98%
921
2 minutes
20
An unprecedented copper-catalysed allylic transposition enables the regioselective synthesis of branched allylic silanes from linear allylic halides through direct C-Si bond formation.
Download full-text PDF |
Source |
---|---|
http://dx.doi.org/10.1039/b920793g | DOI Listing |
Angew Chem Int Ed Engl
September 2025
State Key Laboratory of Low Carbon Catalysis and Carbon Dioxide Utilization, Suzhou Research Institute of LICP, Lanzhou Institute of Chemical Physics (LICP), Chinese Academy of Sciences, Lanzhou, 730000, China.
Allylic alcohols are versatile and essential building blocks in synthetic chemistry, widely used for the preparation of complex molecules, pharmaceuticals, and materials. We report here a regiodivergent reductive hydroxymethylation of terminal alkynes with aqueous formaldehyde to prepare allylic alcohols enabled by visible light photoredox and cobalt dual catalysis. Using readily available, bulk, and cheap aqueous formaldehyde as a simple C1 source, this method allows for the selective production of both linear and branched allylic alcohols in one-step manner.
View Article and Find Full Text PDFJ Am Chem Soc
September 2025
Roger Adams Laboratory, Department of Chemistry, University of Illinois Urbana-Champaign, Urbana, Illinois 61801, United States.
-alkyl arylamines are important structural motifs in pharmaceuticals, yet traditional alkylating methods rely on the nucleophilicity of the amine and make access to such compounds with valuable bioproperties challenging. While metal-mediated reactions may alleviate these limitations, they often encounter amine-metal interactions that can hinder catalysis or lead to deleterious pathways. Herein, we report a palladium(II) [Pd(II)]/sulfoxide-oxazoline(SOX)/phosphoric acid-mediated C(sp)H/N(sp) cross-coupling of 53 arylamine nucleophiles and 39 terminal olefins to furnish >80 diverse tertiary (3°) arylamines in excellent yields (average 82%) and selectivities (>20:1 /, >20:1 linear/branched).
View Article and Find Full Text PDFRSC Adv
August 2025
Área de Química Inorgánica-CIESOL, Universidad de Almería Almería Spain
The isomerization of substituted allylic alcohols, including α-vinyl benzyl alcohol, -1,3-diphenyl-2-propen-1-ol, cinnamyl alcohol, coniferyl alcohol, 4-nitrocinnamyl alcohol, farnesol, 1,5-hexadien-3,4-diol, (1)-(-)-myrtenol and ,-(-)-carveol, catalyzed by the [RuCp(OH)(PTA)](CFSO) (1) and [RuCp(OH)(mPTA)](CFSO) (2) (PTA = 1,3,5-triaza-7-phosphaadamantane, mPTA = -methyl-1,3,5-triaza-7-phosphaadamantane) complexes was examined in pure water and water-containing media. The isomerization of the chalcone -1,3-diphenyl-2-propen-1-ol catalyzed by 1 to produce the natural product propiophenone displays the highest known turnover number for this reaction to date (TON = 200 and TOF = 40 h). A study delving into the catalytic reaction mechanisms was carried out, aiming to understand the influence of different functional groups on the studied isomerization processes.
View Article and Find Full Text PDFOrg Lett
August 2025
School of Pharmaceutical Sciences (Shenzhen), Shenzhen Campus of Sun Yat-sen University, Shenzhen, 518107, P. R. China.
The first iridium-catalyzed direct intermolecular indole C7-allylic alkylation of 4-aminoindoles and racemic branched allylic esters was reported. Various substituted substrates were applicable to give the corresponding C7-allylated products in moderate to high yields (43-80%) with high regio- and enantioselectivities (82-99% ee) under mild reaction conditions. Representative transformations of the vinyl group in the product were carried out to examine the utility of this protocol.
View Article and Find Full Text PDFOrg Lett
August 2025
Department of Organic Chemistry, Indian Institute of Science, Bangalore 560012, India.
The poor acidity of acetonitrile restricted its utility as a C2 synthon of a cyanomethyl group for incorporation into organic compounds. We now employed a 2-azido allylic alcohol as an acetonitrile enolate surrogate for the first enantioselective allenylic cyanomethylation. This mild and base-free protocol utilizes cooperative iridium and Lewis acid catalysis for the activation of branched allenylic alcohols to deliver α-allenylic acetonitriles in moderate to good yields with excellent enantioselectivity.
View Article and Find Full Text PDF