Stereoselective Alder-Ene Reactions of Bicyclo[1.1.0]butanes: Facile Synthesis of Cyclopropyl- and Aryl-Substituted Cyclobutenes.
Stereoselective Alder-Ene Reactions of Bicyclo[1.1.0]butanes: Facile Synthesis of Cyclopropyl- and Aryl-Substituted Cyclobutenes.
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DOI：
10.1021/jacs.3c13080
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发表时间：
2024-01-10
影响因子：
15
通讯作者：
Anderson EA
中科院分区：
文献类型：
--
作者：
Dasgupta A;Bhattacharjee S;Tong Z;Guin A;McNamee RE;Christensen KE;Biju AT;Anderson EA
双环[1.1.0]丁烷（BCB）是由两个稠合的环丙烷环组成的应变碳环，由于其与自由基、亲核试剂、阳离子和卡宾的不同反应特性，已成为有机合成、药物化学和化学生物学中公认的结构单元。双环系统的限制赋予桥头间C-C键高的p-特征，导致这种广泛的反应曲线;然而，迄今为止，在周环过程中使用BCB在很大程度上被忽视，有利于这种逐步的非协同加成。在这里，我们描述了使用BCBs作为底物的烯类反应与应变的烯烃和炔，从而产生环丁烯装饰高度取代的环丙烷和芳烃。前者的产品是从高立体选择性反应与环丙烯，产生在原位从乙烯基重氮乙酸酯在蓝光照射下（440 nm）。通过与芳炔的等价反应，在温和的条件下以高产率制备了具有带季芳基碳原子的环丁烯。机理研究强调了电子效应在这种化学中的重要性，而计算研究支持一个协调一致的途径，并合理化与环丙烯反应的优异立体选择性。
Bicyclo[1.1.0]butanes (BCBs), strained carbocycles comprising two fused cyclopropane rings, have become well-established building blocks in organic synthesis, medicinal chemistry, and chemical biology due to their diverse reactivity profile with radicals, nucleophiles, cations, and carbenes. The constraints of the bicyclic ring system confer high p-character on the interbridgehead C–C bond, leading to this broad reaction profile; however, the use of BCBs in pericyclic processes has to date been largely overlooked in favor of such stepwise, non-concerted additions. Here, we describe the use of BCBs as substrates for ene-like reactions with strained alkenes and alkynes, which give rise to cyclobutenes decorated with highly substituted cyclopropanes and arenes. The former products are obtained from highly stereoselective reactions with cyclopropenes, generated in situ from vinyl diazoacetates under blue light irradiation (440 nm). Cyclobutenes featuring a quaternary aryl-bearing carbon atom are prepared from equivalent reactions with arynes, which proceed in high yields under mild conditions. Mechanistic studies highlight the importance of electronic effects in this chemistry, while computational investigations support a concerted pathway and rationalize the excellent stereoselectivity of reactions with cyclopropenes.
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