Haukaas M H, O'Doherty G A
Department of Chemistry, University of Minnesota, Minneapolis, Minnesota 55455, USA.
Org Lett. 2001 Feb 8;3(3):401-4. doi: 10.1021/ol006907j.
[figure: see text] The Sharpless catalytic asymmetric aminohydroxylation has been applied to 2-vinylfuran, producing beta-hydroxyfurfurylamine 5a with enantioexcess of > 86% and 21% yield from furfural. The Cbz and TBS protected amino alcohol 5a was converted into both the D- and L-isomers of deoxymannojirimycin (DMJ) and deoxygulonojirimycin in five to seven steps and 48% and 66% overall yields. The key steps include the use of an aza-Achmatowicz reaction, a diastereoselective Luche reduction, diastereoselective dihydroxylation, and a tandem Cbz deprotection/reductive amination.
[图：见正文] 夏普莱斯催化不对称氨羟基化反应已应用于2-乙烯基呋喃，以糠醛为原料，生成对映体过量大于86%且产率为21%的β-羟基糠胺5a。经五步至七步反应，Cbz和TBS保护的氨基醇5a被转化为脱氧甘露基吉里霉素（DMJ）和脱氧古洛糖基吉里霉素的D型和L型异构体，总产率分别为48%和66%。关键步骤包括使用氮杂-阿赫马托维奇反应、非对映选择性卢切还原反应、非对映选择性二羟基化反应以及串联的Cbz脱保护/还原胺化反应。
