Rhodium(iii)-catalyzed chemodivergent annulations between N-methoxybenzamides and sulfoxonium ylides via C–H activation

Chemical Communications, Год журнала: 2018, Номер 54(6), С. 670 - 673

Опубликована: Янв. 1, 2018

Rhodium-catalyzed and acid-controlled chemodivergent annulations between N-methoxybenzamides sulfoxonium ylides have been realized.

Язык: Английский

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Iodonium Ylides as Carbene Precursors in Rh(III)-Catalyzed C–H Activation

Organic Letters, Год журнала: 2020, Номер 22(19), С. 7475 - 7479

Опубликована: Сен. 9, 2020

The rhodium(III)-catalyzed coupling of C-H substrates with iodonium ylides has been realized for the efficient synthesis diverse cyclic skeletons, where have identified as and outstanding carbene precursors. reaction systems are applicable to both sp2 sp3 under mild redox-neutral conditions. catalyst loading can be low 0.5 mol % in a gram-scale reaction. Representative products exhibit cytotoxicity toward human cancer cells at nanomolar levels.

Язык: Английский

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Rh(III)-Catalyzed Chemodivergent Annulations between Indoles and Iodonium Carbenes: A Rapid Access to Tricyclic and Tetracyclic N-Heterocylces

Organic Letters, Год журнала: 2021, Номер 23(11), С. 4233 - 4238

Опубликована: Май 21, 2021

Herein, we report an acid-controlled highly tunable selectivity of Rh(III)-catalyzed [4 + 2] and [3 3] annulations N-carboxamide indoles with iodonium ylides lead to form synthetically important tricyclic tetracyclic N-heterocycles. Here, ylide serves as a carbene precursor. The protocol proceeds under operationally simple conditions provides novel scaffolds such 3,4-dihydroindolo[1,2-c]quinazoline-1,6(2H,5H)-dione 1H-[1,3]oxazino[3,4-a]indol-1-one derivatives broad range functional group tolerance moderate excellent yields. Furthermore, the synthetic utility was extended for various chemical transformations easily scaled up large-scale level.

Язык: Английский

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Sigma-Bond Metathesis as an Unusual Asymmetric Induction Step in Rhodium-Catalyzed Enantiodivergent Synthesis of C–N Axially Chiral Biaryls

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(15), С. 8417 - 8429

Опубликована: Март 23, 2023

Mechanistic understanding of asymmetric induction plays a crucial role in designing new catalytic reactions. Reported herein is atroposelective access to C-N axially chiral isoquinolones via rhodium-catalyzed C-H activation N-alkoxy benzamides and annulation with imidoyl sulfoxonium ylides. The coupling system proceeded excellent functional group tolerance, different conditions were identified afford one or the other enantiomeric product each enantioselectivity for representative class ylide reagent, thus making both enantiomers readily available using same catalyst. Experimental computational studies revealed pathway alkylation enantio-determining formal nucleophilic substitution-C-N cyclization that mediated by rhodium catalyst σ-bond metathesis as mechanism. Computational indicated solvent-dependent enatiodivergence originated from levels neutral versus cationic species.

Язык: Английский

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Rh(iii)-Catalyzed straightforward arylation of 8-methyl/formylquinolines using diazo compounds

Chemical Communications, Год журнала: 2019, Номер 55(48), С. 6886 - 6889

Опубликована: Янв. 1, 2019

A straightforward Rh(iii)-catalyzed general strategy was developed for the introduction of naphthol/phenol moieties to 8-methyl and formylquinolines using diazonaphthalen-2(1H)-ones/quinone diazides.

Язык: Английский

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An unusual reaction mode of 1-phenylpyrazolidinones toward diazonaphthalen-2(1H)-ones featuring cascade C(sp²)–H and C(sp³)–H bond cleavage

Organic Chemistry Frontiers, Год журнала: 2021, Номер 8(13), С. 3238 - 3243

Опубликована: Янв. 1, 2021

Herein, a novel synthesis of pyrazolidinone fused 1,3-benzooxazepine derivatives via formal [4 + 3] annulation reaction 1-phenylpyrazolidinones with diazonaphthalen-2(1H)-ones is presented.

