Catalytic Enantioselective Transformations Involving C–H Bond Cleavage by Transition-Metal Complexes

Chemical Reviews, Год журнала: 2017, Номер 117(13), С. 8908 - 8976

Опубликована: Фев. 17, 2017

The development of new methods for the direct functionalization unactivated C-H bonds is ushering in a paradigm shift field retrosynthetic analysis. In particular, catalytic enantioselective represents highly atom- and step-economic approach toward generation structural complexity. However, as result their ubiquity low reactivity, controlling both chemo- stereoselectivity such processes constitutes significant challenge. Herein we comprehensively review all asymmetric transition-metal-catalyzed methodologies that are believed to proceed via an inner-sphere-type mechanism, with emphasis on nature stereochemistry generation. Our analysis serves document considerable rapid progress within field, while also highlighting limitations current methods.

Язык: Английский

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Funktionalisierung von C‐H‐Bindungen: neue Synthesemethoden für Naturstoffe und Pharmazeutika

Angewandte Chemie, Год журнала: 2012, Номер 124(36), С. 9092 - 9142

Опубликована: Авг. 7, 2012

Abstract Die direkte Funktionalisierung von C‐H‐Bindungen in organischen Molekülen hat sich jüngster Zeit zu einer wirksamen und idealen Methode entwickelt, mit der Kohlenstoff‐Kohlenstoff‐ Kohlenstoff‐Heteroatom‐Bindungen geknüpft werden können. Der Aufsatz gibt einen Überblick über die Strategien, durch eine rasche Synthese biologisch aktiven Verbindungen wie Naturstoffen pharmazeutischen Zielsubstanzen ermöglichen.

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Catalytic C–H amination: recent progress and future directions

Chemical Communications, Год журнала: 2009, Номер 34, С. 5061 - 5061

Опубликована: Янв. 1, 2009

Recent developments in catalytic C–H amination are discussed this feature article. The careful design of reagents and catalysts now provides efficient conditions for exquisitely selective intramolecular as well intermolecular nitrene insertion. parallel emergence activation/amination reactions opens new opportunities complementary to those offered by nitrenes.

Язык: Английский

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Cu(II)-Catalyzed Direct and Site-Selective Arylation of Indoles Under Mild Conditions

Journal of the American Chemical Society, Год журнала: 2008, Номер 130(26), С. 8172 - 8174

Опубликована: Июнь 11, 2008

We have developed a new site-selective Cu(II)-catalyzed C−H bond functionalization process that can selectively arylate indoles at either the C3 or C2 position under mild conditions. The scope of arylation is broad and tolerates functionality on both indole aryl unit, which makes it amenable to further elaboration. mechanism reaction proposed proceed via Cu(III)−aryl species undergoes initial electrophilic addition motif. speculate site arises through migration group from C2, this be controlled by nature nitrogen atom; free (NH)- N-alkylindoles deliver C3-arylated product, whereas N-acetylindoles afford isomer, with excellent yield selectivity.

Язык: Английский

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Olefin Cyclopropanation via Carbene Transfer Catalyzed by Engineered Cytochrome P450 Enzymes

Science, Год журнала: 2012, Номер 339(6117), С. 307 - 310

Опубликована: Дек. 21, 2012

Transition metal-catalyzed transfers of carbenes, nitrenes, and oxenes are powerful methods for functionalizing C=C C-H bonds. Nature has evolved a diverse toolbox oxene transfers, as exemplified by the myriad monooxygenation reactions catalyzed cytochrome P450 enzymes. The isoelectronic carbene transfer to olefins, widely used C-C bond-forming reaction in organic synthesis, no biological counterpart. Here we report engineered variants P450(BM3) that catalyze highly diastereo- enantioselective cyclopropanation styrenes from diazoester reagents via putative transfer. This work highlights capacity adapt existing enzymes catalysis synthetically important not previously observed nature.

Язык: Английский

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