The letter describes a novel concept for the synthesis of biologically important arylphenylmethanols. Stereoselective cyclohexadienyl transfer from 1,4-cyclohexadienyltributyltin to various aromatic aldehydes using AgOTf/BINAP as a catalyst precursor provides 1,4-cyclohexadienylphen-ylmethanols that are readily oxidized to the corresponding arylphenylmethanols. Fifteen examples are presented.
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Org Lett
December 2021
Department of Applied Chemistry, National University of Kaohsiung, Kaohsiung 81148, Taiwan.
A carboxylate-assisted palladium-catalyzed Mizoroki-Heck arylation of electron-deficient internal alkenes is described herein. This protocol utilized a free carboxylic acid as the directing group for regio- and stereoselective Mizoroki-Heck arylation of β-cyclohexadienyl acrylates and styrenes with various aryl iodides. The synthetic application has been exhibited by decarboxylative aromatization and iodolactonization/hydrolysis of the resulting polyenes providing trisubstituted alkenes and structurally diverse hydroxyl lactones.
View Article and Find Full Text PDFJ Am Chem Soc
December 2011
School of Chemistry and Chemical Biology, University College Dublin, Belfield, Dublin 4, Ireland.
Cis- and trans-1,2-dihydrodiol isomers of benzene undergo acid-catalyzed dehydration to form phenol. In principle the isomeric substrates react through a common β-hydroxybenzenium (cyclohexadienyl) carbocation. Notwithstanding, the isomers show a large difference in reactivity, k(cis)/k(trans) = 4500.
View Article and Find Full Text PDFOrg Lett
March 2008
Fachbereich Chemie, Organisch-Chemisches Institut, Westfälische Wilhelms-Universität, Corrensstrasse 40, 48149 Münster, Germany.
The letter describes a novel concept for the synthesis of biologically important arylphenylmethanols. Stereoselective cyclohexadienyl transfer from 1,4-cyclohexadienyltributyltin to various aromatic aldehydes using AgOTf/BINAP as a catalyst precursor provides 1,4-cyclohexadienylphen-ylmethanols that are readily oxidized to the corresponding arylphenylmethanols. Fifteen examples are presented.
View Article and Find Full Text PDFJ Am Chem Soc
September 2006
Department of Chemistry & School of Informatics, Indiana University, Bloomington, Indiana 47405-7102, USA.
Carbolithiation has been studied with alkyllithium reagents in a series of six- through nine-membered 3-methylene-1,4-cycloalkadienes, efficiently producing the corresponding cyclic pentadienyl carbanions. These pentadienyl anions display unique reactivity, depending on ring size. Cyclooctadienyl anions readily undergo disrotatory electrocyclization to cis-bicyclo[3.
View Article and Find Full Text PDFJ Am Chem Soc
March 2006
Department of Chemistry, University of Iowa, 305 Chemistry Building, Iowa City, Iowa 52242, USA.
Arene ruthenium complexes possessing beta-amido phosphonate side chains participate in intramolecular spirocyclization reactions to deliver stable cyclohexadienyl ruthenium adducts. Spirocyclization is accomplished via a tandem two-step sequence that involves stereoselective nucleophilic aromatic addition to the ipso position of the coordinated arene, followed by intermolecular Horner-Wadsworth-Emmons olefination. The resulting eta5-cyclohexadienyl complexes can then be diastereoselectively converted to metal-free azaspiro[4.
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