Enantioselective synthesis of tetrafluorinated ribose and fructose

Abstract

A perfluoroalkylidene lithium mediated cyclisation approach for the enantioselective synthesis of a tetrafluorinated aldose (ribose) and of a tetrafluorinated ketose (fructose), both in the furanose and in the pyranose form, is described.

Advances in the Synthesis and Application of Tetrafluoroethylene‐ and 1,1,2,2‐Tetrafluoroethyl‐Containing Compounds

“…The nucleophilic intramolecular addition has become a popular method for the preparation of other fluorinated monosaccharides (Figure ). For instance, Linclau and co‐workers reported several new structures made from bromide 73 as derivatives of reported hexoses 79 and 80 – i.e., furanose 83 and pyranoses 84a , 84b , and 85 , respectively . Recently, they demonstrated enantioselective synthesis of dideoxy‐pyranoses 86 and 87 from 73 .…”

“…For instance, Linclau and co-workers reported several new structures made from bromide 73 as derivatives of reported hexoses 79 and 80 [127] -i.e., furanose 83 and pyranoses 84a, 84b, and 85, respectively. [133] Recently, they demonstrated enantioselective synthesis of dideoxy-pyranoses 86 and 87 from 73. [134] Bromide 73 also proved useful in the [136] Gouverneur and co-workers utilized bromide 73 for the synthesis of tetrafluorinated aryl-C-nucleosides as pure anomers (96 and 97), the former of which was even transformed to aryl-Cnucleotide 98 (Scheme 53).…”

Chemical Biology: What is Its Role in Drug Discovery?

“…Ducatti has reported the use of polysaccharides from red seaweed in the synthesis of useful carbohydrate building blocks . Others have described the synthesis of tetrafluorinated ribose and fructose (Linclau et al, 2009), 6-deoxy-6-fluorohexoses (Caravano et al, 2009), difluorinated carbasugar phosphates (Anderl et al, 2009), and pyrrolidine homoazasugars (Blanco et al, 2009). The synthesis of unnatural inositol phosphates, 4-C-methyl-Ins(1,4,5)P 3 and 4-C-methyl-Ins(1,3,4,5)P 4 has been reported (Swarbrick et al, 2009).…”

Titanium tetrafluoride: An efficient Lewis acid and fluorinating agent for stereoselective synthesis of 4-fluorotetrahydropyran

“…Similarly deoxyfluorosugars have been used to probe the mechanism of action of various enzymes [7]. Recently, the synthesis of fluorinated sugars and related heterocycles is gaining importance due to their varied biological activity [8][9][10][11][12]. The synthesis of substituted tetrahydropyran unit is important in organic chemistry because of its presence in many biologically active natural products [13][14][15][16][17][18][19][20].…”