Density functional theory investigation of the reaction of isodiiodomethane with acetylene: potential utility of isodiiodomethane for cyclopropenation reactions

Dong Ming Chen; Yun-Liang Li; David Lee Phillips

doi:10.1021/jo0200825

Density functional theory investigation of the reaction of isodiiodomethane with acetylene: potential utility of isodiiodomethane for cyclopropenation reactions

J Org Chem. 2002 Jun 28;67(13):4619-22. doi: 10.1021/jo0200825.

Authors

Dong Ming Chen¹, Yun-Liang Li, David Lee Phillips

Affiliation

¹ Department of Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong S. A. R., P. R. China.

PMID: 12076170
DOI: 10.1021/jo0200825

Abstract

We present density functional theory calculations for the reactions of CH2I-I and CH2I with acetylene (HC triple bond CH) to form a cyclopropene product. CH2I-I readily reacts with HC triple bond CH to form a cyclopropene product and an I2 leaving group via a rate-determining step barrier of approximately 3.9 kcal/mol (B3LYP/Sadlej-pVTZ). Calculations indicated that the CH2I radical reacts to form an iodopropenyl radical, which can close to a cyclopropene only with difficulty. Our results indicate that CH2I-I may act as an effective carbenoid to produce cyclopropenated products from alkynes.