Rhodium‐Catalyzed CH Alkynylation of Arenes at Room Temperature

Feng, Chao; Loh, Teck‐Peng

doi:10.1002/ange.201309198

Cited by 66 publications

(9 citation statements)

References 86 publications

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“…Assuming the viability of our proposal, there comes with an affiliated bonus, as no external oxidant was required because of the redox neutral property of this transformation 32 . With our ongoing interest in rhodium and fluorine chemistry 47 48 49 , herein we would like to present the chelation-assisted C–H activation strategy for the direct incorporation of the α-fluoroalkenyl unit using gem -difluoroalkene as the fluoroalkene donor ( Fig. 1e ) 50 .…”

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confidence: 99%

Rhodium-catalysed C(sp2)–C(sp2) bond formation via C–H/C–F activation

2015

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Fluoroalkenes represent a class of privileged structural motifs, which found widespread use in medicinal chemistry. However, the synthetic access to fluoroalkenes was much underdeveloped with previous reported methods suffering from either low step economy or harsh reaction conditions. Here we present a RhIII-catalysed tandem C–H/C–F activation for the synthesis of (hetero)arylated monofluoroalkenes. The use of readily available gem-difluoroalkenes as electrophiles provides a highly efficient and operationally simple method for the introduction of α-fluoroalkenyl motifs onto (hetero)arenes under oxidant-free conditions. Furthermore, the employment of alcoholic solvent and the in-situ generated hydrogen fluoride are found to be beneficial in this transformation, indicating the possibility of the involvement of hydrogen bond activation mode with regards to the C–F bond cleavage step.

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confidence: 99%

Rhodium-catalysed C(sp2)–C(sp2) bond formation via C–H/C–F activation

2015

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“…Following the initial finding by Li and co‐workers (see Section 3.4) that certain hypervalent iodine species provide suitable electrophiles for RhCp*‐catalyzed functionalization reactions of aromatic CH bonds, Loh and co‐workers,33a Li and co‐workers33b and Glorius and co‐workers33c independently reported the first RhCp*‐catalyzed alkynylation using 1‐silylethynyl‐1,2‐benziodoxol‐3(1 H )‐ones (silyl‐EBX), established hypervalent iodine reagents for alkynylation 34…”

Section: Cc Bond Formationsmentioning

confidence: 99%

Formal S_N‐Type Reactions in Rhodium(III)‐Catalyzed CH Bond Activation

2014

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rhodium (RhCp*)-catalyzed C À H transformations have emerged as a prosperous field in C À H bond activation. Recent advances in this area have significantly focused on the development of new strategies for C À C and C À heteroatom bond formation that are characterized by the novel reactivity of the RhCp* catalyst to undergo formal S N-type reactions with electrophilic substrates. This review is intended to give an overview on this rather new class of RhCp*-catalyzed C À H transformations, covering recent C À C and C À heteroatom bond-forming reactions. The nature of the reaction partner in these C À H functionalization reactions serves as a guideline throughout this article and, combined with selected descriptions of mechanistic proposals, should emphasize general characteristics of transformations within this novel reaction class.

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“…[74] Notably, the reaction was highly mono selective and compatible with many functional groups on benzamides. However, the scope of alkynes was limited to those containing very sterically hindered groups (TIPS and t Bu).…”

Section: Rhodium Catalysismentioning

confidence: 99%

A Simple and Versatile Amide Directing Group for C−H Functionalizations

et al. 2016

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Achieving selective C–H activation at a single and strategic site in the presence of multiple C–H bonds can provide a powerful and generally useful retrosynthetic disconnection. In this context, the directing group serves as a compass to guide the transition metal to C–H bonds using distance and geometry as powerful recognition parameters to distinguish between proximal and distal C–H bonds. However, the installation and removal of directing groups is a practical drawback. To improve the utility of this approach, one can seek solutions in three directions. First, simplifying the directing group; Second, use of common functional groups or protecting groups as directing groups; Third, attaching the directing group to substrates via a transient covalent bond to render directing groups catalytic. This review describes the rational development of an extremely simple and yet broadly applicable directing group for Pd(II), Rh(III) and Ru(II) catalysts, namely, the N-methoxy amide (CONHOMe). Through collective efforts in the community, a wide range of C–H activation transformations using this type of simple directing groups has been developed.

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Rhodium‐Catalyzed CH Alkynylation of Arenes at Room Temperature

Cited by 66 publications

References 86 publications

Rhodium-catalysed C(sp2)–C(sp2) bond formation via C–H/C–F activation

Rhodium-catalysed C(sp2)–C(sp2) bond formation via C–H/C–F activation

Formal S_N‐Type Reactions in Rhodium(III)‐Catalyzed CH Bond Activation

A Simple and Versatile Amide Directing Group for C−H Functionalizations

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Rhodium‐Catalyzed CH Alkynylation of Arenes at Room Temperature

Cited by 66 publications

References 86 publications

Rhodium-catalysed C(sp2)–C(sp2) bond formation via C–H/C–F activation

Rhodium-catalysed C(sp2)–C(sp2) bond formation via C–H/C–F activation

Formal SN‐Type Reactions in Rhodium(III)‐Catalyzed CH Bond Activation

A Simple and Versatile Amide Directing Group for C−H Functionalizations

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Formal S_N‐Type Reactions in Rhodium(III)‐Catalyzed CH Bond Activation