Remote site-selective C–H activation directed by a catalytic bifunctional template

Nature, Год журнала: 2017, Номер 543(7646), С. 538 - 542

Опубликована: Март 1, 2017

Язык: Английский

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Meta-Selective C_Ar–H Nitration of Arenes through a Ru₃(CO)₁₂-Catalyzed Ortho-Metalation Strategy

Journal of the American Chemical Society, Год журнала: 2016, Номер 138(27), С. 8470 - 8475

Опубликована: Май 15, 2016

The first example of transition metal-catalyzed meta-selective CAr–H nitration arenes is described. With the use Ru3(CO)12 as catalyst and Cu(NO3)2·3H2O nitro source, a wide spectrum bearing diversified N-heterocycles or oximido directing groups were nitrated with meta-selectivity exclusively. Mechanism studies have demonstrated formation new 18e-octahedral ruthenium species key ortho-CAr–H metalated intermediate, which may be responsible for subsequent electrophilic aromatic substitution (SEAr). Moreover, this approach provides fast-track strategy atom/step economical synthesis many useful pharmaceutical molecules.

Язык: Английский

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Strategic evolution in transition metal-catalyzed directed C–H bond activation and future directions

Coordination Chemistry Reviews, Год журнала: 2020, Номер 431, С. 213683 - 213683

Опубликована: Дек. 9, 2020

Язык: Английский

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Access to the meta position of arenes through transition metal catalysed C–H bond functionalisation: a focus on metals other than palladium

Chemical Society Reviews, Год журнала: 2017, Номер 47(1), С. 149 - 171

Опубликована: Окт. 26, 2017

The elaboration of simple arenes in order to access more complex substitution patterns is a crucial endeavor for synthetic chemists, given the central role that aromatic rings play all manner important molecules. Classical methods are now routinely used alongside stoichiometric organometallic approaches and, most recently, transition metal catalysis range methodologies available elaborate arene C-H bonds. Regioselectivity an consideration when selecting method those available, it arguably target meta position fewest number. rapid development metal-catalysed bond functionalisation over last few decades has opened new possibilities meta-selective through diverse reactivity metals and their compatibility with wide directing groups. pace discovery such processes grown rapidly five years particular purpose this review examine these but doing so place focus on other than palladium, specific contributions which have been very recently reviewed elsewhere. It hoped will serve highlight reader breadth current strategies mechanisms tackle challenge, may inspire further progress field.

Язык: Английский

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Hexafluoroisopropanol: the magical solvent for Pd-catalyzed C–H activation

Chemical Science, Год журнала: 2021, Номер 12(11), С. 3857 - 3870

Опубликована: Янв. 1, 2021

Among numerous solvents available for chemical transformations, 1,1,1,3,3,3-hexafluoro-2-propanol (popularly known as HFIP) has attracted enough attention of the scientific community in recent years.

Язык: Английский

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Ruthenium(II)‐Catalyzed meta C−H Mono‐ and Difluoromethylations by Phosphine/Carboxylate Cooperation

Angewandte Chemie International Edition, Год журнала: 2017, Номер 56(8), С. 2045 - 2049

Опубликована: Янв. 20, 2017

Abstract Ruthenium(II)‐catalyzed meta ‐selective C−H (di)fluoromethylation was accomplished by phosphine and carboxylate cooperation. The remote functionalization characterized ample substrate scope, thereby setting the stage for ‐(di)fluoromethylation through facile cleavage.

Язык: Английский

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Palladium‐Catalyzed Directed para C−H Functionalization of Phenols

Angewandte Chemie International Edition, Год журнала: 2016, Номер 55(27), С. 7751 - 7755

Опубликована: Май 9, 2016

Abstract Various practical methods for the selective C−H functionalization of ortho and recently also meta position an arene have already been developed. Following our recent development directing‐group‐assisted para toluene derivatives, we herein report first remote phenol derivatives by using a recyclable silicon‐containing biphenyl‐based template. The effectiveness this strategy was illustrated with different synthetic elaborations synthesis various phenol‐based natural products.

Язык: Английский

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Palladium(II)‐Initiated Catellani‐Type Reactions

Angewandte Chemie International Edition, Год журнала: 2018, Номер 58(18), С. 5832 - 5844

Опубликована: Дек. 27, 2018

Abstract The Catellani reaction is known as a powerful strategy for the expeditious synthesis of highly substituted arenes and benzo‐fused rings, which are usually difficult to access through traditional cross‐coupling strategies. It utilizes synergistic interplay palladium norbornene catalysis facilitate sequential ortho C−H functionalization ipso termination aryl halides in single operation. In classical Catellani‐type reactions, mainly used substrates, Pd 0 catalyst required initiate reaction. Nevertheless, recent advances showcase that reactions can also be initiated by II with different starting materials instead via mechanisms under conditions. This emerging concept /norbornene cooperative has significantly advanced thus enabling future developments this field. Minireview, ‐initiated their application bioactive molecules summarized.

Язык: Английский

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Remote Meta-C–H Activation Using a Pyridine-Based Template: Achieving Site-Selectivity via the Recognition of Distance and Geometry

ACS Central Science, Год журнала: 2015, Номер 1(7), С. 394 - 399

Опубликована: Окт. 16, 2015

The pyridyl group has been extensively employed to direct transition-metal-catalyzed C-H activation reactions in the past half-century. typical cyclic transition states involved these cyclometalation processes have only enabled of ortho-C-H bonds. Here, we report that pyridine is adapted meta-C-H benzyl and phenyl ethyl alcohols through engineering distance geometry a directing template. This template takes advantage stronger σ-coordinating recruit Pd catalysts desired site for functionalization. U-shaped structure accommodates otherwise highly strained cyclophane-like state. development illustrates potential achieving selectivity via recognition distal geometric relationship between existing functional groups multiple bonds organic molecules.

Язык: Английский

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Recent development in transition metal-catalysed C–H olefination

Chemical Science, Год журнала: 2021, Номер 12(8), С. 2735 - 2759

Опубликована: Янв. 1, 2021

Transition metal-catalysed functionalizations of inert C-H bonds to construct C-C represent an ideal route in the synthesis valuable organic molecules. Fine tuning directing groups, catalysts and ligands has played a crucial role selective bond (sp2 or sp3) activation. Recent developments these areas have assured high level regioselectivity olefination reactions. In this review, we summarized recent progress oxidative sp2 sp3 with special emphasis on distal, atroposelective, non-directed directed olefination. The scope, limitation, mechanism various transition reactions been described briefly.

Язык: Английский

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