Rhodium-Catalyzed Selective C–H Activation/Olefination of Phenol Carbamates

Gong, Tian‐Jun; Xiao, Bin; Liu, Zhao‐Jing; Wan, Jian; Xu, Jun; Luo, Dong‐Fen; Fu, Yao; Liu, Lei

doi:10.1021/ol201140q

Cited by 191 publications

(55 citation statements)

References 36 publications

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“…Other carbonyl compounds, ketones [30], esters [31], and carbamates [32] Similar alkenylation reactions of α,β-unsaturated esters and amides through alkenyl C-H bond cleavage were reported by Glorius and coworkers [33] (Scheme 18.33). In addition, the reactions of N-alkoxybenzamides proceed efficiently without addition of any external oxidant (Scheme 18.34) [34].…”

Section: The Fujiwara-moritani-type Reactionsupporting

confidence: 62%

C–H Bond Alkenylation

Satoh

Miura

2013

Metal‐Catalyzed Cross‐Coupling Reactions and More

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Section: The Fujiwara-moritani-type Reactionsupporting

confidence: 62%

C–H Bond Alkenylation

Satoh

Miura

2013

Metal‐Catalyzed Cross‐Coupling Reactions and More

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“…C-H activation is therefore computed to be rate limiting, consistent with an intramolecular k H /k D KIE of 3.1. Experimentally, the modeled reaction requires 24 h at 110 ∘ C [91]. An alternative mechanism based on initial C-H activation of ethyl acrylate was also considered and found to have a higher barrier of 25.1 kcal mol −1 .…”

Section: Alkenylation and Aminationmentioning

confidence: 99%

Computational Studies of Heteroatom‐Assisted CH Activation at Ru, Rh, Ir, and Pd as a Basis for Heterocycle Synthesis and Derivatization

Carr¹,

Macgregor²,

McMullin³

2016

Transition Metal‐Catalyzed Heterocycle Synthesis via CH Activation

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IntroductionModern computational chemistry is a key tool by which insight into organometallic reaction mechanisms can be gained. The ability to characterize short-lived intermediates and transition states provides an ideal complement to experiment, where such information is often extremely difficult, if not impossible, to obtain. Recent years have seen great advances in understanding the mechanisms of C-H bond activation, and this area was the subject of several major reviews toward the end of the last decade [1,2]. More recently, the focus has shifted to how C-H activation can be integrated into catalytic cycles for useful organic transformations. The C-H bond activation event is itself mechanistically diverse, with oxidative addition (OA), σ-bond metathesis (SBM), and electrophilic activation (EA) all potentially available at late transition metal centers, depending on the metal, its oxidation state, and the coordination environment. C-H activation assisted by a heteroatom base (typically a carboxylate or carbonate) falls into the last of these categories and forms the focus of this chapter. More recently, computational studies of catalytic cycles for C-H activation and functionalization have become more common. These reveal the complexity of what are usually multiple-step processes, and calculations are particularly well placed to test different mechanistic possibilities. Such studies are most effectively pursued through a close interaction between experiment and computation, and increasingly this is allowing for a more quantitative assessment of computed reaction mechanisms.As well as progress in mechanistic understanding, the last 10 years have seen important developments in the computational methodologies available to model transition metal reactivity. While density functional theory (DFT) remains the core method of choice, the ability to model larger systems that more closely reflect experiment has highlighted the known shortcomings of DFT in describing dispersion interactions. These long-range, stabilizing interactions are individually weak, but their cumulative effect in large systems can be significant. Methods to incorporate this component include its separate calculation (e.g., Transition Metal-Catalyzed Heterocycle Synthesis via C-H Activation, First Edition. Edited by Xiao-Feng Wu.

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“…[61][62][63] In 2011, aR h III -catalyzed ortho-CÀHb ond alkenylation of ophenyl carbamate and its derivatives was independently reported by the groups of Liu [62] and Loh [61] (Scheme 7). [61][62][63] In 2011, aR h III -catalyzed ortho-CÀHb ond alkenylation of ophenyl carbamate and its derivatives was independently reported by the groups of Liu [62] and Loh [61] (Scheme 7).…”

Section: Carbamate Formationmentioning

confidence: 99%

Rhodium‐Catalyzed C(sp²)‐ or C(sp³)−H Bond Functionalization Assisted by Removable Directing Groups

2019

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In recent years, transition‐metal‐catalyzed C−H activation has become a key strategy in the field of organic synthesis. Rhodium complexes are widely used as catalysts in a variety of C−H functionalization reactions because of their high reactivity and selectivity. The availability of a number of rhodium complexes in various oxidation states enables diverse reaction patterns to be obtained. Regioselectivity, an important issue in C−H activation chemistry, can be accomplished by using a directing group to assist the reaction. However, to obtain the target functionalized compounds, it is also necessary to use a directing group that can be easily removed. A wide range of directed C−H functionalization reactions catalyzed by rhodium complexes have been reported to date. In this Review, we discuss Rh‐catalyzed C−H functionalization reactions that are aided by the use of a removable directing group such as phenol, amine, aldehyde, ketones, ester, acid, sulfonic acid, and N‐heteroaromatic derivatives.

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Rhodium-Catalyzed Selective C–H Activation/Olefination of Phenol Carbamates

Cited by 191 publications

References 36 publications

C–H Bond Alkenylation

C–H Bond Alkenylation

Computational Studies of Heteroatom‐Assisted CH Activation at Ru, Rh, Ir, and Pd as a Basis for Heterocycle Synthesis and Derivatization

Rhodium‐Catalyzed C(sp²)‐ or C(sp³)−H Bond Functionalization Assisted by Removable Directing Groups

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Rhodium-Catalyzed Selective C–H Activation/Olefination of Phenol Carbamates

Cited by 191 publications

References 36 publications

C–H Bond Alkenylation

C–H Bond Alkenylation

Computational Studies of Heteroatom‐Assisted CH Activation at Ru, Rh, Ir, and Pd as a Basis for Heterocycle Synthesis and Derivatization

Rhodium‐Catalyzed C(sp2)‐ or C(sp3)−H Bond Functionalization Assisted by Removable Directing Groups

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Rhodium‐Catalyzed C(sp²)‐ or C(sp³)−H Bond Functionalization Assisted by Removable Directing Groups