- High-Yielding Diastereoselective syn-Dihydroxylation of Protected HBO: An Access to D-(+)-Ribono-1,4-lactone and 5-O-Protected Analogues
-
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
-
supporting information
p. 1600 - 1604
(2019/01/14)
-
- A general and enantioselective approach to pentoses: A rapid synthesis of PSI-6130, the nucleoside core of sofosbuvir
-
An efficient route towards biologically relevant pentose derivatives is described. The de novo synthetic strategy features an enantioselective α-oxidation reaction enabled by a chiral amine in conjunction with copper(II) catalysis. A subsequent Mukaiyama aldol coupling allows for the incorporation of a wide array of modular two-carbon fragments. Lactone intermediates accessed via this route provide a useful platform for elaboration, as demonstrated by the preparation of a variety of C-nucleosides and fluorinated pentoses. Finally, this work has facilitated expedient syntheses of pharmaceutically active compounds currently in clinical use.
- Peifer, Manuel,Berger, Rapha?lle,Shurtleff, Valerie W.,Conrad, Jay C.,Macmillan, David W. C.
-
p. 5900 - 5903
(2014/05/20)
-
- A SHORT SYNTHESYS OF (S)-5-HYDROXYMETHYL-(5H)-FURAN-2-ONE AND DERIVATIVES FROM D-RIBONOLACTONE
-
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.
-
p. 1471 - 1472
(2007/10/02)
-