Prochiral Diheteroaryl Sulfoxides and Their Reactions with (S)‐Li2‐BINOLate‐Activated Diisobutylmagnesium
Prochiral Diheteroaryl Sulfoxides and Their Reactions with (S)‐Li2‐BINOLate‐Activated Diisobutylmagnesium
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DOI：
10.1002/ejoc.201701309
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发表时间：
2018-01
影响因子：
2.8
通讯作者：
Simon Ruppenthal;R. Brückner
中科院分区：
文献类型：
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作者：
Simon Ruppenthal;R. Brückner
5-元环杂环被α-锂化或α-镁化，使得它们攻击SOCl 2或SO（OMe）2形成对称的-即前手性-二杂芳基亚砜。后者用0.5或1.2倍摩尔量的（S）-BINOLate二锂和二异丁基镁的5：4混合物处理。这使得五个不对称的亚砜/镁交换反应发生。它们以高达77%的产率和高达88%ee提供了不对称亚砜。令人惊讶的是，四种相关的二杂芳基亚砜，双（2-吡啶基）亚砜和双（3-吡啶基）亚砜不适合这种交换，而是分解。
5-Membered ring heterocycles were α-lithiated or α-magnesiated so that they attacked SOCl2 or SO(OMe)2 forming symmetric – i.e. prochiral – diheteroaryl sulfoxides. The latter were treated with a 0.5- or 1.2-fold molar amount of 5:4 mixtures of dilithium (S)-BINOLate and diisobutylmagnesium. This allowed five asymmetric sulfoxide/magnesium exchange reactions to occur. They delivered asymmetric sulfoxides in up to 77 % yield and with up to 88 % ee. Surprisingly, four related diheteroaryl sulfoxides, bis(2-pyridyl) sulfoxide, and bis(3-pyridyl) sulfoxide were unamenable to such exchanges and decomposed instead.