A density functional theory investigation of the Simmons-Smith cyclopropanation reaction: examination of the insertion reaction of zinc into the C-I bond of CH(2)I(2) and subsequent cyclopropanation reactions.
The insertion reaction of zinc into the C-I bond of CH(2)I(2) and subsequent cyclopropanation reactions with CH(2)CH(2) have been investigated using B3LYP level density functional theory calculations. The Simmons-Smith cyclopropanation reaction of olefins does not proceed easily due to the relatively large barriers on the insertion and cyclopropanation pathways. The computed results indicate that the IZnCH(2)I molecule is the active reagent in the Simmons-Smith reaction. This is consistent with the IZnCH(2)I reactive species being generated from diiodomethane and a Zn-Cu couple as proposed by several other research groups. The Simmons-Smith IZnCH(2)I carbenoid and CH(2)I-I carbenoid cyclopropanation reactions with olefins are compared. The reactions of olefins with the radicals from the decomposition of the IZnCH(2)I and CH(2)I-I species were also compared. We found that the chemical reactivity of the carbenoid species is dependent on its electrophilic behavior, steric effects, the leaving group character and the mechanism of the cyclopropanation reactions.
Fang
Wei-Hai
WH
Department of Chemistry, Beijing Normal University, PR China. fangwh@bnu.edu.cn
Phillips
David Lee
DL
Wang
Dong-qi
DQ
Li
Yun-Liang
YL
D003500:Cyclization; D003521:Cyclopropanes / Q000138:chemical synthesis*; D006847:Hydrocarbons, Iodinated / Q000737:chemistry; D008956:Models, Chemical; D013816:Thermodynamics; D015032:Zinc / Q000737:chemistry
D003521:Cyclopropanes; D006847:Hydrocarbons, Iodinated; C027946:methylene iodide; C030797:cyclopropane; D015032:Zinc