Bicyclo[3.1.0]hex-1-ene is a highly strained bicyclic intermediate that generates trimethylenemethane (TMM) diradical through breaking the C–C bond of its methylene cyclopropane moiety. The reactivity of bicyclo[3.1.0]hex-1-enes and trimethylenemethane (TMM) diradicals depend on the reaction temperature and substitution patterns. This short review covers various strain-induced transformations of bicyclo[3.1.0]hex-1-enes and their formal [3+2] cycloadditions through TMM diradicals and presents synthetic applications to natural products containing triquinane and tropone structures.

1 Introduction

2 Early Reports on Bicyclo[3.1.0]hex-1-enes

3 Approaches to Form Bicyclo[3.1.0]hex-1-enes

4 Structure and Reactivity of Bicyclo[3.1.0]hex-1-enes

4.1 Isomerization

4.2 Dimerization

4.3 [3+2] Cycloaddition

4.4 [4+2] Cycloaddition

5 Synthetic Applications to Natural Products

6 Summary and Outlook

双环[3.1.0]己-1-烯是一种高度应变的双环中间体，通过破坏其亚甲基环丙烷部分的C-C键产生三亚甲基甲烷（TMM）双自由基。双环[3.1.0]己-1-烯和三亚甲基甲烷(TMM)双自由基的反应性取决于反应温度和取代模式。这篇简短的综述涵盖了双环 [3.1.0] 己-1-烯的各种应变诱导转化及其通过 TMM 双自由基的形式 [3+2] 环加成，并介绍了对含有三喹烷和托酮结构的天然产物的合成应用。

1 简介

2 双环[3.1.0]hex-1-enes 的早期报告

3 形成双环[3.1.0]己-1-烯的方法

4 双环[3.1.0]hex-1-enes的结构和反应性

4.1 异构化

4.2 二聚化

4.3 [3+2] 环加成

4.4 [4+2] 环加成

5 天然产品的合成应用

6 总结与展望