Язык: Английский

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Transition‐Metal‐Catalyzed C−H Bond Functionalization of Arenes/Heteroarenes via Tandem C−H Activation and Subsequent Carbene Migratory Insertion Strategy

The Chemical Record, Год журнала: 2021, Номер 21(12), С. 4088 - 4122

Опубликована: Окт. 14, 2021

Abstract The past decade has witnessed tremendous developments in transition‐metal‐catalyzed C−H bond activation and subsequent carbene migratory insertion reactions, thus assisting the construction of diverse arene/heteroarene scaffolds. Various transition‐metal catalysts serve this purpose provide efficient pathways for an easy access to substituted heterocycles. A brief introduction metal‐carbenes been provided along with key mechanistic underlying coupling reactions. review is a concise knowledge about directing group‐assisted varied arenes/heteroarenes acceptor‐acceptor/donor‐acceptor diazo compounds. also highlights synthesis various carbocycles fused heterocycles through pathways, via C−C, C−N C−O forming mechanism usually involves process, followed by leading coupling.

Язык: Английский

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Rh(III)-Catalyzed C–H Activation of Benzoylacetonitriles and Tandem Cyclization with Diazo Compounds to Substituted Benzo[de]chromenes

Organic Letters, Год журнала: 2018, Номер 20(7), С. 1720 - 1724

Опубликована: Март 22, 2018

Rh (III)-catalyzed C–H activation of benzoylacetonitriles in coupling with diazo compounds was developed to synthesize diversified substituted benzo[de]chromenes via a formal (4 + 2) cycloaddition compound and subsequent tandem another compound. Intriguingly, synthesis their decarboxylation products could be realized by controlling the reaction conditions. These reactions have broad range substrates, moderate good yields, high regioselectivity.

Язык: Английский

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Ruthenium(II) Porphyrin Quinoid Carbene Complexes: Synthesis, Crystal Structure, and Reactivity toward Carbene Transfer and Hydrogen Atom Transfer Reactions

Journal of the American Chemical Society, Год журнала: 2019, Номер 141(22), С. 9027 - 9046

Опубликована: Май 8, 2019

Reactivity study of novel metal carbene complexes can offer new opportunities in catalytic transfer reactions as well other synthetic protocols. Metal with quinoid (QC) ligands are assumed to be key intermediates a variety metal-catalyzed QC using diazo quinones, which demands development the chemistry characterized metal–QC complexes. Herein we report isolation and ruthenium porphyrins [Ru(Por)(QC)] contribute first examples (i) structurally complex (by X-ray crystallography) (ii) isolated that undergoes reaction. The were prepared from reaction [Ru(Por)(CO)] quinones exhibited dual reactivity, i.e., hydrogen atom (HAT) transfer. stoichiometric these Ru–QC nitrosoarenes (ArNO) afforded nitrones up 90% yield, corresponding also developed. Both for series bearing electron-donating -withdrawing substituents showed reverse substituent effect on reactivity. Complexes reactive toward C–H X–H (X = N, S) bonds catalyze aerobic oxidation 1,4-cyclohexadiene; their HAT unsaturated hydrocarbons gave product yields 88%. unique reactivity electronic feature studied by spectroscopic means density functional theory (DFT) calculations.

Язык: Английский

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Rh^III‐Catalyzed Direct C8‐Arylation of Quinoline N‐Oxides using Diazonaphthalen‐2(1H)‐ones: A Practical Approach towards 8‐aza BINOL

Chemistry - An Asian Journal, Год журнала: 2018, Номер 13(17), С. 2388 - 2392

Опубликована: Апрель 17, 2018

Abstract An efficient Rh III ‐catalyzed redox‐neutral method for the direct C8‐arylation of quinoline N ‐oxides using diazonaphthalen‐2(1 H )‐one as coupling partner has been demonstrated. The developed is simple, scalable and straightforward with a wide range substrate scope. applicative potential was extended late‐stage functionalization synthesis 8‐azaBINOL derivative. A plausible reaction pathway proposed after carrying out preliminary control studies.

Язык: Английский

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