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	一个多用途吡咯烷类氮杂糖中间体的不对称合成; Asymmetric Synthesis of a Key Intermediate for the Synthesis of Pyrrolidine Azasugars
	卓碧钦 ; 王小刚 ; 黄培强
	2011
关键词	吡咯烷 氮杂糖 糖苷酶抑制剂 合成等效体 氮杂半缩醛 pyrrolidine azasugars glycosidase inhibitors synthetic equivalents aza-hemiacetals
英文摘要	报道了多用途的吡咯烷类氮杂糖中间体6的不对称合成.起始原料(2r,3r,4S)-2-苄氧甲基-3,4-二苄氧基-5-氧代吡咯烷-1-羧酸叔丁酯(8)由手性合成砌块酒石酸酰亚胺7按照先前本实验室报道的方法经4步得到.活化的酰胺8经乙烯基加成、立体选择性还原、环化、氧化断裂双键成醛以及还原醛成醇等步骤得到了氮杂糖中间体(2r,3r,4r,5r)-2-羟甲基-3,4-二苄氧基-5-苄氧甲基吡咯烷-1-羧酸叔丁酯(6).从活化的酰胺8出发,经过5步反应,立体选择性地合成了氮杂糖中间体6,总产率46%.中间体6可用于多个吡咯烷类氮杂糖的合成.; A convenient asymmetric synthesis of the protected polyhydroxylated pyrrolidine 6,a key intermediate for the synthesis of pyrrolidine azasugars is reported.The synthesis started with tert-butyl(2R,3R,4S)-3,4-bis(benzyloxy)-2-(benzyloxymethyl)-5-oxopyrrolidine-1-carboxylate 8,which was derived from the fully protected D-tartarimide 7 in 62% overall yield.Addition of vinylmagnesium bromide with compound 8 at-78 ℃ for 2 h afforded the aza-hemiacetal 9a and its tautomer 9b,which,without separation,were treated with NaBH4/CeCl3·H2O to give the reduced product 10 as the only observable diastereomer in 90% yield.Under the mesylation conditions(MsCl:2.0 equiv,Et3N:3 equiv,CH2Cl2,12 h),compound 10 was converted directly to the cyclized product 12 in 89% yield.Oxidative cleavage(RuCl3-NaIO4,MeCN/H2O,rt) of the olefin 12 followed by reduction of the crude aldehyde 13 with NaBH4 afforded the desired pyrrolidine 6,tert-butyl(2R,3R,4R,5R)-3,4-bis(benzyloxy)-2-(benzyloxymethyl)-5-(hydroxy-methyl)pyrrolidine-1-carboxylate in 58% overall yield from 12.Thus,using vinyl group as a synthetic equivalent of hydroxymethyl group,pyrrolidine 6 was synthesized from building block 8 in 46% overall yield.Pyrrolidine 6 is a key intermediate for the synthesis of DMDP and other pyrrolidine azasugars.; 国家自然科学基金项目(20832005)
语种	zh_CN
内容类型	期刊论文
源URL	[http://dspace.xmu.edu.cn/handle/2288/106593]
专题	化学化工－已发表论文
推荐引用方式 GB/T 7714	卓碧钦,王小刚,黄培强. 一个多用途吡咯烷类氮杂糖中间体的不对称合成, Asymmetric Synthesis of a Key Intermediate for the Synthesis of Pyrrolidine Azasugars[J],2011.
APA	卓碧钦,王小刚,&黄培强.(2011).一个多用途吡咯烷类氮杂糖中间体的不对称合成..
MLA	卓碧钦,et al."一个多用途吡咯烷类氮杂糖中间体的不对称合成".(2011).

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