Mechanistic Insight into the Nickel‐Catalyzed Intermolecular [3+2+2] Cocyclization of Ethyl Cyclopropylideneacetate with Alkynes: DFT Calculations | Zendy

An Yanhong | Zendy; Cheng Caihong | Zendy; Pan Ben | Zendy; Wang Zhihong | Zendy

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Mechanistic Insight into the Nickel‐Catalyzed Intermolecular [3+2+2] Cocyclization of Ethyl Cyclopropylideneacetate with Alkynes: DFT Calculations

Author(s) -

An Yanhong,

Cheng Caihong,

Pan Ben,

Wang Zhihong

Publication year - 2012

Publication title -

european journal of organic chemistry

Language(s) - English

Resource type - Journals

SCImago Journal Rank - 0.825

H-Index - 155

eISSN - 1099-0690

pISSN - 1434-193X

DOI - 10.1002/ejoc.201200363

Subject(s) - chemistry , methylenecyclopropane , nickel , moiety , intermolecular force , catalysis , ring (chemistry) , transition state , stereochemistry , reaction mechanism , ring strain , mechanism (biology) , computational chemistry , atom (system on chip) , medicinal chemistry , organic chemistry , molecule , philosophy , epistemology , computer science , embedded system

DFT investigations were employed to explore the complete reaction mechanism of the nickel‐catalyzed [3+2+2] cocyclization of ethyl cyclopropylideneacetate and alkynes. The lowest‐energy pathway involves the formation of a π complex between the methylenecyclopropane moiety and the nickel atom and occurs through a sequence of ring‐opening and ring‐closing reactions with C–C bond formation as the rate‐determining step. The crucial conversion of nickelacycloheptadiene to an eight‐membered nickelacycle was suggested to happen in a stepwise mechanism instead of the previously proposed cyclopropenyl–butenyl rearrangement.

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