Borrowing electron density from a rich friend: transition state stabilization by electron transfer from a remote donor

*Beauty Chabuka K., Nikolaeva Albina A., Ivanova Olga A., Trushkov Igor V. Zhokhov Sergey S., *Igor Alabugin, V.

*Florida State University, Department of Chemistry and Biochemistry
Moscow State University, Department of Organic Chemistry, Laboratory of Organoelement Compounds

Dimethyloxosulfonium methylide can transfer methylene to electrophilic alkenes. This classic reaction is known as Corey–Chaykovsky cyclopropanation¹. In our work, we use computational chemistry to understand the mechanism behind the recent discovery that a new methylene group can be inserted between the aromatic ring and double bond, leading to a chain extension in addition to cyclopropanation. An interesting observation is that the presence of an OH group (or NH₂) in the aromatic ring is essential for the transfer of two CH₂ groups to the alkene: one for the chain extension, another for cyclopropanation. This research project focuses on exploring the proposed mechanistic pathways by using DFT methods to analyze the stereoelectronic requirements for this new process. This analysis led to a better understanding of this new powerful and practical methodology for construction of small cycles.

Oral or poster presentation proposals for consideration at FAME.