A CONVENIENT PROCEDURE FOR THE SYNTHESIS OF 2,3,4,6-TETRA-O-BENZYL-D-GLUCONOLACTAM AND D-NOJIRILACTAM
A CONVENIENT PROCEDURE FOR THE SYNTHESIS OF 2,3,4,6-TETRA-O-BENZYL-D-GLUCONOLACTAM AND D-NOJIRILACTAM
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DOI：
10.1002/hlca.19930760435
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发表时间：
1993-01-01
影响因子：
1.8
通讯作者：
VASELLA, A
中科院分区：
文献类型：
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作者：
HOOS, R;NAUGHTON, AB;VASELLA, A
将2，3，4，6-四-O-苄基-D-葡萄糖（1）进行Swern氧化，然后进行氨解，得到结晶酰胺3，将其氧化（DMSO/吡啶）。SO 3），得到氧代-酰胺4和羟基-内酰胺5和6。通过用在CHCl 3中的AcOH处理完成4环化成非常缓慢平衡的5和6。根据NOE对羟基内酰胺的构型进行了归属。还原（Et 3SiH/BF 3. Et 2 O）单独或作为混合物的羟基-内酰胺得到2，3，4，6-四-O-苄基-D-内酰胺（7）。该方法基于专利的修改，不需要色谱法;从1到7的总产率为43%。7的氢解得到D-野尻内酰胺（8）;苄基化得到已知的五苄基-D-野尻内酰胺（9）和不饱和内酰胺10。
Swern oxidation of 2,3,4,6-tetra-O-benzyl-D-glucose (1) followed by ammonolysis gave the crystalline amide 3 which was oxidized (DMSO/pyridine . SO3) to yield the oxo-amide 4 and the hydroxy-lactams 5 and 6. Cyclization of 4 to the very slowly equilibrating 5 and 6 was completed by treatment with AcOH in CHCl3. The configuration of the hydroxy-lactams was assigned on the basis of NOEs. Reduction (Et3SiH/BF3 . Et2O) of the hydroxy-lactams either individually or as a mixture led to 2,3,4,6-tetra-O-benzyl-D-gluconolactam (7). The procedure, based upon modifications of a patent, does not require chromatography; the overall yield of 7 from 1 is 43%. Hydrogenolysis of 7 gave D-nojirilactam (8); benzylation led to the known pentabenzyl-D-nojirilactam (9) and to the unsaturated lactam 10.