研究室工作進展 May. 16th, 2014

 Diastereoselective Nucleophilic Ring-Opening Reactions of 2,6-Diazasemibullvalenes for the Synthesis of Diverse Functionalized Δ1-Bipyrroline Derivatives

Shaoguang Zhang, Ming Zhan, Wen-Xiong Zhang, and Zhenfeng Xi*

Chem. Eur. J. 2014, DOI: 10.1002/chem.201402911

2,6-Diazasemibullvalenes are a class of structurally and chemically interesting polycyclic strained compounds. However, their reaction chemistry and synthetic applications are rarely explored.

Nucleophilic ring-opening reactions of 2,6-diazasemibullvalenes (NSBVs) were investigated. Different types of nucleophiles including alcohol, phenol, thiol, carboxylic acid, water, enol, amine, indole, metal halide salts, sodium azide, organozinc compounds, lithium alkynyl thiolates and sulfoxonium ylides were used, affording diverse functionalized Δ1-bipyrroline derivatives in good yields with high regio- and diastereo-selectivity. Most of the reactions featured milder conditions and higher reactivity compared with those for common aziridine derivatives, probably owing to the rigid ring system and substitution patterns of NSBVs.

This study not only provides an efficient synthetic method for various Δ1-bipyrroline derivatives, but also adds valuable knowledge to the understanding of the reaction chemistry of diazasemibullvalenes, a class of unique compounds.

亮點介紹

 氮雜半瞬烯 (NSBV)是一類具有特殊骨架和性質的有機分子，曾經得到理論物理有機化學家的很大關注。本實驗室利用自己發展的雙锂試劑，于2012年成功高效地合成了該類化合物。之後，我們對該類化合物的反應化學和應用展開了研究。本工作結果再次說明該類化合物的新穎反應性和在合成一些特殊結構有機分子方面的有用性。本課題已經發表的論文如下。

張韶光、魏俊年、湛明等，J. Am. Chem. Soc. 2012, 134, 11964; Angew. Chem. Int. Ed. 2013, 52, 3485; Chem. Commun. 2013, 49, 6146.