We report a novel organic photoredox catalysis to achieve unprecedented γ-(hetero)aryl/alkenyl-δ-silyl aliphatic amines via silyl-mediated distal (hetero)aryl/alkenyl migration of aromatic/alkenyl amines bearing unactivated alkenes with hydrosilanes. This protocol features mild and metal-free reaction conditions, high atom economy, excellent selectivity, and functional group compatibility. Mechanistic studies suggest that silylation and (hetero)aryl/alkenylation involve photoredox hydrogen atom transfer catalysis and subsequent 1,4-migration of a remote (hetero)aryl/alkenyl group from nitrogen to carbon.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1021/acs.orglett.4c01414 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Recent advances in carbosilylation of alkenes and alkynes.
Org Biomol Chem
March 2023
Department of Chemistry, Visva-Bharati (A Central University), Santiniketan 731235, India.
Alkene and alkyne difunctionalization is a flexible process that allows the construction of two functional groups simultaneously in one step. On the other hand, carbosilylation, an ingenious difunctionalization pathway to concurrently incorporate both a silyl group and an organic functional group (alkyl, (hetero)aryl, alkenyl, alkynyl and allenyl) across a carbon-carbon multiple-bond system, is achieving immense interest in recent days. This review article provides a decade's update on the discoveries and developments in the synthesis of carbosilylated products from two very important carbon-carbon unsaturated substrates, alkenes and alkynes.
View Article and Find Full Text PDFFormal β-C-H Arylation of Aldehydes and Ketones by Cooperative Nickel and Photoredox Catalysis.
Angew Chem Int Ed Engl
August 2022
Organisch-Chemisches Institut, Westfälische Wilhelms-Universität, Corrensstraße 40, 48149, Münster, Germany.
α-C-H-functionalization of ketones and aldehydes has been intensively explored in organic synthesis. The functionalization of unactivated β-C-H bonds in such carbonyl compounds is less well investigated and developing a general method for their β-C-H arylation remains challenging. Herein we report a method that uses cooperative nickel and photoredox catalysis for the formal β-C-H arylation of aldehydes and ketones with (hetero)aryl bromides.
View Article and Find Full Text PDFNickel-Catalyzed Reductive C(sp )-Si Coupling of Chlorohydrosilanes via Si-Cl Cleavage.
Angew Chem Int Ed Engl
May 2022
State Key Laboratory of Applied Organic Chemistry (SKLAOC), College of Chemistry and Chemical Engineering, Lanzhou University, 222 South Tianshui Road, Lanzhou, 730000, China.
We report here a new method for the synthesis of organohydrosilanes from phenols and ketones. This method is established through reductive C-Si coupling of chlorohydrosilanes via unconventional Si-Cl cleavage. The reaction offers access to aryl- and alkenylhydrosilanes with a scope that is complementary to those of the established methods.
View Article and Find Full Text PDFA Silyl Sulfinylamine Reagent Enables the Modular Synthesis of Sulfonimidamides via Primary Sulfinamides.
Org Lett
March 2022
Department of Chemistry, University of Oxford, Chemistry Research Laboratory, Mansfield Road, Oxford, OX1 3TA, U.K.
A new -silyl sulfinylamine reagent allows the rapid preparation of a broad range of (hetero)aryl, alkenyl, and alkyl primary sulfinamides, using Grignard, organolithium, or organozinc reagents to introduce the carbon fragment. Treatment of these primary sulfinamides with an amine in the presence of a hypervalent iodine reagent leads directly to NH-sulfonimidamides. This two-step sequence is straightforward to perform and provides a modular approach to sulfonimidamides, allowing ready variation of both reaction components, including primary and secondary amines.
View Article and Find Full Text PDFCatalyst-free carbosilylation of alkenes using silyl boronates and organic fluorides via selective C-F bond activation.
Nat Commun
June 2021
Department of Nanopharmaceutical Sciences, Nagoya Institute of Technology, Gokiso, Showa-ku, Nagoya, Japan.
A regioselective carbosilylation of alkenes has emerged as a powerful strategy to access molecules with functionalized silylated alkanes, by incorporating silyl and carbon groups across an alkene double bond. However, to the best of our knowledge, organic fluorides have never been used in this protocol. Here we disclose the catalyst-free carbosilylation of alkenes using silyl boronates and organic fluorides mediated by BuOK.
View Article and Find Full Text PDFWant AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!