An Alternative to Precious Metals: Hg(ClO4)2•3H2O as a Cheap and Water-Tolerant Catalyst for the Cycloisomerization of Allenols

被引：14

作者：

Alcaide, Benito ^{[1
]}

Almendros, Pedro ^{[2
]}

Luna, Amparo ^{[1
]}

Soriano, Elena ^{[2
]}

机构：

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

[2] CSIC, Inst Quim Organ Gen, E-28006 Madrid, Spain

来源：

JOURNAL OF ORGANIC CHEMISTRY | 2015年 / 80卷 / 14期

关键词：

GOLD CATALYSIS; MERCURY(II)-CATALYZED SYNTHESIS; ENANTIOSELECTIVE SYNTHESIS; ASYMMETRIC-SYNTHESIS; GAMMA-ALLENOLS; C-C; CYCLIZATION; OXINDOLE; 2,5-DIHYDROFURANS; HYDRATION;

D O I：

10.1021/acs.joc.5b00887

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Hg(ClO4)(2)center dot 3H(2)O, a cheap, water-tolerant, and stable salt, catalyzes the cydoisomerization reaction or alpha-allenols to 2,5-dihydrofurans in an efficient and selective manner. The reaction is general and can be applied to differently functionalized substrates, including alkyl-substituted, aryl-substituted, enantiopure, and tertiary allenols. In addition, density functional theory (DFT) calculations were performed to obtain insight into various aspects of the controlled reactivity of a-allenols under mercury catalysis. They suggest a dual activation of the allenol by the Hg complex that drives the reaction to the chemoselective formation of 2,5-dihydrofurans.

引用

页码：7050 / 7057

页数：8

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