Catalytic Access to 伪-Oxo Gold Carbenes by N鈥揙 Bond Oxidants
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- 作者：Hyun-Suk Yeom ; Seunghoon Shin
- 刊名：Accounts of Chemical Research
- 出版年：2014
- 出版时间：March 18, 2014
- 年：2014
- 卷：47
- 期：3
- 页码：966-977
- 全文大小：740K
- 年卷期：v.47,no.3(March 18, 2014)
- ISSN：1520-4898
文摘
Metal carbenes are highly versatile species that mediate various transformations. Recent advances in gold catalysis have allowed catalytic access to 伪-oxo metal carbenes from the alkyne functionality. Compared with traditional methods that rely upon metal-catalyzed decomposition of diazo precursors, the generation of this synthon occurs in an environmentally more appealing fashion by gold-catalyzed alkyne oxygenation.
Hydroxylamine derivatives are typically prepared from hydroxylamine salts that are cheap and can be handled without special precaution. In reactions with an alkyne activated by gold, relatively stable nitrones and related reagents undergo efficient O-atom transfer to form putative 伪-oxo gold carbenes. The highly reactive nature of these species could be utilized in a variety of cascade transformations. Herein, recent synthetic methods based on this reactivity as well as the currently available mechanistic and structural studies through computational and experimental methods have been discussed.
A variety of tandem reactions performed by our laboratory and others have demonstrated the synthetic utility of catalytically generated 伪-oxo gold carbenes and enabled access to various heterocycles. For example, a reaction between nitrones and alkynes led to azomethine ylides for the [3 + 2] dipolar cycloaddition. Alternatively, 伪-oxo gold carbenes can be transformed into enolate equivalents through a 1,2-pinacol shift. The addition of hydroxylamine derivatives across triple bonds led to oxoamination, providing 伪-aminocarbonyl compounds or regioselective Fisher indole-type synthesis. N鈥揙 bond cleaving redox chemistry paved the way for intermolecular redox processes, most notably by use of pyridine-N-oxide derivatives with expanding synthetic applications.
In closing, other metal-based oxygenations using N鈥揙 bond oxidants will be highlighted. One particularly interesting aspect is the process leading to metal vinylidene complexes. Trapping of this intermediate resulted in opposite regioselectivity from gold catalysis in alkyne oxygenation and led to ketene intermediates for use in subsequent cascade transformations.
Hydroxylamine derivatives are typically prepared from hydroxylamine salts that are cheap and can be handled without special precaution. In reactions with an alkyne activated by gold, relatively stable nitrones and related reagents undergo efficient O-atom transfer to form putative 伪-oxo gold carbenes. The highly reactive nature of these species could be utilized in a variety of cascade transformations. Herein, recent synthetic methods based on this reactivity as well as the currently available mechanistic and structural studies through computational and experimental methods have been discussed.
A variety of tandem reactions performed by our laboratory and others have demonstrated the synthetic utility of catalytically generated 伪-oxo gold carbenes and enabled access to various heterocycles. For example, a reaction between nitrones and alkynes led to azomethine ylides for the [3 + 2] dipolar cycloaddition. Alternatively, 伪-oxo gold carbenes can be transformed into enolate equivalents through a 1,2-pinacol shift. The addition of hydroxylamine derivatives across triple bonds led to oxoamination, providing 伪-aminocarbonyl compounds or regioselective Fisher indole-type synthesis. N鈥揙 bond cleaving redox chemistry paved the way for intermolecular redox processes, most notably by use of pyridine-N-oxide derivatives with expanding synthetic applications.
In closing, other metal-based oxygenations using N鈥揙 bond oxidants will be highlighted. One particularly interesting aspect is the process leading to metal vinylidene complexes. Trapping of this intermediate resulted in opposite regioselectivity from gold catalysis in alkyne oxygenation and led to ketene intermediates for use in subsequent cascade transformations.