Related Experiment Video
Updated: Mar 22, 2026

Accessing Valuable Ligand Supports for Transition Metals: A Modified, Intermediate Scale Preparation of 1,2,3,4,5-Pentamethylcyclopentadiene
Published on: March 20, 2017
Efficient Preparation of TMSCCl2 Br and Its Use in Dichlorocyclopropanation of Electron-Deficient Alkenes
Darren S Lee1, María Jesús Durán-Peña2, Laurence Burroughs2
1School of Chemistry, University of Nottingham, University Park, Nottingham, NG7 2RD, UK. darren.lee@nottingham.ac.uk.
Abstract:
The reaction of excess TMSCl and LiCCl2 Br at low temperature is a technically simple high yield route to TMSCCl2 Br. The latter is a stable source of the dichlorobromomethide carbanion, which undergoes 1,4-addition with cyclic nitroalkenes and (E)-fumarates leading to dichlorocyclopropanes after bromide expulsion. For nitrostyrenes the reaction arrests at the 1,4-addition product. Low temperature NMR spectroscopy studies and DFT calculations suggest the formation of an "ate" species [(nitronate)SiFMe3 ](-) which, upon boil-off of TMSF at 10-20 °C, yields the cyclopropane. DFT calculations also support the experimental differences between fluoride and acetate as promotors.
More Related Videos
07:50Efficient Synthesis of All-Carbon Quaternary Centers via the Conjugate Addition of Functionalized Monoorganozinc Bromides
Published on: May 26, 2019
09:35Preparation of a Corannulene-functionalized Hexahelicene by CopperI-catalyzed Alkyne-azide Cycloaddition of Nonplanar Polyaromatic Units
Published on: September 18, 2016
Related Concept Videos
Halogenation of Alkenes
Consider the bromination of cyclopentene. Molecular bromine is polarized in the proximity of the π electrons of cyclopentene. An electrophilic bromine atom adds across the double bond, forming a cyclic bromonium ion intermediate.
Alkenes via Reductive Coupling of Aldehydes or Ketones: McMurry Reaction
Electrophilic Aromatic Substitution: Chlorination and Bromination of Benzene
Preparation of Alkynes: Dehydrohalogenation
Alkynes can be prepared by dehydrohalogenation of vicinal or geminal dihalides in the presence of a strong base like sodium amide in liquid ammonia. The reaction proceeds with the loss of two equivalents of hydrogen halide (HX) via two successive E2 elimination reactions.
Radical Substitution: Allylic Bromination
Formation of Halohydrin from Alkenes