Regio-selective hydroxylation of gem-difluorinated octanes by alkane hydroxylase (AlkB)

Abstract gem -Difluoromethylene substituted molecules constitute a distinct class of fluorinated compounds. In this study, special chemistry has been developed for their preparation based on the highly selective terminal hydroxylation of these gem -difluorinated octanes by AlkB (alkane hydroxylase) from Pseudomonas putida Gpo1 to form gem -difluorinated octan-1-ols. The hydroxylation reaction is performed by whole-cell catalysis. Identification of the distal- and proximal-hydroxylation products was made by 1 H, 13 C, and 19 F NMR; GC and GC/MSD; and/or by comparison with authentic standards in GC. To the best of our knowledge, we have obtained the first synthesis of 2,2-, 3,3- and 4,4-difluorooctan-1-ols, from simple and inexpensive starting materials.