has been achieved by asymmetric alkynylation and subsequent stereodivergent THF formation. The α-tetrahydrofuranic aldehyde with (S)-3-butyne-1,2-diol derivatives gave good yields erythro- threo-adducts very high diastereoselectivity. These adducts were converted into four types cores via two kinds one-pot
[figure: see text] The first total synthesis of mosin B and a diastereomer was accomplished using asymmetric desymmetrization the sigma-symmetric diol Nozaki-Hiyama-Kishi reaction as key steps. THF core segment stereoselectively constructed employing stereodivergent starting from common intermediate, 4-cyclohexene-1,2-diol, based on strategy. By virtue these synthetic results, it is suggested that absolute configuration 1a.
Eight diastereoisomers of the bistetrahydrofuran ring cores annonaceous acetogenins have been synthesized by asymmetric alkynylation alpha-tetrahydrofuranic aldehydes and stereodivergent one-pot tetrahydrofuran (THF) formation. In all cases, proceeded with very high diastereoselectivity to give eight kinds optically pure THF cores. We also describe a comparison (1)H (13)C NMR spectral data isomers full details construction.
Abstract We have accomplished the first total synthesis of longimicin D ( 1 ), which displays potent cytotoxicity against human pancreatic carcinoma cells. The bis‐THF core bearing congested stereocenters was constructed by our methodology for poly‐THF cores, consists asymmetric alkynylation with C4 unit and stereodivergent THF ring formation. Although we had planned to join C9–C34 segment 2 C1–C8 γ‐lactone 3 , a model study revealed that coupling difficult. resolved problem applying...
The convergent synthesis of dansyl-labeled solamin, an antitumor Annonaceous acetogenin, has been achieved.The carbon skeleton was assembled from three fragments: the THF ring fragment, fluorescent and γ-lactone by asymmetric alkynylation.Annonaceous acetogenins are waxy derivatives long-chain fatty acids (C32 or C34) that linked a 2-propanol unit at C-2 position to form γ-methyl-α,β-unsaturated-γ-lactone. 1 Most characterized one 2,5-disubstituted tetrahydrofuran(s) (THFs) with two flanking...
The asymmetric alkynylation of aliphatic and aromatic aldehydes with propiolates was mediated by dialkylzinc a novel prolinol catalyst without high reagent loading any additives, such as Ti(Oi-Pr)4, to give the corresponding γ-hydroxy-α,β-acetylenic esters enantiomeric excess up 95%.