One-Step Construction of Atropisomers Bearing 1,5-Central and Axial Chirality via Catalytic Diastereo- and Atroposelective Remote Desymmetrizing Alkynylation

ACS Catalysis, Год журнала: 2024, Номер unknown, С. 18872 - 18883

Опубликована: Дек. 11, 2024

Catalytic asymmetric construction of atropisomers with multiple stereogenic elements has recently become an emerging area. However, general methods that produced bearing remote 1,5-axial and central chirality efficiently stereoselectively are scarce yet highly challenging. We herein report a catalytic diastereo- atroposelective desymmetrizing alkynylation axially prochiral dialkynes ortho-quinone methides (o-QMs), furnishing 1,5-remote centrally elements. The control axis far from the reaction site could be simultaneously achieved during stereoselective C(sp3)–C(sp) bond-forming process to generate center. In addition, kinetic resolution racemic alkynes via o-QMs been developed, further enriching structural diversity 1,5-central axial chirality. present method expands chemical space atropisomeric molecules chiral by facile downstream diversification C–C triple bonds. Finally, can also applied for motifs 1,9- 1,10-stereogenic centers.

Язык: Английский

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Atroposelective Synthesis of Axially Chiral Styrenes by Platinum‐ Catalyzed Stereoselective Hydrosilylation of Internal Alkynes

Angewandte Chemie, Год журнала: 2023, Номер 135(30)

Опубликована: Май 25, 2023

Abstract Hydrofunctionalization of alkynes is one the most efficient ways to access axially chiral styrenes with open‐chained olefins. While great advances have been achieved for 1‐alkynylnaphthalen‐2‐ols and analogues, atroposelective hydrofunctionalization unactivated internal lags. Herein we reported a platinum‐catalyzed hydrosilylation first time. With monodentate TADDOL‐derived phosphonite L1 used as ligand, various were in excellent enantioselectivities high E ‐selectivities. Control experiments showed that N H‐arylamide groups significant effects on both yields could act directing groups. The potential utilities products shown by transformations amide motifs products.

Язык: Английский

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Quinolinamide-Enabled Nickel-Catalyzed Regio- and Diastereoselective γ,δ-Arylalkylation of Nonactivated Alkenes

Synlett, Год журнала: 2023, Номер 35(10), С. 1121 - 1126

Опубликована: Окт. 16, 2023

Abstract A quinolinamide-enabled nickel-catalyzed γ,δ-arylalkylation of homoallylic amines with aryl iodides and organozinc compounds has been developed. The cleavable quinolinamide directing group facilitates the stabilization a five-membered nickelacycle, enables dicarbofunctionalization nonactivated alkenes excellently regio-, chemo-, diastereoselectivity. reaction internal proceeds stereospecifically to provide valuable γ-alkyl-δ-aryl-substituted two vicinal stereocenters. scope substrates utility protocol have thoroughly studied.

Язык: Английский

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Iridium-Catalyzed Regio- and Enantioselective Propargylic C−H Silylation

Опубликована: Июнь 9, 2023

ABSTRACT: We report a highly enantioselective intermolecular silylation of the propargylic C(sp3)−H bonds alkynes for formation silanes. The optimized protocol afforded enantioenriched α-silylated in good to high yield with excellent levels stereocontrol under mild conditions. A variety silyl triflates, either commercial or situ-generated, were used as reagents, and broad range simple functionalized alkynes, including aryl alkyl acetylenes, dialkyl 1,3-enynes, successfully employed substrates. In case acetylene substrates, took place regi-oselective manner. Preliminary mechanistic experiments suggest catalytic cycle which electrophilic addition triflate reagent Ir center subsequent deprotonation dicationic Ir–alkyne complex are key steps.

Язык: Английский

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Catalytic Addition of C–H Bonds Across C–C π-Bonds

Elsevier eBooks, Год журнала: 2023, Номер unknown

Опубликована: Янв. 1, 2023

Язык: Английский

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