- Intramolecular Photoreactions of (5S)-5-Oxymethyl-2(5H)-furanones as a Tool for the Stereoselective Generation of Diverse Polycyclic Scaffolds
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The photoactivated evolution of a series of enantiomerically pure 5-oxymethyl-2(5H)-furanones has been investigated. The observed intramolecular photoreactions have proven to be a straightforward entry to diverse and stereochemically rich fragment-molecul
- Lejeune, Guillaume,Font, Josep,Parella, Teodor,Alibés, Ramon,Figueredo, Marta
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- High-Yielding Diastereoselective syn-Dihydroxylation of Protected HBO: An Access to D-(+)-Ribono-1,4-lactone and 5-O-Protected Analogues
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A diastereoselective chemoenzymatic synthetic pathway to D-(+)-ribono-1,4-lactone, a versatile chiral sugar derivative widely used for the synthesis of various natural products, has been designed from cellulose-based levoglucosenone (LGO). This route involves a sustainable Baeyer-Villiger oxidation of LGO to produce enantiopure (S)-γ-hydroxymethyl-α,β-butenolide (HBO) that is further functionalized with various protecting groups to provide 5-O-protected γ-hydroxymethyl-α,β-butenolides. The latter then undergo a diastereoselective and high-yielding syn-dihydroxylation of the α,β-unsaturated lactone moiety followed by a deprotection step to give D-(+)-ribono-1,4-lactone. Through this 4-step synthetic route from LGO, D-(+)-ribono-1,4-lactone is obtained with d.r. varying from 82:18 to 97:3 and in overall yields between 32 and 41 % depending on the protecting group used. Moreover, valuable synthetic intermediates 5-O-tert-butyldimethylsilyl-, 5-O-tert-butyldiphenylsilyl- as well as 5-O-benzyl-ribono-1,4-lactones are obtained in 3 steps from LGO in 58, 61 and 40 %, respectively.
- Moreaux, Maxime,Bonneau, Guillaume,Peru, Aurélien,Brunissen, Fanny,Janvier, Marine,Haudrechy, Arnaud,Allais, Florent
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p. 1600 - 1604
(2019/01/14)
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- Stereoselective photochemical 1,3-dioxolane addition to 5-alkoxymethyl-2(5H)-furanone: Synthesis of bis-tetrahydrofuranyl ligand for HIV protease inhibitor UIC-94017 (TMC-114)
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A convenient synthesis of (3R,3aS,6aR)-3-hydroxyhexahydrofuro[2,3-b]furan, a high-affinity non-peptidal ligand for HIV protease inhibitor UIC-94017, is described. This inhibitor is undergoing advanced clinical trials. The synthesis utilizes a novel stereoselective photochemical 1,3-dioxolane addition to 5(S)-benzyloxymethyl-2(5H)-furanone as the key step. The requisite furanone derivative was prepared in high enantiomeric excess by an immobilized lipase-catalyzed selective acylation of (±)-1-(benzyloxy)-3-buten-2-ol and a ring-closing olefin metathesis with Grubbs' catalyst. Optically active bis-THF was converted to protease inhibitor 2 (UIC-94017).
- Ghosh, Arun K.,Leshchenko, Sofiya,Noetzel, Marcus
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p. 7822 - 7829
(2007/10/03)
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- METHOD OF PREPARING (3R, 3aS, 6aR) -3- HYDROXYHEXAHYDROFURO [2, 3-b] FURAN AND RELATED COMPOUNDS
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A method of synthesizing (3R, 3aS, 6aR) -3- hydroxyhexahydrofuro [2, 3-b] furan (I), and related compounds, in high yield and high enantiomeric selectivity is disclosed. Also disclosed is a method of manufacturing (5S) -5-(benzyloxymethyl) -5H-furan-2-one.
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- Synthesis of optically active 4-benzyloxymethyl- and 4-(4-methoxyphenoxy)methylbuten-2-olides via lipase-mediated resolution
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A new preparation of optically active 4-benzyloxymethyl- and 4-(4-methoxyphenoxy)methylbuten-2-olides has been developed by employing lipase-mediated resolution and palladium-mediated carbomethoxylation as key steps.
- Takano,Setoh,Yamada,Ogasawara
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p. 1253 - 1256
(2007/10/02)
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- PREPARATION OF ENANTIOMERICALLY PURE BUTENOLIDES: 4-HYDROXYMETHYL BUTYROLACTONE DERIVATIVES FROM (+)-(R)-3-(4-METHYLPHENYL)SULPHINYLPROPIONIC ACID
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The condensation of the dilithium derivative of (+)-(R)-3-sulphinyl propionic acid on protected glycolaldehydes allowed to obtain both enantiomeres of 4-alkoxymethylbutenolides in optically pure form.When glycolic esters were employed as electrophiles, re
- Bravo, Pierfrancesco,Resnati, Giuseppe,Viani, Fiorenza
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p. 747 - 750
(2007/10/02)
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- ASYMMETRIC TOTAL SYNTHESIS OF NATURAL (-)- AND UNNATURAL (+)-STEGANACIN DETERMINATION OF THE ABSOLUTE CONFIGURATION OF NATURAL ANTITUMOR STEGANACIN
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A virtually complete asymmetric control in the synthesis of 2,3-disubstituted butan-4-olide (10) was demonstrated by employing the butenolide (12) as the chiral acceptor for the conjugate 1,4-addition.Highly efficient asymmetric total synthesis of natural (-)- and unnatural (+)-steganacin was accomplished.The absolute stereostructure of natural antitumor steganacin was determined to be 1.
- Tomioka, Kiyoshi,Ishiguro, Tsuneo,Iitaka, Yoichi,Koga, Kenji
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p. 1303 - 1312
(2007/10/02)
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- STUDIES ON STRUCTURALLY SIMPLE α,β-BUTENOLIDES-II (-)-(S)-γ-HYDROXYMETHYL-α,β-BUTENOLIDE AND DERIVATIVES FROM D-RIBONOLACTONE EFFICIENT SYNTHESIS OF (-)-RANUNCULIN
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A short synthesis of the title compound, 16, from D-ribonolactone is described.Two alternative approaches differing in the timing of the C=C double bond creation are used to prepare some chiral derivatives of 16. (-)-Ranunculin, a glycoside present in Ranunculaceae, has been synthetized for the first time.
- Camps, P.,Cardellach, J.,Font, J.,Ortuno, R. M.,Ponsati, O
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p. 2395 - 2402
(2007/10/02)
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- A SHORT SYNTHESYS OF (S)-5-HYDROXYMETHYL-(5H)-FURAN-2-ONE AND DERIVATIVES FROM D-RIBONOLACTONE
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We describe a short synthesis of (S)-5-hydroxymethyl-(5H)-furan-2-one and some 5-O-derivatives, which are being used as key starting products for the synthesis of several antileukaemic lignan lactones, from D-ribonolactone.
- Camps, P.,Font, J.,Ponsati, O.
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p. 1471 - 1472
(2007/10/02)
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