Synthesis of Fluorinated Chitin Derivatives via Enzymatic Polymerization

Summary: Synthesis of fluorinated chitin derivatives has been achieved using chitinase from Bacillus sp. as a catalyst. 6′‐Fluoro‐ ( 1a ), 6‐fluoro‐ ( 1b ) and 6,6′‐difluoro‐ ( 1c ) chitobiose oxazoline derivatives were newly prepared as TSAS monomers for chitinase. Ring‐opening polyaddition of these monomers proceeded effectively at pH 8.0–9.0 and 30–40 °C, giving rise to alternatingly 6‐fluorinated chitin derivatives ( 2a and 2b ) from 1a and 1b , and fully 6‐fluorinated chitin derivative ( 2c ) from 1c under total control of regioselectivity and stereochemistry. XRD measurements revealed that polysaccharides 2a and 2b had crystalline structures similar to that of α ‐chitin.