Catalytic Asymmetric Cascade Dearomatization of Indoles via a Photoinduced Pd‐Catalyzed 1,2‐Bisfunctionalization of Butadienes

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(26)

Опубликована: Апрель 20, 2024

Photoinduced Pd-catalyzed bisfunctionalization of butadienes with a readily available organic halide and nucleophile represents an emerging attractive method to assemble versatile alkenes bearing various functional groups at the allylic position. However, enantiocontrol and/or diastereocontrol in C-C or C-X bond-formation step have not been solved due open-shell process. Herein, we present cascade asymmetric dearomatization reaction indoles via photoexcited 1,2-biscarbonfunctionalization 1,3-butadienes, wherein control on both electrophile part is achieved for first time photoinduced butadienes. This delivers structurally novel chiral spiroindolenines two contiguous stereogenic centers high diastereomeric ratios (up >20 : 1 dr) good excellent enantiomeric 97 3 er). Experimental computational studies mechanism confirmed radical pathway involving excited-state palladium catalysis. The alignment non-covalent interactions between substrate catalyst were found be essential stereocontrol.

Язык: Английский

---

Selective 1,4-syn-Addition to Cyclic 1,3-Dienes via Hybrid Palladium Catalysis

ACS Central Science, Год журнала: 2024, Номер 10(6), С. 1191 - 1200

Опубликована: Май 15, 2024

1,4-cis-Disubstituted cyclic compounds play a pivotal role in pharmaceutical development, offering enhanced potency and bioavailability. However, their stereoselective modular synthesis remains long-standing challenge. Here, we report an innovative strategy for accessing these structures via mild conditions employing 1,3-dienes/alkyl(aryl)halides amines. This procedure exhibits wide substrate scope that tolerates various functional groups. The utility of this method is demonstrated the efficient TRPV6 inhibitor, CFTR modulator, other bioactive molecules. Combined experimental computational studies suggest hybrid palladium-catalyzed radical-polar crossover mechanism crucial achieving exceptional 1,4-syn-addition selectivity (dr > 20:1).

Язык: Английский

---

Photoinduced Electron Donor Acceptor Complex‐Enabled α‐C(sp³)−H Alkenylation of Amines

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(44)

Опубликована: Июль 13, 2024

Allylic amines are prevalent and vital structural components present in many bioactive compounds natural products. Additionally, they serve as valuable intermediates building blocks, with wide-ranging applications organic synthesis. However, direct α-C(sp

Язык: Английский

---

Illuminating Palladium Catalysis

Accounts of Chemical Research, Год журнала: 2025, Номер unknown

Опубликована: Фев. 26, 2025

ConspectusThe past decade has witnessed significant advancements of visible-light-induced photocatalysis, establishing it as a powerful and versatile tool in organic synthesis. The major focus this field centered on the development methodologies that either rely solely photocatalysts or combine photocatalysis with other catalytic methods, such transition metal catalysis, to address broader more diverse array transformations. Within rapidly evolving area, subfield we refer garnered attention due its growing impact mechanistic uniqueness. A distinguishing feature is dual functionality single complex, which not only acts photocatalyst initiate photochemical processes but also functions traditional catalyst, facilitating key bond-breaking bond-forming events. As such, an exogenous required photocatalysis. However, implications harnessing both excited- ground-state reactivities complex can extend beyond simplification. One most compelling aspects area photoexcited complexes exhibit unique inaccessible through conventional thermal photocatalytic approaches. These distinct be leveraged accomplish novel transformations by engaging entirely different substrate pool unlocking new known substrates.In 2016, our group pioneered use phosphine-ligated palladium catalysts upon visible-light irradiation engage substrates radical reactions. In initial discovery, showed photoexcitation redirect well-established oxidative addition Pd(0) into aryl iodides toward unprecedented process, generating hybrid Pd(I) species. We subsequently extended strategy formation alkyl radicals from halides. reactive intermediates have been harnessed wide variety transformations, including desaturation, Heck reactions, alkene difunctionalization cascades, among others.Seeking further expand avenue, achieved first example asymmetric context allylic C–H amination, where catalyst now plays triple duty additionally controlling stereochemical outcome reaction. parallel reaction established diazo compounds, strained molecules, electron-deficient alkenes serve precursors halides redox-active esters. Notably, engagement made possible photoinduced hydricity enhancement Pd–H species, representing mode reactivity.This Account presents discovery organized type explored. Given rapid progress field, anticipate will provide readers guiding principles inspiration for designing developing efficient

Язык: Английский

---

Photoinduced Pd-Catalyzed Formal Asymmetric Allylic Substitution of Piperidine Scaffolds

ACS Catalysis, Год журнала: 2025, Номер unknown, С. 4384 - 4393

Опубликована: Фев. 26, 2025

Язык: Английский

---

Escape from Hydrofunctionalization: Palladium Hydride‐Enabled Difunctionalization of Conjugated Dienes and Enynes

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(47)

Опубликована: Окт. 3, 2023

Abstract Palladium hydrides are traditionally employed in hydrofunctionalization (i.e. monofunctionalization) of conjugated dienes and enynes, owning to its facile protic hydropalladation electron‐rich (or neutral) unsaturated bonds. Herein, we report a mild PdH‐catalyzed difunctionalization enynes. This protocol is enabled by the chemoselectivity switch initial step achieved visible light enhancement hydricity PdH species. method allows for cascade annulation enynes with various easily available abundant substrates, such as acrylic acids, amides, Baylis–Hillman adducts, toward wide range alkenyl or alkynyl lactones, lactams, tetrahydrofurans. also provides an easy access complex spiro‐fused tricyclic frameworks.

Язык: Английский

---

Selective Access to Functional Fluoroenones via Palladium-Catalyzed Selenofluoroalkylacylation of Terminal Alkynes

Organic Letters, Год журнала: 2024, Номер 26(4), С. 906 - 911

Опубликована: Янв. 19, 2024

The trifluoromethylacyl group (-COCF

Язык: Английский

---

Ruthenium-Catalyzed γ-Selective Intermolecular Amidation of Nonactivated Distal Methylene C–H Bonds of Terminal Alkenes via Olefin Chain-Walking Isomerization

ACS Catalysis, Год журнала: 2025, Номер unknown, С. 3980 - 3991

Опубликована: Фев. 20, 2025

Язык: Английский

---

Mononuclear palladium(I) and palladium(III) coordination compounds

Coordination Chemistry Reviews, Год журнала: 2025, Номер 535, С. 216605 - 216605

Опубликована: Март 17, 2025

---

Allylation of C‐, N‐, and O‐Nucleophiles via a Mechanochemically‐Driven Tsuji–Trost Reaction Suitable for Late‐Stage Modification of Bioactive Molecules

Angewandte Chemie International Edition, Год журнала: 2023, Номер 63(1)

Опубликована: Ноя. 6, 2023

Abstract We present the first solvent‐free, mechanochemical protocol for a palladium‐catalyzed Tsuji–Trost allylation. This approach features exceptionally low catalyst loadings (0.5 mol %), short reaction times (<90 min), and simple setup, eliminating need air or moisture precautions, making process highly efficient environmentally benign. introduce solid, nontoxic, easy‐to‐handle allyl trimethylammonium salts as valuable alternative to volatile hazardous reagents. Our enables allylation of various O ‐, N C ‐nucleophiles in yields up 99 % even structurally complex bioactive compounds, owing its mild conditions exceptional functional group tolerance.

Язык: Английский

---