Synthesis of (2R,5S)-dihydroxymethyl-(3R,4R)-dihydroxypyrrolidine (DGDP) via stereoselective amination using chlorosulfonyl isocyanate

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• 作者：In Su Kim ; Sin Jung Kim ; Jae Koo Lee ; Qing Ri Li ; Young Hoon Jung
• 关键词：Chlorosulfonyl isocyanate ; Amination ; 2 ; 5-Dideoxy-2 ; 5-imino-d-glucitol ; DGDP
• 刊名：Carbohydrate Research
• 出版年：2007
• 出版时间：13 August 2007
• 年：2007
• 卷：342
• 期：11
• 页码：1502-1509
• 全文大小：189 K

文摘

A stereoselective approach for synthesizing (2R,5S)-dihydroxymethyl-(3R,4R)-dihydroxypyrrolidine 1 (2,5-dideoxy-2,5-imino-d-glucitol, DGDP) was achieved using a seven-step approach starting from 2,3,4,6-tetra-O-benzyl-d-mannose (7). Key steps for the preparation of the title compound 1 involved the regioselective and diastereoselective amination of the cinnamyl anti-1,2-polybenzyl ethers 5 and 6 using chlorosulfonyl isocyanate (CSI) and ring cyclization to form the pyrrolidine ring. The reaction between anti-1,2-polybenzyl ether 5 and CSI in toluene at 0 °C afforded the corresponding anti-1,2-amino alcohol 4 as a major product with a diastereoselectivity of 16:1 in 76 % yield. The mechanism underlying these reactions may be explained by the neighboring-group effect leading to the retention of stereochemistry.