Ruthenium-Catalyzed Ortho C(sp2)–H Amidation of Benzaldehydes with Organic Azides

Rasheed, Omer K.

doi:10.1055/s-0036-1591765

Cited by 19 publications

(15 citation statements)

References 5 publications

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“…Zhang also showed that Ru was a suitable catalyst for ortho-C-H amination with organic azides, using electron poor anilines as the TDG (Scheme 3g). 34 In 2017, Yu exemplified the use of palladium catalysis with TiDGs for the ortho-arylation of benzaldehydes. Bulky quaternary amino acid (2-aminoisobutyric acid) afforded the optimal bite angle to facilitate arylation (Scheme 4a).…”

Section: C(sp 2 )-H Functionalisation Of Benzaldehydesmentioning

confidence: 99%

Transient imines as ‘next generation’ directing groups for the catalytic functionalisation of C–H bonds in a single operation

2018

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C-H functionalisation promises a paradigm shift in synthetic planning. However, the additional steps often required to install and remove directing groups currently detract from the efficiency. The strategy of reversible installation of a directing group via an imine linkage has recently emerged, with the imine formed and hydrolysed in situ. Such transient directing groups can promote transition metal catalysed functionalisation of unactivated C-H bonds of aldehydes, ketones and amines. This approach removes additional steps usually required for covalent directing groups and can use catalytic quantities of the imine forming component. This review updates the rapidly developing field of transient directing groups for C-H functionalisation on sp and sp carbon centres, to form new C-C and C-X bonds. We focus on the structures of the transient directing groups as mono or bidentate coordinating groups for various metal catalysts.

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Section: C(sp 2 )-H Functionalisation Of Benzaldehydesmentioning

confidence: 99%

Transient imines as ‘next generation’ directing groups for the catalytic functionalisation of C–H bonds in a single operation

2018

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“…[4] In this context, the transient directing group (TDG) strategy [1f,5] has emerged as an excellent alternative for aldehydes since the pioneering work by Jun and coworkers. [6] However, transition metal-catalyzed amidation of benzaldehydes is still limited to precious metals such as Rh, [7] Ru, [8] and Ir. [9] For example, Wang,[7e] Kim,[9a] and Cui [9c] reported Cp*Rh(III) or Ir(III)-catalyzed ortho-amidation of aldehydes using aldimines or nitrones as 'preinstalled directing groups'.…”

Section: Abstract: Aldehydes; Amidation; Co-catalysis; Transient Dirementioning

confidence: 99%

“…Other cobalt precursors did not afford the amidated product, however no product formation observed with Cp*CoI 2 dimer; this is unexpected and unexplainable at this stage (entries [6][7][8]. In order to improve the efficiency of the product formation, a series of carboxylate additives such as NaOPiv, PhCO 2 Na, NaOAc were tested and among them NaOPiv offered satisfactory yield (entries [9][10][11].…”

Section: Abstract: Aldehydes; Amidation; Co-catalysis; Transient Dirementioning

confidence: 99%

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Cp*Co(III)‐Catalyzed o‐Amidation of Benzaldehydes with Dioxazolones Using Transient Directing Group Strategy

2020

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Transition metal‐catalyzed ortho‐selective C(sp2)−H amidation of weakly coordinating aldehydes remains limited to precious metals such as Ir, Rh, Ru, etc. Herein, we put forward a novel report on ortho‐amidation of benzaldehydes employing user‐friendly dioxazolones under cost‐effective and air‐stable Cp*Co(III) catalysis. This catalytic transformation involves transient directing group strategy to enhance the ligating capability of weakly chelating aldehydes.

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“…After choosing the transient directing group and optimizing reaction conditions next is to explore the substrate scope of benzaldehydes carrying either electron donating or withdrawing groups with p ‐toluenesulphonylazide and offers a convenient method for the synthesis of various 2‐sulfonylamino‐benzaldehydes in good yield. Recently, Rasheed, studied the ruthenium‐catalyzed functionalization of benzaldehyde substrate with organic azide promoted by various transient directing groups.…”

Section: Covalent Reversible Interaction For Metal Catalyzed C–h Actimentioning

confidence: 99%

Advances in Development of C–H Activation/Functionalization Using a Catalytic Directing Group

Rasheed

Sun

2018

ChemistrySelect

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The transition metal catalyzed direct site‐selective carbon –hydrogen functionalization is ubiquitous in organic synthesis and has reached an impressive level of sophistication and efficiency emerging as a powerful synthetic strategy for C–C bond and C–X bond formation to access various useful arylated organic molecules. For the past two decades, directing group strategy has been used for selective activation and functionalization of certain inert C–H bonds. Despite the enormous development in this field, still, the majority of systems require two redundant steps, i. e. installation and removal of DGs. To overcome these limitations, recently, traceless and multitasking groups were invented as a partial solution to DG release however installation still remains unsolved. Ideally, use of the catalytic directing group, which can be reversibly linked to the substrate and can serve as an efficient directing role would circumvent this problem and is considered as one of the most efficient and powerful strategies for the non‐activated C–H functionalization (C(sp2)–H or C(sp3)–H). In this review, we describe the enormous advances in this field for direct selective C–H functionalization without involving additional steps, i. e. installation and removal of directing groups and also discuss less explored but significant non‐covalent interactions such as hydrogen bonding or ion pairing, which helps to control the selectivity of a substrate in a catalytic organic reaction.

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Ruthenium-Catalyzed Ortho C(sp2)–H Amidation of Benzaldehydes with Organic Azides

Abstract: A ruthenium-catalyzed functionalization of benzaldehyde substrate with organic azides promoted by various transient directing groups has been developed. In this approach, C–H amination is achieved via a transient aldimine intermediate in good to excellent yields.

Cited by 19 publications

References 5 publications

Transient imines as ‘next generation’ directing groups for the catalytic functionalisation of C–H bonds in a single operation

Transient imines as ‘next generation’ directing groups for the catalytic functionalisation of C–H bonds in a single operation

Cp*Co(III)‐Catalyzed o‐Amidation of Benzaldehydes with Dioxazolones Using Transient Directing Group Strategy

Advances in Development of C–H Activation/Functionalization Using a Catalytic Directing Group

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