Kinetic Studies of Donor–Acceptor Cyclopropanes: The Influence of Structural and Electronic Properties on the Reactivity
M. Sc. Alexander Kreft
Technische Universität Braunschweig, Institut für Organische Chemie, Hagenring 30, 38106 Braunschweig, Germany
These authors contributed equally to this work.
Search for more papers by this authorM. Sc. Alexander Lücht
Technische Universität Braunschweig, Institut für Organische Chemie, Hagenring 30, 38106 Braunschweig, Germany
These authors contributed equally to this work.
Search for more papers by this authorProf. Dr. Jörg Grunenberg
Technische Universität Braunschweig, Institut für Organische Chemie, Hagenring 30, 38106 Braunschweig, Germany
Search for more papers by this authorProf. Dr. Peter G. Jones
Technische Universität Braunschweig, Institut für Anorganische und Analytische Chemie, Hagenring 30, 38106 Braunschweig, Germany
Search for more papers by this authorCorresponding Author
Prof. Dr. Daniel B. Werz
Technische Universität Braunschweig, Institut für Organische Chemie, Hagenring 30, 38106 Braunschweig, Germany
Search for more papers by this authorM. Sc. Alexander Kreft
Technische Universität Braunschweig, Institut für Organische Chemie, Hagenring 30, 38106 Braunschweig, Germany
These authors contributed equally to this work.
Search for more papers by this authorM. Sc. Alexander Lücht
Technische Universität Braunschweig, Institut für Organische Chemie, Hagenring 30, 38106 Braunschweig, Germany
These authors contributed equally to this work.
Search for more papers by this authorProf. Dr. Jörg Grunenberg
Technische Universität Braunschweig, Institut für Organische Chemie, Hagenring 30, 38106 Braunschweig, Germany
Search for more papers by this authorProf. Dr. Peter G. Jones
Technische Universität Braunschweig, Institut für Anorganische und Analytische Chemie, Hagenring 30, 38106 Braunschweig, Germany
Search for more papers by this authorCorresponding Author
Prof. Dr. Daniel B. Werz
Technische Universität Braunschweig, Institut für Organische Chemie, Hagenring 30, 38106 Braunschweig, Germany
Search for more papers by this authorDedicated to Professor Armin de Meijere on the occasion of his 80th birthday
Graphical Abstract
Who is faster? The reactivity of donor–acceptor cyclopropanes was investigated in (3+n) cycloaddition reactions with an aldehyde, a nitrone, and an isobenzofuran by NMR and in operando IR spectroscopy. The obtained reaction rates were compared with the structural and electronic properties of the donor–acceptor cyclopropanes.
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 1H and 13C 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.
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=1553 cm−1 (nitrone) and 
=768, 1495 cm−1 (isobenzofuran).
