Bromine induced spiro cyclization of biaryl ynones facilitated the synthesis of spiro[5,5]trienones suitable for extended functionality at the C(3') position. Herein, a step-economic photo-oxidative brominative carbannulation of biaryl ynones employing ammonium bromide and riboflavin tetraacetate (RFTA) has been developed. The reactivity between distal phenyl C-H activated -annulation and dearomative -annulation is well exemplified. The eminent features of the methodology include metal-free, external additive free, low-loading photocatalyst (0.1 mol %), and use of a simple precursor.
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http://dx.doi.org/10.1021/acs.joc.3c00941 | DOI Listing |
Chem Asian J
January 2025
Indian Institute of Technology Guwahati, Chemistry, Department of Chemistry, Indian Institute of Technology Guwahati, 781039, Guwahati, INDIA.
Ferric chloride mediated dearomative spirocyclization of biaryl ynones for the synthesis of new series of densely functionalized 3,3-spiroindanone derivatives has been reported. This study is the first to describe the regioselective synthesis of a five-membered ring from biaryl ynones. The scope of the reaction is broad and the spirocyclic products were obtained in moderate to good yields (up to 87%) and with high stereoselectivities.
View Article and Find Full Text PDFOrg Biomol Chem
May 2024
Organic Synthesis and Molecular Engineering Laboratory, Department of Chemistry, IIT Indore, Madhya Pradesh, 453552, India.
Sulfinyls are valuable structural moieties used for developing synthetically new pharmaceuticals and agrochemicals. Herein, we disclose a straightforward synthesis of sulfinylated spiro[5.5]trienones proceeding an unprecedented BF·EtO-promoted spirocyclization of biaryl ynones.
View Article and Find Full Text PDFOrg Biomol Chem
May 2024
Department of Chemistry, Indian Institute of Technology Guwahati, 781039, India.
This report covers boron tribromide (BBr) mediated dearomative spirocyclization of biaryl ynones. The direct synthesis of spiro[5.5]dienones with a tri-substituted double bond is described for the first time in this paper.
View Article and Find Full Text PDFMolecules
January 2024
Jiangsu Key Laboratory of Chiral Pharmaceuticals Biosynthesis, Taizhou University, Taizhou 225300, China.
The oxidative radical cascade cyclization of alkynes has emerged as a versatile strategy for the efficient construction of diverse structural units and complex molecules in organic chemistry. This work reports an alkyl radical initiated 5--trig cyclization of biaryl ynones with 1,4-dihydropyridines to selectively synthesize indenones.
View Article and Find Full Text PDFOrg Lett
December 2023
Key Laboratory of Organic Chemistry of Jiangxi Province, Jiangxi Science & Technology Normal University, Nanchang, 330013, China.
Herein, a novel electrochemical arene radical cation promoted dearomative spirocyclization of biaryl ynones with alcohols is described, providing a conceptually novel transformation mode for producing diverse alkoxylated spiro[5,5]trienones. The catalyst- and chemical-oxidant-free spirocyclization protocol features broad substrate scope and high functional group tolerance. Mechanistic studies reveal that the generation of arene radical cation via anodic single-electron oxidation is crucial, with sequential 6-- cyclization, dissociation of hemiketal, anodic oxidation, and nucleophilic attack of alcohols.
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