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Density functional computations of alkynylation of ethanimine catalyzed by chiral zinc(II)‐complexes
Author(s) -
Meng Qingxi,
Wang Fen,
Li Ming
Publication year - 2007
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.21477
Subject(s) - alkynylation , chemistry , catalysis , density functional theory , chirality (physics) , exothermic reaction , transition state , amine gas treating , zinc , electrophile , computational chemistry , ring (chemistry) , medicinal chemistry , organic chemistry , physics , quantum mechanics , symmetry breaking , chiral symmetry breaking , nambu–jona lasinio model
The alkynylation of ethanimine catalyzed by chiral zinc(II)‐complexes was studied by means of the density functional theory (DFT). All the intermediates and transition states were optimized completely at the B3LYP/6‐31G(d,p) level. Calculation results confirm that the alkynylation of ethanimine is exothermic and the total released energy is about −13 kJ/mol. The formation of the catalyst–alkynyl complexes M4 is the rate‐determining step for this alkynylation, and the formation of the catalyst–amine complexes M5 is the chirality‐limiting step for this alkynylation. The transition states for the chirality‐limiting step have a HOZnCCN six‐membered ring. The dominant products predicted theoretically for this alkynylation are, respectively, S ‐amine for ethanimine anti and R ‐amine for ethanimine syn . © 2007 Wiley Periodicals, Inc. Int J Quantum Chem, 2008