MPV-Reduction of C=O bond with Al-substituted-dialkylalan; A Theoretical Study on Relative Reactivity of Various Carbonyl Substrates

Title
MPV-Reduction of C=O bond with Al-substituted-dialkylalan; A Theoretical Study on Relative Reactivity of Various Carbonyl Substrates
Author(s)
남기평
Keywords
MEERWEIN-PONNDORF-VERLEY; DENSITY-FUNCTIONAL THEORY; METALLORGANISCHE VERBINDUNGEN; SELECTIVE REDUCTION; METAL REAGENTS; HARTREE-FOCK; THERMOCHEMISTRY; FREQUENCIES; ALUMINUM; HYDRIDES
Issue Date
201402
Publisher
KOREAN CHEMICAL SOC
Citation
BULLETIN OF THE KOREAN CHEMICAL SOCIETY, v.35, no.2, pp.546 - 550
Abstract
Relative reactivity of various carbonyl and acid derivatives in MPV-type (Meerwein-Pormdorf-Verley) reduction with an DIBAL(F) model has been studied via DFT and MP2 methods. Free energies of initial adduct formation (Delta G(add)) of DIBAL(F) model and carbonyls are in the order of amide < ester < aldehyde < ketone < acid chloride; in the alan-amide adduct, the developed positive charge at carbonyl carbon is expected to be stabilized by amide resonance, but in the acid chloride adduct it is destabilized by inductive effect of chloride. However the TS barrier energies (Delta G(TS)) for the MPV-type hydride reduction of the carbonyl adducts are in the order of aldehyde < ketone < acid chloride ester < amide; presumably decreasing order of electrophilicity of carbonyl carbon at adducts, which is well correlated with experimental data. It is noted that the relative reactivity of carbonyl derivatives in MPV-type reduction with DIBAL(X) is not governed by the alan-adduct formation energies, but follows the order of electrophilicity of carbonyl carbon of transition states.
URI
http://hdl.handle.net/YU.REPOSITORY/33197http://dx.doi.org/10.5012/bkcs.2014.35.2.546
ISSN
0253-2964
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이과대학 > 화학생화학부 > Articles
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