Origin of Octafluorocyclopentene Polyelectrophilicity
Origin of Octafluorocyclopentene Polyelectrophilicity
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DOI：
10.1021/jacs.3c12690
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发表时间：
2024-02-14
影响因子：
15
通讯作者：
Houk，K. N.
中科院分区：
文献类型：
--
作者：
Tian，Haowen;Lee，William;Houk，K. N.
八氟环戊烯(OFCP)在形成复杂大环化合物的取代级联反应中被用作多聚体。大环多肽的Harran基团合成依赖于OFCP作为连接物，与一个多肽的四个不同的亲核单元结合。我们报道了对OFCP反应性起源的计算研究，以及用杂原子亲核试剂控制氟离子的单、二、三、四取代的理论基础。探讨了含氟取代基的诱导、负超共轭和共振给电子作用在OFCP、低氟类似物和常见亲电烯烃与几种不同亲核试剂的反应中的作用。
Octafluorocyclopentene (OFCP) has found utility as a polyelectrophile in substitution cascades that form complex macrocyclic compounds. The Harran group synthesis of macrocyclic polypeptides depends on OFCP as a linker, combining with four different nucleophilic units of a polypeptide. We report a computational investigation of the origins of OFCP reactivity and a rationale for controlled mono-, di-, tri-, and tetrasubstitution of fluoride ions by heteroatomic nucleophiles. The roles of inductive, negative hyperconjugative, and resonance electron-donation by fluoride substituents are explored for the reaction of OFCP, less-fluorinated analogues, and common electrophilic alkenes with several different nucleophiles.