Role of Heavy Atom Tunneling in Myers-Saito Cyclization of Cyclic Enyne-Cumulene Systems

The Journal of Physical Chemistry. B
Sharmistha Karmakar, Ayan Datta

Abstract

Direct dynamics calculation using canonical variational transtition state theory (CVT) inclusive of small curvature tunneling (SCT) reveals heavy atom tunneling in Myers-Saito cyclization of 10- and 9-membered cyclic enyne-cumulene systems like 1,6-didehydro[10]annulene and derivative of neocarzinostatin, respectively. The pure density functional theory functional, BLYP at a 6-31+G (d,p) basis set reproduce the observed reaction energies and barriers within 1.0 kcal/mol. The calculated rate constants of cyclization inclusive of heavy atom tunneling (k(CVT+SCT) = 3.26 × 10(-4) s(-1) at 222 K; t1/2 = 35 min) are in excellent agreement with experiments (t1/2 ∼ 21-31 min). Both primary and secondary kinetic isotope effect (KIE) become enhanced significantly upon inclusion of quantum mechanical tunneling. An Arrhenius plot of KIE shows measurable curvature at the experimental temperature of 222 K. The translation vector for the cyclization reactions in the transition-states (TS) show significant motion of primary and secondary carbon atoms explaining the origin of large KIE.

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Citations

May 26, 2017·The Journal of Physical Chemistry. a·Tumpa SadhukhanSourav Pal
Nov 2, 2018·Physical Chemistry Chemical Physics : PCCP·Kalyanashis Jana, Bishwajit Ganguly
Mar 9, 2021·Physical Chemistry Chemical Physics : PCCP·Luís P ViegasRui Fausto
Mar 9, 2019·Journal of the American Chemical Society·Cameron S MichelWilliam L Karney
May 31, 2019·The Journal of Physical Chemistry. B·Malgorzata KowalikAdri C T van Duin

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