Transition-metal-catalyzed hydrofunctionalization of methylenecyclopropanes presents a useful but challenging transformation due to the complex selectivity and multiple reaction pathways. We describe herein an unprecedented highly efficient and selective palladium-catalyzed hydrocyanation of methylenecyclopropanes to give various 2-substituted allylic nitriles. Mechanistic studies demonstrated that the transformation may undergo Markovnikov-type hydrometalation and β-carbon elimination.
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Pd-Catalyzed Hydrocyanation of Methylenecyclopropanes: A Highly Selective Ring-Opening Access to 2-Substituted Allylic Nitriles.
Org Lett
November 2024
Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education, Key Laboratory of Organosilicon Material Technology of Zhejiang Province, College of Material, Chemistry and Chemical Engineering, Hangzhou Normal University, 2318 Yuhangtang Road, Hangzhou 311121, China.
Transition-metal-catalyzed hydrofunctionalization of methylenecyclopropanes presents a useful but challenging transformation due to the complex selectivity and multiple reaction pathways. We describe herein an unprecedented highly efficient and selective palladium-catalyzed hydrocyanation of methylenecyclopropanes to give various 2-substituted allylic nitriles. Mechanistic studies demonstrated that the transformation may undergo Markovnikov-type hydrometalation and β-carbon elimination.
View Article and Find Full Text PDFCobalt-Catalyzed Hydrocyanation of Methylenecyclopropanes to Homoallylic Nitriles.
Org Lett
December 2022
Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs, School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai 200240, China.
We describe herein a novel synthesis of various homoallylic nitriles via cobalt-catalyzed hydrocyanation of methylenecyclopropanes. Excellent selectivity, mild reaction conditions, good functional group compatibility, gram-scale reaction, and product transformations demonstrate the power of this protocol. This extraordinary selectivity can probably be attributed to the stronger aptitude of the alkyl-cobalt cyanide intermediate to undergo reductive elimination rather than β-hydride elimination.
View Article and Find Full Text PDFHighly Enantioselective Nickel-Catalyzed Hydrocyanation of Disubstituted Methylenecyclopropanes Enabled by TADDOL-based Diphosphite Ligands.
Org Lett
January 2020
Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs, School of Chemistry and Chemical Engineering , Shanghai Jiao Tong University, 800 Dongchuan Road , Shanghai 200240 , People's Republic of China.
A vast range of novel TADDOL-based diphosphite ligands were first synthesized and applied in the nickel-catalyzed asymmetric hydrocyanation of disubstituted methylenecyclopropanes. By employing these new catalysts, the conversion of diverse methylenecyclopropanes into their corresponding allylic nitriles was first enabled, in good yield with excellent enantioselectivities.
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