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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.