Nickel Catalyzed Enantioselective 1,4-Hydroamination of 1,3-Dienes

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(27), P. 18440 - 18450

Published: July 1, 2024

Transition metal-catalyzed enantioselective hydroamination of 1,3-dienes provides a direct methodology for the construction chiral allylamines. So far, all reported examples used nucleophilic amines and proceeded with 3,4-regioselectivity. Herein, we describe first example nickel-catalyzed 1,4-hydroamination using trimethoxysilane hydroxylamines structurally adaptable aromatic spiroketal based diphosphine (SKP) as ligand, affording wide array α-substituted allylamines in high yields excellent regio- enantioselectivities. This operationally simple protocol demonstrated broad substrate scope functional group compatibility, significantly expanding chemical space Experimental DFT studies were performed to elucidate mechanism rationalize enantioselectivities reaction.

Language: Английский

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Palladium(II)-Catalyzed Regioselective Hydroamination of Allylamines to N-Alkyl Sulfoximines

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 14, 2025

An intermolecular coupling between sulfoximines and allyl amines, linked to the picolinamide directing group, is developed by leveraging a nucleopalladation-guided regioselective hydroamination strategy, enabling production of range valuable N-alkyl in high yields. The protocol features operational simplicity broad substrate scope was also amenable aniline nucleophiles. Synthetic utilities were showcased through scale-up reactions product diversifications, leading biorelevant molecules.

Language: Английский

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Base-free NiH-catalyzed regio- and stereo-selective hydroacylation of allenes: A new route to synthesis of tetra-substituted olefins

Chem Catalysis, Journal Year: 2023, Volume and Issue: 3(5), P. 100606 - 100606

Published: April 17, 2023

Language: Английский

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Rhodium‐Catalyzed Asymmetric Macrocyclization towards Crown Ethers Using Hydroamination of Bis(allenes)

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(14)

Published: Feb. 7, 2024

Abstract Enantiomerically enriched crown ethers (CE) exhibit strong asymmetric induction in phase transfer catalysis, supramolecular catalysis and molecular recognition processes. Traditional methods have often been used to access these valuable compounds, which limit their diversity consequently applicability. Herein, a practical catalytic method is described for the gram scale synthesis of class chiral CEs (aza‐crown ethers; ACEs) using Rh‐catalyzed hydroamination bis(allenes) with diamines. Using this approach, wide range vinyl functionalized ring sizes ranging from 12 36 successfully prepared high yields up 92 %, dr >20 : 1 er >99 1. These substituted allow further diversification giving facile various CE derivatives as well three‐dimensional analogues ring‐closing metathesis. Some themselves display potential use catalysis.

Language: Английский

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O-Benzoylhydroxylamines: A Versatile Electrophilic Aminating Reagent for Transition Metal-Catalyzed C–N Bond-Forming Reactions

Topics in Current Chemistry, Journal Year: 2022, Volume and Issue: 381(1)

Published: Dec. 18, 2022

Language: Английский

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