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Boyd Group Electronegativity Influence on the Parr Global Electrophilicity of Vilsmeier Reagent‐Derived Imidates: New Insights toward Improving Mitsunobu Chemistry
Author(s) -
Carr Jeremy M.,
Tschumper Gregory S.,
Paige Lathem A.
Publication year - 2015
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/hlca.201400340
Subject(s) - chemistry , electronegativity , electrophile , reagent , reactivity (psychology) , computational chemistry , polar effect , group (periodic table) , homo/lumo , stereochemistry , medicinal chemistry , organic chemistry , combinatorial chemistry , catalysis , molecule , medicine , alternative medicine , pathology
Reactivities of 19 methylated imidate analogs were examined using B3LYP and M06‐2X DFT methods. The resulting HOMO and LUMO energies of each optimized structure were used to calculate corresponding Parr global electrophilicity ( ω ) values. When the resulting quantities were compared against Boyd group electronegativity ( X G ) values, a clear correlation was observed, suggesting that electron‐withdrawing effects influence the reactivity of imidates. These findings represent an important first step in developing a novel method toward improving traditional Mitsunobu functionalization reactions.