通过逆克莱森重排一锅法合成亚稳2,5-二氢恶庚英：方法与应用
One-Pot Synthesis of Metastable 2,5-Dihydrooxepines through Retro-Claisen Rearrangements: Method and Applications.
作者信息
Zhang Wei, Baudouin Emmanuel, Cordier Marie, Frison Gilles, Nay Bastien
机构信息
Laboratoire de Synthèse Organique, Ecole Polytechnique, CNRS, ENSTA, Institut Polytechnique de Paris, 91128, Palaiseau, France.
Unité Molécules de Communication et Adaptation des Micro-organismes, Muséum National d'Histoire Naturelle, CNRS, 57 rue Cuvier, 75005, Paris, France.
出版信息
Chemistry. 2019 Jun 26;25(36):8643-8648. doi: 10.1002/chem.201901675. Epub 2019 May 27.
A one-pot methodology to synthesize metastable bicyclic 2,5-dihydrooxepines from cyclic 1,3-diketones and 1,4-dibromo-2-butenes through the retro-Claisen rearrangement of syn-2-vinylcyclopropyl diketone intermediates is reported. DFT calculations were performed to understand the reaction selectivity and mechanisms towards [1,3]- or [3,3]-sigmatropic rearrangements, highlighting the crucial influence of the temperature. The reaction was successfully applied to a short protecting group-free total synthesis of radulanin A, a natural 2,5-dihydrobenzoxepine. Moreover, the strong herbicidal potential of this natural product is demonstrated for the first time.
报道了一种一锅法，通过顺式-2-乙烯基环丙基二酮中间体的逆克莱森重排，从环状1,3-二酮和1,4-二溴-2-丁烯合成亚稳双环2,5-二氢噁庚因。进行了密度泛函理论（DFT）计算，以了解反应对[1,3]-或[3,3]-σ迁移重排的选择性和机理，突出了温度的关键影响。该反应成功应用于天然产物拉杜拉宁A（一种天然的2,5-二氢苯并噁庚因）的无保护基短全合成。此外，首次证明了这种天然产物具有很强的除草潜力。
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