Diacetone-D-glucose

Reagent 7 is easily prepared from commercially available diacetone-D-glucose and trichloro(cyclopentadienyl)titanium35 (Section 1.3.3.3.8.1.). The monomeric structure of reagent 7 was confirmed by an X-ray crystal structure analysis1 7. Complex 9 is obtained36 analogously from (7 .7 )-tartaric acid derived (R,7 )-2,3-CMsopropylidene-l,l,4,4-tetraphenyl-1,2,3,4-butanetetrol. 

The Merck compound MK-0608 is a 2 -C-Me-7-deaza-adenosine analog, which has recently been reported to show a 5.7 log drop in viral load in HCV-infected chimpanzees after dosing QD at 2mg/kg (Olsen 2006). An efQcient and practical process for preparing kilogram quantities has been described (Bio et al. 2004). The 12-step synthesis provides an impressive 35% overall yield and starts from the inexpensive diacetone-D-glucose. The synthesis features a novel acyl migration in route to prepare the key crystalline furanose diol intermediate (Fig. 5). The conditions... 

L-aspartic acid L-tartaric acid Diacetone-D-glucose... 

In a variation of this method, Garcia Ruano and workers prepared 5-alkyl sulfinimines from the diacetone-D-glucose derived sulfinate 50.38 Subsequent treatment with LiHMDS, aldehyde, and CsF afforded S-te/t-butyl sulfinimines 51 in enantiomerically pure form.38... 

Eguchi, T, Koudate, T, Kakinuma, K, The Overman-rearrangement on a diacetone-D-glucose template, Tetrahedron, 49, 4527-4540, 1993. 

In the recent total synthesis of sphingofungin E (90), Overman rearrangement of an allylic trichloroacetimidate derived from diacetone-D-glucose 91 generated tetra-substituted carbon... 

In another paper from the Kakinuma group, further result on the chirality s transfer realized using the diacetone-D-glucose template was described [41]. 

A novel series of chiral grass herbicides based on the benzyloxy substituted tetrahydrofuran ring system has been prepared. These compounds are readily accessible synthetically from diacetone-D-glucose which serves as a chiral template possessing the appropriate stereochemistry for elaboration to the active herbicides. The degree of herbicidal activity is related to the molecular shape of these compounds and especially to the orientation of the substituents around the tetrahydrofuran ring. The chemistry and empirical structure-activity relationships of these compounds will be discussed. 

The first step in the 5-step synthesis sequence of RE 39571 involved benzylation of the commercially available diacetone-D-glucose with a-chloro-o-xylene employing either NaH or NaOH as base. The use of differently substituted benzyl halides afforded the corresponding substituted products. Selective deisopropylidenation at the 5,6-position with aqueous acetic acid then gave the terminal diol (Scheme 1). The terminally unsaturated sugar can be generated from the 5,6-diol via a... 

The 3-epimer sugar derivative was synthesized in a similar manner as the parent compound except that the hydroxyl group at the C-3 position in diacetone-D-glucose was initially epimerized (13) by oxidation with methyl sulfoxide and acetic anhydride followed by reduction with sodium borohydride. 

Di-0-isopropylidene-D-glucose (diacetone-D-glucose Aldrich Chemical Company, Inc., 98%) was used without purification. 

---