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A solvent- and catalyst-free protocol for the selective reductive deoxygenation of α,β-unsaturated ketones with pinacolborane (HBpin) has been developed. -OH/NH groups efficiently direct the transformation, affording 2-allylphenols and 2-allylanilines under mild conditions with excellent chemo- and regioselectivity. Mechanistic studies indicate a boron-assisted hydride transfer and carbocation pathway. This work provides a sustainable and practical approach to valuable allylic scaffolds with potential applications in medicinal chemistry and materials science.
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http://dx.doi.org/10.1039/d5ob01345c | DOI Listing |
Org Biomol Chem
September 2025
School of Chemistry and Material Engineering, Anhui Provincial Key Laboratory of Green Carbon Chemistry, Engineering Research Center of Biomass Conversion and Pollution Prevention of Anhui Educational Institutions, Biomass-derived Functional Oligosaccharides Engineering Technology Research Center of
A solvent- and catalyst-free protocol for the selective reductive deoxygenation of α,β-unsaturated ketones with pinacolborane (HBpin) has been developed. -OH/NH groups efficiently direct the transformation, affording 2-allylphenols and 2-allylanilines under mild conditions with excellent chemo- and regioselectivity. Mechanistic studies indicate a boron-assisted hydride transfer and carbocation pathway.
View Article and Find Full Text PDFOrg Lett
September 2025
Dipartimento di Chimica 'Ugo Schiff' (DICUS), Università di Firenze, via della Lastruccia 3-13, 50019 Sesto Fiorentino (FI), Italy.
The first synthesis of polyhydroxylated 3-methylindolizidines is reported. A straightforward domino butenylmagnesium bromide addition/Cope-House reaction to carbohydrate-derived nitrones afforded efficiently the methyl pyrrolidine moiety with good stereoselectivity, which can be reversed by use of Lewis acids. A subsequent one-pot deprotection/deoxygenation/reductive amination step furnished the desired bicyclic architecture, allowing us to afford the desired final products in 3-4 steps from the starting nitrones and 18-30% overall yields.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
August 2025
Department of Chemistry, Chemistry Research Laboratory, University of Oxford, 12 Mansfield Road, Oxford, OX1 3TA, UK.
The synthesis of sterically hindered α-tertiary and β-quaternary (neopentylic) ethers has long been constrained by the limitations of traditional S2 and related S1 approaches, namely low or inexistent reactivity arising from severe steric hindrance or competitive elimination/rearrangement pathways diverting the reaction outcome. Herein, we describe a general solution to the synthesis of sterically hindered ethers via an iridium-catalyzed reductive deoxygenation reaction of readily available ester and lactone starting materials. Employing commercially available, bench-stable IrCl(CO)(P[OCH(CF)]) as a precatalyst at 1 mol% loading with 4 equivalents of tetramethyldisiloxane (TMDS) as the terminal reductant at room temperature, this practical synthetic approach to hindered ethers features a simple, mix-and-stir, single-vessel protocol under ambient conditions and produces a diverse range of both acyclic and cyclic ether products in good to excellent yields.
View Article and Find Full Text PDFChem Commun (Camb)
August 2025
Department of Chemistry, College of Science, China Agricultural University, 2 Yuanmingyuan West Road, Beijing 100193, P. R. China.
Reduction reactions are among the most commonly employed methods in organic synthesis, both in the laboratory and industry. Typical reductants include hydrogen gas, as well as metal-, silicon-, and boron-based hydrides. Although hydrogen gas is considered the greenest reductant, its production currently depends heavily on fossil fuel-derived processes.
View Article and Find Full Text PDFJ Am Chem Soc
August 2025
State Key Laboratory of Chemical Biology, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, China.
Harziane diterpenoids possess a highly caged 6/5/7/4 core framework and four contiguous stereocenters, including two quaternary ones, and present significant challenges to chemical synthesis. Herein, we report an efficient strategy to rapidly access harziane diterpenoids by merging local desymmetrization and radical retrosynthesis. The strained bicyclo[5.
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