On the Discovery of Direct Ortho‐Magnesiation

Philip E. Eaton, Yusheng Xiong, Chih‐Hung Lee

doi:10.1002/jccs.199100052

On the Discovery of Direct Ortho‐Magnesiation

DOI Web Site Web Site 被引用文献9件

書誌事項

公開日: 1991-08

権利情報

http://onlinelibrary.wiley.com/termsAndConditions#vor

DOI

10.1002/jccs.199100052

公開者: Wiley

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<jats:title>Abstract</jats:title><jats:p>Metalation of 2,4‐dicyanocubanecarboxamide (4) with lithium tetramethylpiperidide (LiTMP) followed by quenching with CO<jats:sub>2</jats:sub> is non‐regioselective and results in carboxylation at the 3 (→ 5) and 6 (→ 6 ) positions. However, when the reaction was repeated with LiTMP pre‐treated with more than 0.5 equivalent of MgBr<jats:sub>2</jats:sub>, only 6 was produced. This was shown to occur by direct, regiospecific ortho‐magnesiation by the bases BrMgTMP and MgTMP<jats:sub>2</jats:sub>. This initial observation of ortho‐magnesiation has opened the way to wide application of this new methodology, a valuable and useful complement to ortho‐lithiation.</jats:p>