Post-synthetic modification of dual-porous UMCM-1-NH2 with palladacycle complex as an effective heterogeneous catalyst in Suzuki and Heck coupling reactions

Journal of Organometallic Chemistry, Год журнала: 2023, Номер 989, С. 122646 - 122646

Опубликована: Фев. 15, 2023

Язык: Английский

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Design of C1-symmetric tridentate ligands for enantioselective dearomative [3 + 2] annulation of indoles with aminocyclopropanes

Nature Communications, Год журнала: 2023, Номер 14(1)

Опубликована: Апрель 20, 2023

Chiral polycyclic indolines are widely present in natural products and have become the focus of extensive synthetic efforts. Here, we show catalytic asymmetric dearomative [3 + 2] annulation indoles with donor-acceptor aminocyclopropanes to construct tricyclic indolines. Key success reaction is rational design C1-symmetric bifunctional tridentate imidazoline-pyrroloimidazolone pyridine ligand. Under 5 mol% Ni(OTf)2-ligand complex, diverse containing cyclopentamine moieties obtained good chemoselectivities, high diastereoselectivities, excellent enantioselectivities. An unusual cis-configuration ligand superior trans-configuration corresponding C2-symmetric nitrogen ligands reaction. Mechanistic studies by control experiments density functional theory calculations reveal a dual activation manner, where Ni(II) complex activates aminocyclopropane via coordination geminal diester, imidazolidine NH forms H-bond succinimide moiety.

Язык: Английский

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Stereodivergent Construction of 1,5/1,7‐Nonadjacent Tetrasubstituted Stereocenters Enabled by Pd/Cu‐Cocatalyzed Asymmetric Heck Cascade Reaction

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(35)

Опубликована: Май 16, 2024

Abstract The construction of chiral motifs containing nonadjacent stereocenters in an enantio‐ and diastereoselective manner has long been a challenging task synthetic chemistry, especially with respect to their stereodivergent synthesis. Herein, we describe protocol that enables the 1,5/1,7‐nonadjacent tetrasubstituted through Pd/Cu‐cocatalyzed Heck cascade reaction. Notably, C=C bond relay strategy involving shift π‐allyl palladium intermediate was successfully applied asymmetric 1,7‐nonadjacent stereocenters. current method allows for efficient preparation molecules bearing two privileged scaffolds, oxindoles non‐natural α‐amino acids, good functional group tolerance. full complement four stereoisomers products could be readily accessed by simple combination metal catalysts different enantiomers.

Язык: Английский

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Photoinduced Pd-Catalyzed Dearomative 2,5-Difunctionalizition of Furans via Cascade C–C/C–O Bond Formation

Organic Letters, Год журнала: 2024, Номер 26(5), С. 1083 - 1087

Опубликована: Янв. 26, 2024

We report an efficient and mild approach for radical dearomatization via photoinduced palladium-catalyzed reaction of three components (i.e., furans, alcohols, bromoalkanes). In this strategy, various functionalized spiro-heterocycles were prepared from furans in one step cascade C–C/C–O bond formation under redox neutral conditions.

Язык: Английский

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Recent Developments in Enantioselective Domino Reactions. Part A: Noble Metal Catalysts

Advanced Synthesis & Catalysis, Год журнала: 2023, Номер 365(5), С. 620 - 681

Опубликована: Янв. 17, 2023

Abstract This review updates the field of enantioselective domino reactions promoted by chiral catalysts derived from noble metals, including palladium, silver, rhodium, ruthenium, iridium and gold, published since beginning 2019. It illustrates how much a diversity these allow unprecedented asymmetric many types to be achieved with excellent enantioselectivity, giving direct access wide variety complex molecules. magnified image

Язык: Английский

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Divergent Rh Catalysis: Asymmetric Dearomatization Versus C–H Activation Initiated by C–C Activation

ACS Catalysis, Год журнала: 2023, Номер 13(7), С. 4873 - 4881

Опубликована: Март 27, 2023

The divergent catalytic reactions based on C–C activation of benzocyclobutenones have been discovered, consisting a highly enantioselective dearomatic "Cut & Sew" transformation and cascade C–C/C–H activation/annulation process. asymmetric dearomatization was achieved with 2.5 mol % [Rh(HQ)(cod)]BF4 3 (S)-dtbm-Segphos, leading to variety enantioenriched polyfused rings (21 examples, up 99% yield enantiometric excess (ee)). While the tandem yields series amide-linked biaryl tricycles (29 89% yield) through net C1–C2 bond Caryl–H metathesis. A detailed density functional theory (DFT) computation revealed that an amide-directed regioselective Rh complex is realized, in contrast known C1–C8 cleavage. origins were further elucidated.

