Asymmetric synthesis and properties of sulfinimines (thiooxime S-oxides)
Asymmetric synthesis and properties of sulfinimines (thiooxime S-oxides)
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DOI：
10.1021/jo970077e
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发表时间：
1997-04-18
影响因子：
3.6
通讯作者：
Carroll, PJ
中科院分区：
文献类型：
--
作者：
Davis, FA;Reddy, RE;Carroll, PJ
对映体纯的亚磺胺（硫代肟 S-氧化物 10）是胺衍生物不对称合成中的重要组成部分，由芳香族、杂芳香族和脂肪族醛一步制备而成，产率良好至优异。该方案涉及用 LiHMDS 处理市售的 (R)-或 (S)-薄荷基对甲苯磺酸盐（Andersen 试剂 4），然后处理醛，仅得到 (E)-10。亚磺亚胺10通过甲硅烷基亚磺酰胺阴离子13与醛的Peterson型烯化反应形成。阴离子13是通过薄荷醇锂(12a)与双(三甲基甲硅烷基)亚磺酰胺11反应产生的，双(三甲基甲硅烷基)亚磺酰胺11是在4与LiHMDS的反应中形成的。形成的另一种产物是 O-(三甲基甲硅烷基)薄荷醇 (12c)，其分离回收率 >80%。讨论了另外两种效率较低的 10 不对称合成方法：(i) 亚磺亚胺 6 与手性非外消旋氮丙啶的不对称氧化，以及 (ii) 由腈制备的金属醛亚胺与 4 的反应。所有这些方案均不适用于酮。
Enantiomerically pure sulfinimines (thiooxime S-oxides 10), important building blocks in the asymmetric synthesis of amine derivatives, are prepared in good to excellent yields in one step from aromatic, heteroaromatic, and aliphatic aldehydes. This protocol involves treating commercially available (R)-or (S)-menthyl p-toluenesufinate (Andersen reagent 4) with LiHMDS, followed by the aldehyde, affording (E)-10 exclusively. The sulfinimines 10 are formed via a Peterson-type olefination reaction of silylsulfinamide anion 13 with the aldehyde. Anion 13 is generated by reaction of lithium menthoxide (12a) with bis(trimethylsilyl)sulfinamide 11, which is formed in the reaction of 4 with LiHMDS. The other product formed is O-(trimethylsilyl)menthol (12c), which is isolated in >80% yield for recycling. Two other less efficient methods for the asymmetric synthesis of 10 are discussed: (i) the asymmetric oxidation of sulfenimines 6 with chiral nonracemic oxaziridines and (ii) the reaction of metal aldimines, prepared from nitriles, with 4. All of these protocols fail with ketones.