Synthesis and applications of chiral organoboranes generated from sulfonium ylides
Synthesis and applications of chiral organoboranes generated from sulfonium ylides
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DOI：
10.1021/ja043632k
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发表时间：
2005-02-16
影响因子：
15
通讯作者：
Schmidt, AT
中科院分区：
文献类型：
--
作者：
Aggarwal, VK;Fang, GY;Schmidt, AT
研究了芳基稳定的硫叶立德与三烷基/三芳基硼烷的反应。观察到硼烷的清洁单同系化，仅具有少量的较高同系化产物（<10%）。同系化产物被分离为醇（用H2 O2/NaOH处理）和胺（用NH 2 OSO 3 H处理）。虽然反应可以在5 °C下进行，但叶立德与三丁基硼烷的反应即使在−78 °C下也非常快（15分钟后完成）。使用手性硫化物使得反应不对称，并且在所有情况下观察到高的对映选择性（> 95%ee）。叶立德-硼烷反应被应用于抗炎药新苯诺定和西替利嗪的短合成，这两种药物分别含有手性二芳基甲基烷氧基和二芳基甲基氨基部分。
The reactions of aryl-stabilized sulfonium ylides with trialkyl/triarylboranes have been investigated. Clean monohomologation of the boranes with only a small amount of the higher homologation products (<10%) was observed. The homologation products were isolated as the alcohols (treatment with H2O2/NaOH) and amines (treatment with NH2OSO3H). Although the reactions were conveniently conducted at 5 °C, the ylide reaction with tributylborane was very fast even at −78 °C (complete after 15 min). Use of chiral sulfides rendered the reactions asymmetric, and high enantioselectivity (>95% ee) was observed in all cases. The ylide−borane reaction was applied to short syntheses of the anti-inflammatory agents neobenodine and cetirizine, both of which contain a chiral diarylmethylalkoxy and diarylmethylamino moiety, respectively.