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The synthesis of fluorinated complex molecules via direct C(sp(3))-H fluorination is attractive yet remains challenging. Here we describe the Pd(II)-catalyzed fluorination of unactivated methylene C(sp(3))-H bonds by an inner-sphere mechanism. This method allows the site- and diastereoselective fluorination of β-methylene C(sp(3))-H bonds of α-amino acid derivatives. A range of substrates containing both aliphatic and benzylic C(sp(3))-H bonds were compatible with this protocol, leading to an array of β-fluorinated α-amino acids. Stoichiometric fluorination of an isolated palladacycle intermediate takes place rapidly under very mild reaction conditions (room temperature, 5-10 min). Data from preliminary mechanistic studies are consistent with direct C-F reductive elimination from a high-valent intermediate.

Data are presented for the amino acid and sugar compositions of gum talha (tahl), i.e. the exudate from Acacia seyal Del., and for four sequential Smith-degradation (SD) products (0.10, 0.19, 0.38, 1.60 and 2.22% N respectively). Gum talha, which is not permitted as a food additive, is liable to occur as a contaminant of shipments of legitimate gum arabic (Acacia senegal (L.) Willd.). The molar polysaccharide/protein ratio in the whole gum (113:1) decreased to 58:1, 27:1, 5.5:1 and 4:1 in the first, second, third and fourth SD products respectively. From previous studies, SD-IV is known to be a branched galactan; hydroxyproline, aspartic acid, serine, valine, proline, and leucine account jointly for 70% of its amino acids. The first SD eliminated large amounts of sugars (ca 50%, including all of the rhamnose and glucuronic acid present) but only very small amounts of amino acids (molar ratio 807/1). The second and third degradations eliminated all of the arabinose and 99% of the galactose originally present. The very small yield of the final SD product is an established characteristic of dextrorotatory Acacia exudates of the A. seyal type (Bentham's Gummiferae). Overall (four SD stages), 99.7% of the original sugars but only 91.3% of the amino acids were eliminated. Hydroxyproline accounts for ca 25% of the low amino acid content of A. seyal gum and each of its SD products; the proteinaceous enrichment of the branched galactan core also involves aspartic acid, glutamic acid and iso-leucine.(ABSTRACT TRUNCATED AT 250 WORDS)