Carbonylation of acyclic diaminocarbenes

无环二氨基卡宾的羰基化

• 批准号: 207291904
• 负责人: Professor Dr. Ulrich Siemeling
• 金额: --
• 依托单位: Leibniz-Institut für Katalyse e. V. an der Universität Rostock (LIKAT)
• 依托单位国家: 德国
• 项目类别: Research Grants
• 财政年份: 2011
• 资助国家: 德国
• 起止时间: 2010-12-31 至 2018-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/207291904?language=en
• 关键词: Carbonylation; acyclic; diaminocarbenes

The project deals with the reaction of CO with acyclic diaminocarbenes R2N-C-NR'2 (ADACs). Our results to date allow the following conclusions: It is the exception that stable or persistent ADACs are inert towards CO. Usually, they react with CO already under mild conditions, affording a highly reactive diaminoketene (R2N)(R'2N)C=C=O as the primary carbonylation product. Except in sterically highly demanding cases, subsequent nucleophilic addition of unreacted diaminocarbene to the diaminoketene takes place, affording a betainic oxyallyl system [(R2N)(R'2N)C]2CO. In sterically overcrowded cases, an intramolecular follow-up reaction takes place instead, viz. a retro-Wolff rearrangement, affording an (amino)(carboxamido)carbene R2N-C-C(O)NR'2. This undergoes an alpha-C-H insertion typical of push-pull carbenes, yielding a beta-lactam as the final product. Antibiotically active bicyclic beta-lactams, too, are accessible this way. Now our main goal is to understand the surprisingly variant reaction behaviour of ADACs which differ only marginally in their substituents. This concerns the carbonylation itself (reactive versus inert) and also the follow-up reactions of the diaminoketene, viz. betain versus beta-lactam formation. In view of the enormous relevance of bicyclic beta-lactams, a focus will be on the potential formation of such compounds in this context. An additional important goal is to identify ADACs which will give rise to stable or persistent diaminoketenes, since these compounds have great potential for Organic Synthesis.

该项目研究了CO与非环二氨基卡宾R2N-C-NR‘2(ADAC)的反应。到目前为止，我们的结果支持以下结论：稳定或持久的ADAC对CO是惰性的，这是一个例外。通常，它们已经在温和的条件下与CO反应，生成高活性的二氨基酮酮(R2N)(R‘2N)C=C=O作为初级羰化产物。除非在空间要求很高的情况下，随后发生未反应的二氨基卡宾与二氨基酮的亲核加成反应，得到甜菜碱氧烯丙基体系[(R2N)(R‘2N)C]2CO。在空间过度拥挤的情况下，分子内的后续反应会发生，即。一种逆沃尔夫重排反应，得到(氨基)(羧氨基)卡宾R2N-C-C(O)NR‘2。这一重排反应经历了典型的推拉卡宾的α-C-H插入反应，最终产物为β-内酰胺。具有抗菌活性的双环β-内酰胺类药物也可以通过这种方式获得。现在我们的主要目标是了解ADAC令人惊讶的不同反应行为，这些反应行为在取代基上只有微小的差异。这涉及到羰化反应本身(反应性和惰性)，以及二氨基酮的后续反应，即。甜菜碱与β-内酰胺的形成。鉴于双环β-内酰胺类化合物的巨大相关性，在这方面的重点将放在这种化合物的潜在形成上。另外一个重要的目标是鉴定能够产生稳定或持久的二氨基烯酮的ADAC，因为这些化合物在有机合成中具有巨大的潜力。

项目成果

New Stable and Persistent Acyclic Diaminocarbenes.

新型稳定且持久的无环二氨基卡宾

• DOI: 10.1002/chem.201502315
• 发表时间: 2015
• 期刊: Chemistry
• 作者: T. Schulz;D. Weismann;L. Wallbaum;R. Guthardt;C. Thie;M. Leibold;C. Bruhn;U. Siemeling
• 通讯作者: U. Siemeling

Stable and Persistent Acyclic Diaminocarbenes with Cycloalkyl Substituents and Their Transformation to β-Lactams by Uncatalysed Carbonylation with CO.

具有环烷基取代基的稳定且持久的无环二氨基卡宾及其通过CO非催化羰基化转化为β-内酰胺

• DOI: 10.1002/chem.201805307
• 期刊: Chemistry
• 作者: L. Wallbaum;D. Weismann;D. Löber;C. Bruhn;P. Prochnow;J. E. Bandow;U. Siemeling
• 通讯作者: U. Siemeling

The reaction of a particularly electrophilic acyclic diaminocarbene with carbon monoxide: formation of β- and γ-lactams

特别亲电的无环二氨基卡宾与一氧化碳的反应：形成β-和γ-内酰胺

• DOI: 10.1515/znb-2018-0255
• 期刊: Zeitschrift für Naturforschung B
• 作者: L. Wallbaum;T. Schulz;C. Bruhn;U. Siemeling
• 通讯作者: U. Siemeling