Dissociative reactions of benzonorbornadienes with tetrazines: scope of leaving groups and mechanistic insights†,Organic & Biomolecular Chemistry

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Dissociative reactions of benzonorbornadienes with tetrazines: scope of leaving groups and mechanistic insights†
Organic & Biomolecular Chemistry ( IF 2.9 ) Pub Date : 2017-11-15 00:00:00 , DOI: 10.1039/c7ob02191g
M. Xu _{1,

2,

3,

4,

5} , R. Galindo-Murillo _{1,

2,

3,

4,

5} , T. E. Cheatham _{1,

2,

3,

4,

5} , R. M. Franzini _{1,

2,

3,

4,

5}

Affiliation

Bioorthogonal dissociative reactions boast diverse potential applications in chemical biology and drug delivery. The reaction of benzonorbornadienes with tetrazines to release amines from carbamate leaving groups was recently introduced as a bioorthogonal bond-cleavage reaction. The present study aimed at investigating the scope of leaving groups that are compatible with benzonorbornadienes. Synthesis of several benzonorbornadienes with different releasable groups is reported, and the reaction of these molecules with tetrazine was found to be rapid and afforded high release yields. The tetrazine-induced release of molecules proceeds in a cascade of steps including inverse-electron demand cycloaddition and cycloreversion reactions that form unstable isoindoles/isobenzofuran intermediates and spontaneously eliminate a leaving group of interest. In the case of oxygen-bridged BNBDs at room temperature, we observed the formation of an unproductive byproduct.

中文翻译：

苯并降冰片二烯与四嗪的解离反应：离去基团的范围和机理见解†

生物正交解离反应在化学生物学和药物递送中具有多种潜在应用。苯并降冰片二烯与四嗪的反应从氨基甲酸酯离去基团释放胺的反应最近被引入作为生物正交键裂解反应。本研究旨在调查与苯并降冰片二烯相容的离去基团的范围。报道了几种具有不同可释放基团的苯并降冰片二烯的合成，并且发现这些分子与四嗪的反应是快速的并且提供了高释放率。四嗪诱导的分子释放以一系列步骤进行，这些步骤包括反电子需求环加成反应和环还原反应，形成不稳定的异吲哚/异苯并呋喃中间体，并自发消除感兴趣的离去基团。

更新日期：2017-11-15

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