Ring opening of boriranes vis‐à‐vis aziridines: An ab initio and DFT probe on the mechanisms |
| |
Authors: | Anbarasan Kalaiselvan Ponnambalam Venuvanalingam |
| |
Affiliation: | 1. School of Chemistry, Bharathidasan University, Tiruchirappalli 620024, India;2. School of Chemistry, Bharathidasan University, Tiruchirappalli 620024, IndiaSchool of Chemistry, Bharathidasan University, Tiruchirappalli 620024, India |
| |
Abstract: | Borirane undergoes ring opening reaction with NOCl and HNF2 yielding the corresponding alkenes. Ab initio and density functional investigations of this reaction with cis‐ and trans‐2,3‐dimethylboriranes reveal that these reactions take place in a single step through the formation of a prereactive complex and a transition state giving the alkene with the same stereochemistry. Calculations clearly show that the concerted cleavage of C? B bonds leads to retention of stereochemistry. Further, it shows that HNF2 cleaves boriranes more efficiently than does NOCl. Intrinsic reaction coordinate analyses and bond order analysis describe the nature of the transition state very well and fix the reaction mechanism. Solvent effect calculations through PCM model, with acetonitrile and CCl4 as solvents, do not alter the gas phase results significantly. © 2007 Wiley Periodicals, Inc. Int J Quantum Chem, 2007 |
| |
Keywords: | borirane ab initio and DFT aziridines ring opening stereochemistry |
|
|