Computational Analysis of the Stereochemical Outcome in the Imidazolidinone-Catalyzed Enantioselective (4 + 3)-Cycloaddition Reaction | Zendy

Elizabeth H. Krenske | Zendy; K. N. Houk | Zendy; Michael Harmata | Zendy

Open Access

Computational Analysis of the Stereochemical Outcome in the Imidazolidinone-Catalyzed Enantioselective (4 + 3)-Cycloaddition Reaction

Author(s) -

Elizabeth H. Krenske,

K. N. Houk,

Michael Harmata

Publication year - 2014

Publication title -

the journal of organic chemistry

Language(s) - English

Resource type - Journals

SCImago Journal Rank - 1.2

H-Index - 228

eISSN - 1520-6904

pISSN - 0022-3263

DOI - 10.1021/jo501906m

Subject(s) - cycloaddition , chemistry , enantioselective synthesis , iminium , intramolecular force , catalysis , selectivity , silylation , stereochemistry , computational chemistry , medicinal chemistry , organic chemistry

Computations show why the catalytic, asymmetric (4 + 3)-cycloaddition reaction developed in the Harmata laboratories proceeds with facial selectivity opposite to that for models proposed for related catalyzed Diels-Alder reactions. Computations with M06-2X/6-311+G(d,p)//B3LYP/6-31G(d) show that iminium ions derived from MacMillan's chiral 2-tert-butyl-5-benzylimidazolidinone and siloxypentadienals undergo (4 + 3)-cycloadditions with furans preferentially on the more crowded face. Conformational reorganization of the benzyl group, to avoid intramolecular interaction with the silyl group, is responsible for differentiating the activation barriers of top- and bottom-face attack.

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