Theoretical insight into stereoselective reaction mechanisms of 2,4-pentanediol-tethered ketene-olefin [2 + 2] cycloaddition.
We report ab initio molecular dynamics calculations based on density functional theory performed on an intramolecular [2 + 2] cycloaddition between ketene and olefin linked with a 2,4-pentanediol (PD) tether. We find that the encounter of the ketene and olefin moieties could be prearranged in the thermal equilibrated state before the cycloaddition. The reaction mechanism is found to be stepwise, similar to that of intermolecular ketene [2 + 2] cycloadditions with ordinary alkenes. A distinct feature of the reaction pathway for a major diastereoisomer is a differential activation free energy of about 1.5 kcal/mol, including 2.8 kcal/mol as the differential activation entropy, with a transition state consisting of a flexible nine-membered ring in the olefin-PD-ketene moiety. This theoretical study provides a reasonable explanation for the strict stereocontrollability of the PD-tethered ketene-olefin cycloaddition, irrespective of reaction types or conditions.
Graduate School of Pure and Applied Sciences, University of Tsukuba, 1-1-1 Tennodai, Tsukuba, Ibaraki, 305-8571, Japan. kkamiya@comas.frsc.tsukuba.ac.jp
Katsumasa
K
Kamiya
Toru
T
Matsui
Takashi
T
Sugimura
Yasuteru
Y
Shigeta
D000475:Alkenes / Q000737:chemistry*; D003500:Cyclization; D005030:Ethylenes / Q000737:chemistry*; D006018:Glycols / Q000737:chemistry*; D007659:Ketones / Q000737:chemistry*; D008968:Molecular Conformation; D056004:Molecular Dynamics Simulation; D013237:Stereoisomerism
D000475:Alkenes; D005030:Ethylenes; D006018:Glycols; D007659:Ketones; C065140:2,4-pentanediol; C008223:ketene