Asymmetric synthesis of 3-substituted γ- and δ-sultams
Asymmetric synthesis of 3-substituted γ- and δ-sultams
复制标题
DOI：
10.1002/ejoc.200500860
复制
发表时间：
2006-02-27
影响因子：
2.8
通讯作者：
Bats, JW
中科院分区：
文献类型：
--
作者：
Enders, D;Moll, A;Bats, JW
描述了各种3-取代的γ-和δ-磺内酰胺的高效且灵活的不对称合成。关键步骤是各种有机铈化合物与 omega-SAMP-腙磺酸盐的 CN 双键进行非对映选择性亲核 1,2-加成。得到的肼具有良好至极好的非对映体过量（de = 78 至 >= 96 %）。通过还原性 N,N-键断裂除去手性助剂，得到相应的氨基磺酸盐，而没有外消旋作用。酯水解和随后在甲苯中用光气处理所得磺酸产生氨磺酰氯，其以良好至优异的总收率（39-51%）和高对映体过量（ee = 78-99%）环化为标题化合物。绝对构型通过X射线结构分析确定，并且符合非对映选择性1,2-加成的假设机制。 （(c) Wiley-VCH Verlag GmbH & Co. KGaA，69451 Weinheim，德国，2006 年）。
An efficient and flexible asymmetric synthesis of various 3-substituted gamma- and delta-sultams is described. The key step is a diastereoselective nucleophilic 1,2-addition of various organocerium compounds to the CN double bond of omega-SAMP-hydrazonosulfonates. The resulting hydrazines were obtained in good to excellent diastereomeric excesses (de = 78 to >= 96 %). Removal of the chiral auxiliary by reductive N,N-bond cleavage afforded the corresponding aminosulfonates without racemisation. Ester hydrolysis and subsequent treatment of the resulting sulfonic acids with phosgene in toluene led to the ammosulfonyl chlorides, which were cyclised to the title compounds in good to excellent overall yields (39-51 %) and high enantiomeric excesses (ee = 78-99 %). The absolute configuration was determined by X-ray structure analysis and is in accordance with the postulated mechanism for the diastereoselective 1,2-addition. ((c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006).