Divergence in Ynone Reactivity: Atypical Cyclization by 3,4-Difunctionalization versus Rare Bis(cyclization)

被引：22

作者：

Alcaide, Benito ^{[1
]}

Almendros, Pedro ^{[2
]}

Lazaro-Milla, Carlos ^{[1
]}

Delgado-Martinez, Patricia ^{[3
]}

机构：

[1] Univ Complutense Madrid, Dept Quim Organ 1, Unidad Asociada CSIC, Grp Lactamas & Heterociclos Bioact,Fac Quim, E-28040 Madrid, Spain

[2] CSIC, IQOG, Juan Cierva 3, Madrid 28006, Spain

[3] Univ Complutense Madrid, Fac Quim, CAI Difracc Rayos 10, Madrid, Spain

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2018年 / 24卷 / 32期

关键词：

alkynes; cyclization; fluorine; heterocycles; synthetic methods; PHOSPHINE-CATALYZED 3+2; CONJUGATE ADDITION; METAL-FREE; ACCESS; ANNULATION; ACID; SPIROOXINDOLES; DERIVATIVES; ALKYNONES; OXINDOLES;

D O I：

10.1002/chem.201800630

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Functionalized ynones can be activated by Tf2C=CH2, which was generated in situ, to form zwitterionic species. These species were trapped in an intramolecular fashion by several nucleophiles to generate two major types of triflones in a divergent manner. Through fine-tuning of the reaction temperature, bis(triflyl)-6-membered- or (triflyl)-5-membered-fused-heterocycles were achieved in reasonable yields in a totally selective manner. In this way, bis(triflyl)flavones, bis(triflyl)thioflavones, bis(triflyl)selenoflavones, (triflyl)benzothienopyrans, (triflyl)benzoselenophenopyrans, (triflyl)vinyl aurones, and (triflyl)pyranoindoles were constructed. Conceivable mechanistic pathways were suggested on the basis of the isolation of several intermediates and the results from control experiments.

引用

页码：8186 / 8194

页数：9

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