Relative Reactivity of Various Al-substituted-dialkylalans in Reduction of Carbonyl Compounds; A Theoretical Study on Substituent Effect

Title
Relative Reactivity of Various Al-substituted-dialkylalans in Reduction of Carbonyl Compounds; A Theoretical Study on Substituent Effect
Author(s)
남기평차진순
Keywords
MEERWEIN-PONNDORF-VERLEY; DENSITY-FUNCTIONAL THEORY; SELECTIVE REDUCTION; ALPHA,BETA-UNSATURATED ALDEHYDES; METALLORGANISCHE VERBINDUNGEN; ORGANIC-COMPOUNDS; ALLYLIC ALCOHOLS; METAL REAGENTS; HARTREE-FOCK; ALUMINUM
Issue Date
201308
Publisher
KOREAN CHEMICAL SOC
Citation
BULLETIN OF THE KOREAN CHEMICAL SOCIETY, v.34, no.8, pp.2335 - 2339
Abstract
Relative reactivity of various Al-substituted dialkylalans (AlR2(X)) in reduction of acetone has been studied with density functional theory and MP2 method. Formation of the alan dimers and the alan-acetone adduct, and the transition state for the Meerwein-Ponndorf-Verley (MPV) type reduction of the adduct were calculated to figure out the energy profile. Formation of dimeric alans is highly exothermic. Both the relative free energies for acetone-alan adduct formation and the TS barriers for the MPV type reduction with respect to alan dimers and acetone were calculated and they show the same trend. Based on these energetic data, relative reactivity of alans is expected to be; AlR2(Cl) > AlR2(OTf) > AlR2(O2CCF3) > AlR2(F) > AlR2(OMs) > AlR2(OAc) > AlR2(OMe) > AlR2(NMe2). The energy profile is relatively well correlated with the experimental order of the reactivity of Al-substituted dialkylalans. It is noted that the substituents of alans have initial effects on the relative free energies for the carbonyl-adduct formation. Therefore, an AlR2(X) which forms a more stable carbonyl-adduct is more reactive in carbonyl reduction.
URI
http://hdl.handle.net/YU.REPOSITORY/29265http://dx.doi.org/10.5012/bkcs.2013.34.8.2335
ISSN
0253-2964
Appears in Collections:
이과대학 > 화학생화학부 > Articles
문과대학 > 중국언어문화학과 > Articles
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