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原位格氏金属化法，第二部分：有机钙化合物一锅法合成的范围

In situ Grignard Metalation Method, Part II: Scope of the One-Pot Synthesis of Organocalcium Compounds.

作者信息

Schüler Philipp, Sengupta Simon, Koch Alexander, Görls Helmar, Krieck Sven, Westerhausen Matthias

机构信息

Institute of Inorganic and Analytical Chemistry, Friedrich Schiller University Jena, Humboldtstraße 8, 07743, Jena, Germany.

出版信息

Chemistry. 2022 Oct 18;28(58):e202201897. doi: 10.1002/chem.202201897. Epub 2022 Aug 23.

DOI:10.1002/chem.202201897
PMID:35912418
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC9804548/
Abstract

The in situ Grignard Metalation Method (iGMM) is a straightforward one-pot strategy to synthesize alkaline-earth metal amides in multi-gram scale with high yields via addition of bromoethane to an ethereal suspension of a primary or secondary amine and magnesium (Part I) or calcium (Part II). This method is highly advantageous because no activation of calcium is required prior to the reaction. Contrary to the magnesium-based iGMM, there are some limitations, the most conspicuous one is the large influence of steric factors. The preparation of Ca(hmds) succeeds smoothly within a few hours with excellent yields opening the opportunity to prepare large amounts of this reagent. Side reactions and transfer of the iGMM to substituted anilines and N-heterocycles as well as other H-acidic substrates such as cyclopentadienes are studied. Bulky amidines cannot be converted directly to calcium amidinates via the iGMM but stoichiometric calciation with Ca(hmds) enables their preparation.

摘要

原位格氏金属化法（iGMM）是一种直接的一锅法策略，通过向伯胺或仲胺与镁（第一部分）或钙（第二部分）的醚悬浮液中加入溴乙烷，以多克规模高产率合成碱土金属酰胺。该方法具有很大优势，因为反应前无需对钙进行活化。与基于镁的iGMM相反，存在一些局限性，最明显的是空间因素的影响很大。Ca(hmds)的制备在几小时内顺利完成，产率优异，为大量制备该试剂提供了机会。研究了iGMM对取代苯胺、N-杂环以及其他H-酸性底物（如环戊二烯）的副反应和转移。庞大的脒不能通过iGMM直接转化为钙脒，但与Ca(hmds)进行化学计量煅烧可实现其制备。

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