Oxidative Olefination of Anilides with Unactivated Alkenes Catalyzed by an (Electron‐Deficient η<sup>5</sup>‐Cyclopentadienyl)Rhodium(III) Complex Under Ambient Conditions

Takahama, Yuji; Shibata, Yu; Tanaka, Ken

doi:10.1002/chem.201501232

Cited by 102 publications

(20 citation statements)

References 90 publications

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“…In our previous reports, electron‐deficient Cp E Rh III and amide‐pendant Cp A Rh III complexes showed high catalytic activity toward the ortho ‐C−H bond functionalization of electron‐rich anilides . We anticipated that these Rh III complexes would show high catalytic activity towards the ortho ‐C−H bond bromination of O‐phenyl carbamates due to their electron‐rich nature.…”

Section: Methodsmentioning

confidence: 92%

Rhodium‐Catalyzed ortho‐Bromination of O‐Phenyl Carbamates Accelerated by a Secondary Amide‐Pendant Cyclopentadienyl Ligand

Tanaka

Shibata

Joseph

et al. 2020

Chemistry A European J

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It has been established that an ewly developed cyclopentadienylr hodium(III) [Cp A Rh III ]c omplex,b earing an acidic secondary amide moiety on the Cp ring, is able to catalyzet he ortho-bromination of O-phenyl carbamates with N-bromosuccinimide (NBS) at room temperature. The presence of the acidic secondary amide moiety on the Cp A ligand accelerates the bromination by the hydrogen bond between the acidic NH group of the Cp A ligand and the carbonyl group of NBS.[a] J.Supporting information and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.org/10.1002/chem.202000253.Scheme1.Electrophilic and transition-metal-catalyzed bromination of protected phenols. Ts OH = p-toluenesulfonic acid. TfOH = trifluoromethanesulfonic acid.

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Section: Methodsmentioning

confidence: 92%

Rhodium‐Catalyzed ortho‐Bromination of O‐Phenyl Carbamates Accelerated by a Secondary Amide‐Pendant Cyclopentadienyl Ligand

Tanaka

Shibata

Joseph

et al. 2020

Chemistry A European J

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“…In 2015, Tanaka and co‐workers developed an electron‐deficient‐rhodium‐catalyzed method for oxidative olefination with unactivated olefins and N ‐acetyl anilides . The precatalyst – an ethoxycarbonyl‐substituted cyclopentadienyl‐Rh III [{Cp*RhCl 2 } 2 ] complex developed by the same group – was found to be effective for these olefination reaction at room temperature.…”

Section: Linear‐selective Olefinationmentioning

confidence: 99%

Emergence of Unactivated Olefins for the Synthesis of Olefinated Arenes

Deb

Maiti

2016

Eur J Org Chem

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Mizoroki–Heck olefination is one of the most exquisite methods for making carbon–carbon bonds. Numerous methods have been reported for olefination with electronically biased olefins such as acrylates and styrenes. In the absence of suitable bias, olefination with unactivated olefins suffers from regioselectivity issues. Because of these problematic regiochemical outcomes, there are only scattered examples of olefination with unactivated olefins. Both linear‐selective and branched‐selective protocols , based on control over the selectivity of olefin insertion and β‐hydride elimination, have been reported. In this microreview, different branched‐selective and linear‐selective olefination protocols with unactivated olefins are discussed, starting from the invention of Heck olefination. Throughout this microreview, different aspects associated with olefination protocols – such as the factors underlying selectivity, functional group tolerance and, more specifically, the use of a variety of unactivated olefins – are discussed.

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“…Interest in olefin coupling reactions, such as oxidative olefination and related olefinic homo‐ and cross‐coupling reactions that are predicated on the activation of alkenyl CH bonds, continues to grow. In recent studies, we have found that the square pyramidal pentaruthenium cluster complex [Ru 5 (µ 5 ‐C)(CO) 15 ] ( 1 ) is able to activate the formyl CH bond in dimethylformamide by a cluster‐opening C–H oxidative addition to the Ru 5 cluster with formation of a bridging formamido ligand [Equation (1)] …”

Section: Introductionmentioning

confidence: 99%

Substituent‐Directed Activation of CH Bonds in Activated Olefins by Ru₅(µ₅‐C)(CO)₁₅

2018

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Reactions of [Ru 5 (μ 5 -C)(CO) 15 ] with methylacrylate and vinyl acetate have yielded the products [Ru 5 (μ 5 -C)-(CO) 14 [CH=CHC(=O)OMe](μ-H)] (2) and [Ru 5 (μ 5 -C)(CO) 14 -[C(=CH 2 )OC(OMe)](μ-H)] (3), formed by cluster-opening transformations accompanied by the activation of alkenyl CH bonds at the -and α-carbon atoms of the vinyl groups, respectively, Results and DiscussionThe reaction of 1 with methylacrylate, CH 2 =CHC(=O)OMe, in benzene solvent at reflux for 48 h provided the new compound [a]

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Oxidative Olefination of Anilides with Unactivated Alkenes Catalyzed by an (Electron‐Deficient η⁵‐Cyclopentadienyl)Rhodium(III) Complex Under Ambient Conditions

Cited by 102 publications

References 90 publications

Rhodium‐Catalyzed ortho‐Bromination of O‐Phenyl Carbamates Accelerated by a Secondary Amide‐Pendant Cyclopentadienyl Ligand

Rhodium‐Catalyzed ortho‐Bromination of O‐Phenyl Carbamates Accelerated by a Secondary Amide‐Pendant Cyclopentadienyl Ligand

Emergence of Unactivated Olefins for the Synthesis of Olefinated Arenes

Substituent‐Directed Activation of CH Bonds in Activated Olefins by Ru₅(µ₅‐C)(CO)₁₅

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Oxidative Olefination of Anilides with Unactivated Alkenes Catalyzed by an (Electron‐Deficient η5‐Cyclopentadienyl)Rhodium(III) Complex Under Ambient Conditions

Cited by 102 publications

References 90 publications

Rhodium‐Catalyzed ortho‐Bromination of O‐Phenyl Carbamates Accelerated by a Secondary Amide‐Pendant Cyclopentadienyl Ligand

Rhodium‐Catalyzed ortho‐Bromination of O‐Phenyl Carbamates Accelerated by a Secondary Amide‐Pendant Cyclopentadienyl Ligand

Emergence of Unactivated Olefins for the Synthesis of Olefinated Arenes

Substituent‐Directed Activation of CH Bonds in Activated Olefins by Ru5(µ5‐C)(CO)15

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Oxidative Olefination of Anilides with Unactivated Alkenes Catalyzed by an (Electron‐Deficient η⁵‐Cyclopentadienyl)Rhodium(III) Complex Under Ambient Conditions

Substituent‐Directed Activation of CH Bonds in Activated Olefins by Ru₅(µ₅‐C)(CO)₁₅