一些与丙氨酸和6-脱氧甘露基野尻霉素相关的糖氨基酸的合成与结构测定

Synthesis and structure determination of some sugar amino acids related to alanine and 6-deoxymannojirimycin.

作者信息

Koós M, Steiner B, Micová J, Langer V, Durík M, Gyepesová D

机构信息

Institute of Chemistry, Slovak Academy of Sciences, Dúbravská cesta 9, SK-84238, Bratislava, Slovak Republic.

出版信息

Carbohydr Res. 2001 Jun 15;332(4):351-61. doi: 10.1016/s0008-6215(01)00109-4.

DOI:10.1016/s0008-6215(01)00109-4

PMID:11438092

Abstract

(5'R)-5'-Methyl-5'-[methyl (4S)-2,3-O-isopropylidene-beta-L-erythrofuranosid-4-C-yl]-imidazolidin-2',4'-dione was synthesised starting from methyl 6-deoxy-2,3-O-isopropylidene-alpha-D-lyxo-hexofuranosid-5-ulose applying the Bucherer-Bergs reaction. Its 5'-R configuration was confirmed by X-ray crystallography. Corresponding alpha-amino acid-methyl (5R)-5-amino-5-C-carboxy-5,6-dideoxy-alpha-D-lyxo-hexofuranoside (alternative name: 2-[methyl (4S)-2,3-O-isopropylidene-beta-L-erythrofuranosid-4-C-yl]-D-alanine) was obtained from the above hydantoin by acid hydrolysis of the isopropylidene group followed by basic hydrolysis of the hydantoin ring. Total deprotection afforded 5-C-carboxy-6-deoxymannojirimycin. Analogously, methyl (5S)-5-amino-5-C-carboxy-5,6-dideoxy-alpha-L-lyxo-hexofuranoside and 5-C-carboxy-6-deoxy-L-mannojirimycin were prepared from the corresponding (5'S)-5'-methyl-5'-[methyl (4R)-2,3-O-isopropylidene-beta-D-erythrofuranosid-4-C-yl]-imidazolidin-2',4'-dione starting from methyl 6-deoxy-2,3-O-isopropylidene-alpha-L-lyxo-hexofuranosid-5-ulose.

摘要

以6-脱氧-2,3-O-异亚丙基-α-D-吡喃阿洛糖-5-酮为原料，通过布赫勒尔-贝格斯反应合成了(5'R)-5'-甲基-5'-[甲基(4S)-2,3-O-异亚丙基-β-L-赤藓呋喃糖苷-4-C-基]-咪唑啉-2',4'-二酮。其5'-R构型通过X射线晶体学得到确证。通过对异亚丙基进行酸水解，然后对咪唑啉环进行碱水解，从上述乙内酰脲中得到相应的α-氨基酸-甲基(5R)-5-氨基-5-C-羧基-5,6-二脱氧-α-D-吡喃阿洛糖苷（别名：2-[甲基(4S)-2,3-O-异亚丙基-β-L-赤藓呋喃糖苷-4-C-基]-D-丙氨酸）。完全脱保护得到5-C-羧基-6-脱氧甘露基吉里霉素。类似地，从相应的(5'S)-5'-甲基-5'-[甲基(4R)-2,3-O-异亚丙基-β-D-赤藓呋喃糖苷-4-C-基]-咪唑啉-2',4'-二酮出发，以6-脱氧-2,3-O-异亚丙基-α-L-吡喃阿洛糖-5-酮为原料，制备了甲基(5S)-5-氨基-5-C-羧基-5,6-二脱氧-α-L-吡喃阿洛糖苷和5-C-羧基-6-脱氧-L-甘露基吉里霉素。