Related Experiment Video
Updated: Dec 31, 2025
![Solid-phase Synthesis of [4.4] Spirocyclic Oximes](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F58508.jpg&w=3840&q=50)
Solid-phase Synthesis of [4.4] Spirocyclic Oximes
Published on: February 6, 2019
Cycloaddition Chemistry of a Silylene-Nickel Complex toward Organic π-Systems: From Reversibility to C-H Activation
Terrance J Hadlington1, Arseni Kostenko1, Matthias Driess1
1Department of Chemistry, Metalorganics and Inorganic Materials, Technische Universität Berlin, Strasse des 17. Juni 135, Sekr. C2, 10623, Berlin, Germany.
Abstract:
The versatile cycloaddition chemistry of the Si-Ni multiple bond in the acyclic (amido)(chloro)silylene→Ni0 complex 1, [(TMS L)ClSi→Ni(NHC)2 ] (TMS L=N(SiMe3 )Dipp; Dipp=2,6-iPr2 C6 H4 ; NHC=C[(iPr)NC(Me)]2 ), toward unsaturated organic substrates is reported, which is both reminiscent of and expanding on the reactivity patterns of classical Fischer and Schrock carbene-metal complexes. Thus, 1:1 reaction of 1 with aldehydes, imines, alkynes, and even alkenes proceed to yield [2+2] cycloaddition products, leading to a range of four-membered metallasilacycles. This cycloaddition is in fact reversible for ethylene, whereas addition of an excess of this olefin leads to quantitative sp2 -CH bond activation, via a 1-nickela-4-silacyclohexane intermediate. These results have been supported by DFT calculations giving insights into key mechanistic aspects.
More Related Videos
10:17Efficient Construction of Drug-like Bispirocyclic Scaffolds Via Organocatalytic Cycloadditions of α-Imino γ-Lactones and Alkylidene Pyrazolones
Published on: February 7, 2019
07:50Efficient Synthesis of All-Carbon Quaternary Centers via the Conjugate Addition of Functionalized Monoorganozinc Bromides
Published on: May 26, 2019
Related Concept Videos
Cycloaddition Reactions: Overview
[4+2] Cycloaddition of Conjugated Dienes: Diels–Alder Reaction
Pericyclic Reactions: Introduction
Pericyclic reactions can be classified into three categories: electrocyclic reactions, cycloaddition reactions, and sigmatropic rearrangements. Electrocyclic reactions and sigmatropic...
Cycloaddition Reactions: MO Requirements for Thermal Activation
Diels–Alder Reaction Forming Cyclic Products: Stereochemistry
Cycloaddition Reactions: MO Requirements for Photochemical Activation