High-Yielding Diastereoselective syn -Dihydroxylation of Protected HBO: An Access to D-(+)-Ribono-1,4-lactone and 5- O -Protected Analogues

Maxime Moreaux (1, 2) , Guillaume Bonneau (1, 2) , Aurélien Peru (1) , Fanny Brunissen (1) , Marine Janvier (1) , Arnaud Haudrechy (2) , Florent Allais (1)

1 ABI - Agro-Biotechnologies Industrielles
2 ICMR - Institut de Chimie Moléculaire de Reims - UMR 7312

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.

Domaines: Chimie organique

Maxime Moreaux, Guillaume Bonneau, Aurélien Peru, Fanny Brunissen, Marine Janvier, et al.. High-Yielding Diastereoselective syn -Dihydroxylation of Protected HBO: An Access to D-(+)-Ribono-1,4-lactone and 5- O -Protected Analogues. European Journal of Organic Chemistry, 2019, 2019 (7), pp.1600-1604. ⟨10.1002/ejoc.201801780⟩. ⟨hal-02052678⟩