cis-Arenediols as versatile chiral synthons in the synthesis of prostaglandins, cyclitols, carbohydrates, and alkaloids

The oxidation of simple benzene derivatives by a mutant of Pseudomonas putida, called 39-D, produces cis-arenediols (1). The diols are enantiomerically pure and can be used as synthons for the preparation of a variety of interesting compounds because of their stereochemistry and the special array of functional groups.

See: Figure 1

cis -Toluenedio] (2) served as a chiral intermediate in an efficient synthesis of enone (3). which has been used to attain prostaglandin Fra and Neplanocin A. The same diol (2) was transformed into both enantiomers of a terpene synthon (4).

See: Figures 2, 3, 4

Oxidative functionalization of cis-chlorobenzenediol (5) afforded intermediates suitable for transformation into L-erythrose (6), conduritol C (7), dihydroconduritol C (8) and aminoconduntol F-4 (9).

See: Figures 5, 6, 7, 8

The application of this versatile synthetic protocol culminated in an approach to kifunensine (10), an important glycosidase inhibitor, which was approached according to the following retrosynthetic analysis:

See: Figures 10, 11, 12, 5, 14, 13

A detailed study of the nucleophilic opening of epoxide 13 was carried out in order to better understand the parameters of the diastereoselective functionalization of arenediols. Details are provided for the oxidative functionalization of chlorobenzenediol (5), the key compound in all of the projects discussed.