The Origin of endo Stereoselectivity in the Hetero‐Diels–Alder Reactions of Aldehydes with ortho‐Xylylenes: CH–π, π–π, and Steric Effects on Stereoselectivity
Chemistry–A European Journal, 2002•Wiley Online Library
Theoretical studies of stereoselectivity have been carried out with B3LYP and MP2
calculations. The high endo selectivity of hetero‐Diels–Alder reactions of ortho‐xylylenes
with acetaldehydes is shown to result from attractive CH–π interactions between alkyl
groups of the aldehyde and the aromatic ring in the transition states of the reaction. For the
hetero‐Diels–Alder reactions of ortho‐xylylenes with benzaldehyde, the stereoselectivity is
shown to be mainly governed by the attractive π–π interactions between the phenyl rings of …
calculations. The high endo selectivity of hetero‐Diels–Alder reactions of ortho‐xylylenes
with acetaldehydes is shown to result from attractive CH–π interactions between alkyl
groups of the aldehyde and the aromatic ring in the transition states of the reaction. For the
hetero‐Diels–Alder reactions of ortho‐xylylenes with benzaldehyde, the stereoselectivity is
shown to be mainly governed by the attractive π–π interactions between the phenyl rings of …
Abstract
Theoretical studies of stereoselectivity have been carried out with B3LYP and MP2 calculations. The high endo selectivity of hetero‐Diels–Alder reactions of ortho‐xylylenes with acetaldehydes is shown to result from attractive CH–π interactions between alkyl groups of the aldehyde and the aromatic ring in the transition states of the reaction. For the hetero‐Diels–Alder reactions of ortho‐xylylenes with benzaldehyde, the stereoselectivity is shown to be mainly governed by the attractive π–π interactions between the phenyl rings of the benzaldehyde and the ortho‐xylylene. MP2 calculations are necessary to reproduce the stabilizing dispersion interactions.
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