Rhodium(III)‐Catalyzed CH Activation of Arenes Using a Versatile and Removable Triazene Directing Group

Wang, Chengming; Chen, Hu; Wang, Zhaofeng; Chen, Jiean; Huang, Yong

doi:10.1002/anie.201203230

Cited by 249 publications

(51 citation statements)

References 76 publications

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“…For these limitations to be resolved, strategies for traceless directing group-assisted C–H functionalization have been developed. 7a–d,15 For instance, Gevorgyan 7a,b,16 and Ge 7c reported remarkable C–H ortho -alkenylation, oxygenation, and carboxylation of phenols with silanol traceless directing groups. However, a traceless directing group approach for ortho -C–H silylation has not been reported to date.…”

Section: Introductionmentioning

confidence: 99%

Catalytic Reductive ortho-C–H Silylation of Phenols with Traceless, Versatile Acetal Directing Groups and Synthetic Applications of Dioxasilines

et al. 2016

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A new, highly selective, bond functionalization strategy, achieved via relay of two transition metal catalysts and the use of traceless acetal directing groups, has been employed to provide facile formation of C–Si bonds and concomitant functionalization of a silicon group in a single vessel. Specifically, this approach involves the relay of Ir-catalyzed hydrosilylation of inexpensive and readily available phenyl acetates, exploiting disubstituted silyl synthons to afford silyl acetals and Rh-catalyzed ortho-C–H silylation to provide dioxasilines. A subsequent nucleophilic addition to silicon removes the acetal directing groups and directly provides unmasked phenol products and, thus, useful functional groups at silicon achieved in a single vessel. This traceless acetal directing group strategy for catalytic ortho-C–H silylation of phenols was also successfully applied to preparation of multisubstituted arenes. Remarkably, a new formal α-chloroacetyl directing group has been developed that allows catalytic reductive C–H silylation of sterically hindered phenols. In particular, this new method permits access to highly versatile and nicely differentiated 1,2,3-trisubstituted arenes that are difficult to access by other catalytic routes. In addition, the resulting dioxasilines can serve as chromatographically stable halosilane equivalents, which allow not only removal of acetal directing groups but also introduce useful functional groups leading to silicon-bridged biaryls. We demonstrated that this catalytic C–H bond silylation strategy has powerful synthetic potential by creating direct applications of dioxasilines to other important transformations, examples of which include aryne chemistry, Au-catalyzed direct arylation, sequential orthogonal cross-couplings, and late-stage silylation of phenolic bioactive molecules and BINOL scaffolds.

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Section: Introductionmentioning

confidence: 99%

Catalytic Reductive ortho-C–H Silylation of Phenols with Traceless, Versatile Acetal Directing Groups and Synthetic Applications of Dioxasilines

et al. 2016

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“…However, removal of these ortho-directing groups from the hydroarylation products requires additional chemical transformations and is not always achievable [21][22][23] . Thus, access to ortho-substituted alkenylarenes by alkyne hydroarylation is limited by the nature of the ortho-directing groups, and access to meta-or para-substituted alkenylarenes has not been achieved selectively by existing methods for alkyne hydroarylation 24,25 .…”

mentioning

confidence: 99%

A decarboxylative approach for regioselective hydroarylation of alkynes

et al. 2016

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“…This protocol allows for the synthesis of novel tetrahydroisoquinolones under mild and efficient conditions. In 2012, Wang et al [53] reported the application of a versatile and removable triazene DG. The trifluoroborate salts were then amenable to a Buchwald-Hartwig coupling/oxidation sequence (Figure 4.24b).…”

Section: With Rhodiummentioning

confidence: 99%

C–H Bond Activation for Arylations

2014

Catalytic Arylation Methods

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Rhodium(III)‐Catalyzed CH Activation of Arenes Using a Versatile and Removable Triazene Directing Group

Cited by 249 publications

References 76 publications

Catalytic Reductive ortho-C–H Silylation of Phenols with Traceless, Versatile Acetal Directing Groups and Synthetic Applications of Dioxasilines

Catalytic Reductive ortho-C–H Silylation of Phenols with Traceless, Versatile Acetal Directing Groups and Synthetic Applications of Dioxasilines

A decarboxylative approach for regioselective hydroarylation of alkynes

C–H Bond Activation for Arylations

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