Chromium-catalyzed cyclopropanation of alkenes with bromoform was achieved to produce the corresponding bromocyclopropanes. In this catalytic cyclopropanation, an organosilicon reductant, 2,3,5,6-tetramethyl-1,4-bis(trimethylsilyl)-1,4-dihydropyrazine (), was indispensable for reducing CrCl(thf) to CrCl(thf), as well as for generation of (bromomethylidene)chromium(iii) species from (dibromomethyl)chromium(iii) species. The (bromomethylidene)chromium(iii) species are proposed to react spontaneously with alkenes to give the corresponding bromocyclopropanes. This catalytic cyclopropanation was applied to various olefinic substrates, such as allyl ethers, allyl esters, terminal alkenes, and cyclic alkenes.
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http://dx.doi.org/10.1039/d0sc00964d | DOI Listing |
Angew Chem Int Ed Engl
July 2023
Key Laboratory of Precise Synthesis of Functional Molecules of Zhejiang Province, Department of Chemistry, School of Science, Westlake University, Hangzhou, 310024, China.
Chiral cyclopropane derivatives are essential in synthetic chemistry and drug discovery. Their synthesis commonly relies on asymmetric cyclopropanation of diazo compounds, potentially explosive and needing stabilizing substituents. Thus, asymmetric catalytic transformations of non-stabilized carbenes or carbenoids remain a formidable challenge.
View Article and Find Full Text PDFChem Sci
March 2020
Department of Chemistry, Graduate School of Engineering Science, Osaka University Toyonaka Osaka 560-8531 Japan
J Am Chem Soc
June 2010
Texas A&M University, Department of Chemistry, P.O. Box 30012, College Station, Texas 77842-3012, USA.
A scalable, highly regioselective chromium-catalyzed homoaldol equivalent reaction employing 3-bromopropenyl acetate as a masked homoenolate nucleophile in additions to aromatic, aliphatic, and alpha,beta-unsaturated aldehydes under mild Cr/Mn redox conditions in good to excellent yields is reported. The resulting vinyl acetate-containing adducts are easily hydrolyzed with mild base to provide formal homoaldol adducts, or transformed to other more functionalized products by stereoselective transformations including epoxidation and cyclopropanation.
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