Kinetic Studies of Donor-Acceptor Cyclopropanes: The Influence of Structural and Electronic Properties on the Reactivity

Abstract

The kinetics of (3+2) cycloaddition reactions of 18 different donor-acceptor cyclopropanes with the same aldehyde were studied by in situ NMR spectroscopy. Increasing the electron density of the donor residue accelerates the reaction by a factor of up to 50 compared to the standard system (donor group=phenyl), whereas electron-withdrawing substituents slow down the reaction by a factor up to 660. This behavior is in agreement with the Hammett substituent parameter σ. The obtained rate constants from the (3+2) cycloadditions correlate well with data from additionally studied (3+n) cycloadditions with a nitrone (n=3) and an isobenzofuran (n=4). A comparison of the kinetic data with the bond lengths in the cyclopropane (obtained by X-ray diffraction and computation), or the ¹ H and ¹³ C NMR shifts, revealed no correlation. However, the computed relaxed force constants of donor-acceptor cyclopropanes proved to be a good indicator for the reactivity of the three-membered ring.

Keywords: catalysis; cycloaddition; cyclopropanes; donor-acceptor compounds; reactivity studies.