Molecular dynamics of the intramolecular 1, 3-dipolar ene reaction of a nitrile oxide and an alkene: non-statistical behavior of a reaction involving a diradical intermediate^*

* Dedicated to the memory of the great theoretician and friend, Dieter Cremer.

ABSTRACT

Potential energy surfaces and molecular dynamics of the intramolecular 1, 3-dipolar cycloaddition and ene reaction of a nitrile oxide with an alkene were performed in the gas phase and in dichloromethane with density functional theory. One hundred trajectories were propagated in the gas phase and in dichloromethane, respectively. Twenty percent of the trajectories in the gas phase involve bicyclic intermediate and the mean time gap is 472fs. A dynamically stepwise reaction is observed. In dichloromethane, more reactive trajectories were obtained and the time gap is larger than that in the gas phase.

GRAPHICAL ABSTRACT

KEYWORDS:

• Molecular reaction dynamics
• intramolecular 1, 3-dipolar cycloaddition
• carbene-type mechanism
• diradical intermediate

Acknowledgment

We are grateful to the National Science Foundation (NSF) (CHE-1361104) for financial support. Computational resources were provided by the UCLA Institute for Digital Research and Education (IDRE) and the Extreme Science and Engineering Discovery Environment (XSEDE), which is supported by the NSF (OCI-1053575). Y. Y also thanks Beijing municipal high level innovative team building programme (IDHT20180504) and China Scholarship Council (CSC) for financial support of this research.

Disclosure statement

No potential conflict of interest was reported by the authors.

ORCID

Zhongyue Yang http://orcid.org/0000-0003-0395-6617

Notes

* Dedicated to the memory of the great theoretician and friend, Dieter Cremer.

Additional information

Funding

We are grateful to the National Science Foundation (NSF) (CHE-1361104) for financial support. Computational resources were provided by the UCLA Institute for Digital Research and Education (IDRE) and the Extreme Science and Engineering Discovery Environment (XSEDE), which is supported by the NSF (OCI-1053575). Y. Y also thanks Beijing municipal high level innovative team building programme (IDHT20180504) and China Scholarship Council (CSC) for financial support of this research.