Enantio- and Regioselective Ni-Catalyzed Radical Relay 1,4-Arylalkylation of 1,3-Enynes to Access Chiral Tetrasubstituted Allenes

ACS Catalysis, Год журнала: 2024, Номер 14(18), С. 13940 - 13946

Опубликована: Сен. 5, 2024

Язык: Английский

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Metallaphotoredox Synthesis of Axially Chiral Tetrasubstituted Allenes through Regio- and Enantioselective 1,4-Carbocyanation of 1,3-Enynes

ACS Catalysis, Год журнала: 2024, Номер 14(18), С. 14048 - 14057

Опубликована: Сен. 10, 2024

Язык: Английский

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Ni‐Catalyzed Synthesis of Multisubstituted Allenes via Reductive Cross‐Coupling of Propargylic Acetates with Chlorohydrosilanes

European Journal of Organic Chemistry, Год журнала: 2024, Номер unknown

Опубликована: Дек. 12, 2024

Abstract This paper introduces an innovative strategy for the synthesis of multisubstituted allenes via nickel‐catalyzed reductive cross‐coupling reactions. The approach utilizes propargyl acetates and chlorosilanes to produce a variety silyl‐substituted allenes. reaction conditions are notably mild, process is characterized by high chemo‐ regioselectivity, as well impressive substrate scope. Furthermore, method can be readily extended use chlorogermane chlorostannane, facilitating germanium or stannium‐substituted research not only offers valuable preparation but also significantly broadens synthetic repertoire construction highly functionalized molecules.

Язык: Английский

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Axial Ligand Enables Synthesis of Allenylsilane through Dirhodium(II) Catalysis

Angewandte Chemie, Год журнала: 2024, Номер 136(38)

Опубликована: Июнь 18, 2024

Abstract Described herein is a dirhodium(II)‐catalyzed silylation of propargyl esters with hydrosilanes, using tertiary amines as axial ligands. By adopting this strategy, range versatile and useful allenylsilanes can be achieved good yields. This reaction not only represents S N 2′‐type the derivatives bearing terminal alkyne moiety to synthesize from simple but also new application dirhodium(II) complexes in catalytic transformation carbon‐carbon triple bond. The highly functionalized that are produced transformed into series synthetically organic molecules. In reaction, an intriguing ON‐OFF effect amine ligand was observed. almost did occur ( OFF ) without addition Lewis base ligand. However, took place smoothly ON after amount Detailed mechanistic studies density functional theory (DFT) calculations indicate reactivity delicately improved by use amine. fine‐tuning crucial formation Rh−Si species via concerted metalation deprotonation (CMD) mechanism facilitating β‐ oxygen elimination.

Язык: Английский

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Elektrochemische Gerüst‐Editierung von Indolen durch Stickstoffatom‐Insertion mit nachhaltiger Sauerstoff‐Reduktionsreaktion

Angewandte Chemie, Год журнала: 2024, Номер 136(41)

Опубликована: Июль 3, 2024

Abstract Molekulares Editieren hat in letzter Zeit stark an Bedeutung gewonnen und sich als einzigartiges Werkzeug für Late‐Stage Diversifizierungen erwiesen. Bislang waren die Indol‐Editierung meist überstöchiometrische Mengen teuren hochvalenten Iod(III)‐Reagenzien erforderlich. Im Gegensatz dazu zeigen wir hier, dass Elektrizität nachhaltige Stickstoffatom‐Insertionsreaktionen ermöglicht, um bio‐relevante Chinazolin‐Gerüste ohne stöchiometrische chemische Redox‐Abfallprodukte zu erhalten. Die Übergangsmetall freie Elektro‐Editierung wurde durch Sauerstoff‐Reduktionsreaktion (ORR) ermöglicht erwies großem Maßstab robust, wobei eine Vielzahl wertvoller funktioneller Gruppen toleriert wurden.

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