Synthesis of (1→6)-2,5-anhydro-D-glucitol through cyclopolymerization of 3,4-di-O-allyl-1,2 : 5,6-dianhydro-D-mannitol and optical resolution ability of its derivative in HPLC

✍ Scribed by Satoshi Umeda; Toshifumi Satoh; Kei Saitoh; Kazuaki Yokota; Toyoji Kakuchi

• Publisher: John Wiley and Sons
• Year: 1998
• Tongue: English
• Weight: 185 KB
• Volume: 36
• Category: Article
• ISSN: 0887-624X
• DOI: 10.1002/(sici)1099-0518(19980430)36:6<901::aid-pola5>3.0.co;2-j

✦ Synopsis

The cyclopolymerization of 3,4-di-O-allyl-1,2 : 5,6-dianhydro-D-mannitol ( 1) was carried out using BF 3 rOEt 2 and t-BuOK. The polymer obtained by the polymerization with BF 3 rOEt 2 mainly consisted of (1r6)-bonded 3,4-di-O-allyl-2,5-anhydro-Dglucitol as the five-membered constitutional repeating unit, though it contained a small amount of other cyclic repeating units. On the other hand, during the polymerization using t-BuOK, the stereoregular polymer (1 r6)-linked 3,4-di-O-allyl-2,5-anhydro-Dglucitol (2) was synthesized via a regio-and stereoselective mechanism. Cleavage of the allyl ether linkage in polymer 2 occurred to produce the polymer consisting of only 2,5-anhydro-D-glucitol units, i.e., (1r6)-2,5-anhydro-D-glucitol (3). Chromatographic enantioseparation of chloroquine and tro ¨ger base has been performed on (3,5-dimethylphenyl)carbamate and 4-methylbenzoate derivatives of 3 as a chiral stationary phase for high-performance liquid chromatography.