Язык: Английский

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Cobalt-Catalyzed Asymmetric Dearomative [3 + 2] Annulation of Quinolines, Isoquinolines, and Pyridines

ACS Catalysis, Год журнала: 2023, Номер 13(17), С. 11528 - 11540

Опубликована: Авг. 16, 2023

A highly enantioselective dearomative [3 + 2] annulation of quinolines, isoquinolines, and pyridines with donor–acceptor aminocyclopropanes was achieved. With C1-symmetric imidazoline-pyrroloimidazolone pyridine as the tridentate ligand Co(OTf)2 Lewis acid, diverse chiral indolizidine benzo-fused derivatives were obtained in good yields (up to 98% yield), excellent diastereoselectivities (>20:1 dr), enantioselectivities ee). Mechanistic experiments density functional theory (DFT) calculations revealed that nitrogen acted a bifunctional ligand. The not only coordinated Co(II) salt activate aminocyclopropane via bidentate coordination, but also formed H-bond oxygen atom succinimide moiety fix orientation aminocyclopropane, thus facilitating nucleophilic attack N-heteroaromatics. Additionally, high enantioselectivity reaction governed by steric factors.

Язык: Английский

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Palladium-Catalyzed Enantioselective Multicomponent Cross-Coupling of Trisubstituted Olefins

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(24), С. 16892 - 16901

Опубликована: Июнь 6, 2024

The development of a catalytic method for stereogenic carbon center formation holds immense significance in organic synthesis. Transition-metal-catalyzed cross-coupling reaction has been regarded as straightforward and efficient tool stereoselectively forging C–C bond. Nevertheless, the creation acyclic all-carbon quaternary-containing vicinal stereocenters remains notoriously challenging within domain chemistry despite their prominence various bioactive small molecules. Herein, we describe palladium-catalyzed asymmetric multicomponent trisubstituted alkene with aryl diazonium salts arylboronic acids to realize tertiary-quaternary centers high regio-, distereo-, enantioselectivity. Specifically, precise manipulation stereoconfiguration alkenes enables divergent stereoselective reaction, thus allowing facile construction all four enantiomers. Harnessing ligand-swap strategy involving chiral bisoxazoline an achiral fumarate individually accelerates enantioselective migratory insertion reductive elimination step process, supported by density functional theory (DFT) calculations, obviating requirement neighboring directing group internal olefin skeleton.

Язык: Английский

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Enantioselective Construction of Anthracenylidene-Based Axial Chirality by Asymmetric Heck Reaction

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(28), С. 19137 - 19145

Опубликована: Июль 2, 2024

Anthracenylidene is an intriguing structural unit with potential in various fields. The study presents a novel approach to introducing axial chirality into this all-carbon core skeleton through remotely controlled desymmetrization strategy. A palladium-catalyzed enantioselective Heck arylation of exocyclic double bond anthracene two distinct substituents at the C10 position harnessed realize such transformation. judicious identification P-centrally chiral ligand pivotal ensure competitive competence reactivity and stereocontrol when heteroatom handle absent from anthracenylidene skeleton. Both mono- disubstituted substrates were compatible for established catalytic system, structurally diverse anthracenylidene-based frameworks forged good-to-high enantiocontrol. subsequent derivatization obtained products yielded valuable array centrally axially molecules, thus emphasizing practicality chemistry. DFT calculations shed light on mechanism provided insights origin experimentally observed enantioselectivity reaction.

Язык: Английский

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Catalytic Asymmetric Dearomatization of 2,3-Disubstituted Indoles by a [4 + 2] Cycloaddition Reaction with In Situ Generated Vinylidene ortho-Quinone Methides: Access to Polycyclic Fused Indolines

Organic Letters, Год журнала: 2024, Номер 26(24), С. 5057 - 5062

Опубликована: Март 15, 2024

A protocol of enantioselective dearomatization 2,3-disubstituted indoles by an organocatalytic intermolecular (4 + 2) cycloaddition reaction with in situ generated vinylidene ortho-quinone methide has been documented. wide range polycyclic 2,3-fused indolines containing vicinal quaternary carbon stereocenters was readily prepared high yields and excellent diastereo- enantioselectivities.

Язык: Английский

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