A strategy for cross-electrophile coupling has been developed via the merger of photoredox and transition metal catalysis. In this report, we demonstrate the use of commercially available tris(trimethylsilyl)silane with metallaphotoredox catalysis to efficiently couple alkyl bromides with aryl or heteroaryl bromides in excellent yields. We hypothesize that a photocatalytically generated silyl radical species can perform halogen-atom abstraction to activate alkyl halides as nucleophilic cross-coupling partners. This protocol allows the use of mild yet robust conditions to construct Csp(3)-Csp(2) bonds generically via a unique cross-coupling pathway.
Download full-text PDF |
Source |
|---|---|
| http://www.ncbi.nlm.nih.gov/pmc/articles/PMC5103281 | PMC |
| http://dx.doi.org/10.1021/jacs.6b04818 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
One-Pot, Telescoped Aryl Nitrile Synthesis from Benzylic Silyl Ethers.
J Org Chem
January 2025
Laboratory of Pharmaceutical Chemistry, Kyoto Pharmaceutical University, Yamashina-ku, Kyoto 607-8412, Japan.
A one-pot, telescoped transformation of silyl ethers into cyanides that proceeds via silyl-ether oxidation mediated by nitroxyl-radical catalyst and [bis(trifluoroacetoxy)iodo]benzene followed by an imine formation-oxidation sequence using iodine and aqueous ammonia is reported. This transformation is effective for the site-selective transformation of benzylic and allylic silyl ethers in the presence of other silyl ethers. Using an -protected oxime and a catalytic amount of triflic acid instead of iodine/aqueous ammonia is also effective for cyanation.
View Article and Find Full Text PDFTotal Syntheses of Bryostatins 1, 7, 9 and 9-N3.
Angew Chem Int Ed Engl
January 2025
Sichuan University, West China School of Pharmacy, Renmin Sout Road, 3rd Section, 17#, 610041, Chengdu, CHINA.
Bryostatins are a family of marine natural products that have garnered significant interests, as evidenced by over 40 clinical trials. However, their extremely low natural abundance has severely limited further research. Despite significant efforts, which have led to the total synthesis of seven bryostatin members by eight independent research groups, these complex molecules present persistent challenges for stereocontrolled, large-scale, and especially divergent synthesis.
View Article and Find Full Text PDFRecent advances and perspectives in synthetic applications of silylboronates as silyl radical precursors.
Chem Sci
December 2024
State Key Laboratory of Petroleum Molecular & Process Engineering, Shanghai Engineering Research Center of Molecular Therapeutics and New Drug Development, School of Chemistry and Molecular Engineering, East China Normal University Shanghai 200062 P. R. China
Silylboronates, as powerful and versatile reagents, have been widely used in synthetic chemistry over the past few decades, due to their ability to incorporate silicon and boron atoms into organic molecules. With the rapid development of radical chemistry, the use of silylboronates as silyl radical precursors has recently become a research focus in organic synthesis. Significant achievements have been made in the synthetic applications of silylboronates as silyl radical sources for various C-Si and C-X bond forming transformations.
View Article and Find Full Text PDFVisible-Light-Mediated Deaminative Alkylation of Primary Amines with Silacarboxylic Acids via Isonitrile Formation.
Org Lett
January 2025
Organic Chemistry Department, Faculty of Science, Autonomous University of Madrid, 28049 Madrid, Spain.
The functionalization of the C-N bond of amines is a straightforward strategy for the construction of complex scaffolds or for the late-stage functionalization of pharmaceuticals. Herein, we describe a photoredox-catalyzed strategy for the deaminative alkylation of primary amine-derived isonitriles that provides unnatural amino acid derivatives under mild conditions. The use of silacarboxylic acids as silyl radical precursors enables the generation of carbon-centered radicals that allow the construction of Csp-Csp bonds via a Giese-type addition, avoiding the undesired hydrodeamination product.
View Article and Find Full Text PDFPhotoredox/Nickel Dual-Catalytic Asymmetric Silylarylation of Alkenes.
Org Lett
January 2025
Shanghai Frontiers Science Center of Optogenetic Techniques for Cell Metabolism, Shanghai Key Laboratory of New Drug Design, and School of Pharmacy, East China University of Science and Technology, Shanghai 200237, P. R. China.
The efficient construction of chiral aryl-containing organosilicon frameworks via catalytic enantioselective three-component silylarylation of alkenes remains a great challenge. Herein, a photoredox/nickel dual-catalytic asymmetric protocol has been disclosed by using a chiral biimidazoline (BiIM) as the ligand, silylboranes as the silyl radical precursors, aryl bromides as the coupling partners, and morpholine as the promoter. Remarkably, the reaction features mild and green conditions, high reaction efficiency, and excellent enantioselectivity, enabling the facile synthesis of valuable chiral tropic acid and sila-isoflavanone structures.
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!