Stereospecific Synthesis of Protected Gal(α1→2)Glc
TANG Qiu-e， SHI Shen-de， CHEN Lang-qiu， LU Gao-chao， ZENG Sen， LIU Yu-miao
Author information+
College of Chemistry， Key Laboratory of Environmentally Friendly Chemistry and Application of Ministry of Education， Xiangtan University， Xiangtan 411105，China
{{custom_zuoZheDiZhi}}
{{custom_authorNodes}}
{{custom_bio.content}}
{{custom_bio.content}}
{{custom_authorNodes}}
Collapse
History+
Received
Revised
Published
2011-11-18
2012-10-18
2012-10-18
Issue Date
2012-10-18
Abstract
OBJECTIVE To stereospecifically synthesize disaccharide galactopyranosyl(α1→2)glucopyranoside with protecting groups which are easily and selectively deprotected. METHODS With D-glucose as a raw material， a donor methyl 3，4，6-tri-O-benzoyl-β-D-glucopyranoside was synthesized through acetylation， bromination， methylation， deacetylation， benzylidenation， selective benzoylation， chloroacetylation， and dechloroacetylation；the glucopyranosyl acceptor and a donor isopropyl 3-O-allyl-2-O-benzoyl-4，6-O-benzylidene-β-D-1-thiogalactopyranoside were reacted at catalysis to achieve an α-coupled product. RESULTS At the catalysis of TMSOTf/NIS， galactopyranosyl donor and glucopyranosyl acceptor were coupled to afford stereospecifically a full protected disaccharide galactopyranosyl(α1→2)glucopyranoside fragment， methyl 3-O-allyl-2-O-benzoyl-4，6-O-benzylidene-α-D-galactopyranosyl(1→2)-3，4，6-tri-O-benzoyl-β-D-glucopyranoside. All products were characterized with NMR and MS etc. CONCLUSION A full protected 1，2-cis disaccharide fragment was stereospecifically obtained through coupling reaction due to concerted effect of the special configurations of the galactopyranosyl donor and the glucopyranosyl acceptor.
TANG Qiu-e， SHI Shen-de， CHEN Lang-qiu， LU Gao-chao， ZENG Sen， LIU Yu-miao.
Stereospecific Synthesis of Protected Gal(α1→2)Glc[J]. Chinese Pharmaceutical Journal, 2012, 47(19): 1592-1597
{{custom_sec.title}}
{{custom_sec.title}}
{{custom_sec.content}}
References
[1] GHAZARIAN H， IDONI B， OPPENHEIMER S B. A glycobiology review： carbohydrates， lectins and implications in cancer therapeutics[J]. Acta Histochem， 2011，113（1）： 236-247. [2] CHEN L， SHI S D， LIU Y Q， et al. Studies on the stereoselective synthesis of a protected α-D-Gal-(1→2)-D-Glc fragment[J]. Carbohydr Res， 2011， 346(10)： 1250-1256. [3] ZHU X， SCHMIDT R R. New principles for glycoside-bond formation[J]. Angew Chem Int Ed， 2009， 48（26）： 1900-1934. [4] LI Z， ZHU L， KALIKANDA J. Development of a highly α-selective galactopyranosyl donor based on a rational design[J]. Tetrahedron Lett， 2011， 52（67）： 5629-5632. [5] JEON I， LEE D， KRAUSS I J， et al. A new model for the presentation of tumor-associated antigens and the quest for an anticancer vaccine： a solution to the synthesis challenge via ring-closing metathesis[J]. J Am Chem Soc， 2009， 131(40)： 14337-14344. [6] FU Q F， GOWDA D C. Carbohydrate-directed conjugation of cobra venom factor to antibody by selective derivatization of the terminal galactose residues[J]. Bioconjug Chem， 2001， 12（1）： 271-279. [7] LI K， LUO J， WANG C， et al. α-Galactosylceramide potently augments M2e-induced protective immunity against highly pathogenic H5N1 avian influenza virus infection in mice[J]. Vaccine， 2011， 29（44）： 7711-7717. [8] LUO S Y， KULKARNI S S， CHOU C H， et al. A concise synthesis of tetrahydroxy-LCB， α-galactosyl ceramide， and 1，4-dideoxy-1，4-imino-L-ribitol via D-allosamines as key building blocks[J]. J Org Chem， 2006， 71（24）： 1226-1229. [9] CHEN L， KONG F. Unusual α-glycosylation with galactosyl donors with a C2 ester capable of neighboring group participation[J]. Tetrahedron Lett， 2003， 44(18)： 3691-3695. [10] CHEN L Q， LAI D， GUO Q， et al. Synthesis of p-methoxyphenyl 3-O-allyl-2-O-benzoyl-4，6-O-benzylidene-α-D-galactopyranosyl-(1→4)-6-O-acetyl-2，3-di-O-benzoyl-β-D-glucopyranose[J]. Nat Sci J Xiangtan Univ（湘潭大学自然科学学报）， 2008， 30(4)： 89-93. [11] JEANLOZ R W， JEANLOZ D A. Partial esterification of methyl 4，6-O-benzylidene-α-D-glucopyranoside in pyridine solution[J]. J Am Chem Soc， 1957， 79(10)： 2579-2583. [12] WANG H， SHE J， ZHANG L H， et al. Silver(I) oxide mediated selective monoprotection of diols in pyranosides[J]. J Org Chem， 2004， 69(17)： 5774-5777. [13] CHEN L， KONG F. An efficient and practical synthesis of β-(1→3)-linked xylooligosaccharids[J]. Carbohydr Res， 2002， 337： 2335-2341. [14] WHISTLER R L， WOLFROM M L. Methods in Carbohydrate Chemistry[M]. Vol 2， New York： Academic Press， 1963： 221-222. [15] YI X， SHI S D， CHEN L Q， et al. Synthesis of protected disaccharide Galp(α1→2)Glcp[J]. Chin J Spectrosc Lab（光谱实验室）， 2011， 28(5)：2532-2535. [16] SHAFER C M， MOLINSKI T F. Practical synthesis of 2，6-dideoxy-D-lyxo-hexose(“2-deoxy-D-fucose”) from D-galactose[J]. Carbohydr Res， 1998， 310（4）： 223-228. [17] CHEN L Q， SHI S D， XIA S， et al. Stereoselective synthesis of protected galactopyranosyl(α1→2)glucopyranoside[J]. Chin Pharm J（中国药学杂志）， 2011， 46(8)： 630-634.
PDF(1329 KB)
