About two decades after Kobayashi's discovery in 1983 of a very mild way of generating highly reactive aryne intermediates, the synthetic community embraced o-(trimethylsilyl)aryl triflates as convenient and versatile aryne precursors for the synthesis of carbocycles and heterocycles, as well as natural products and pharmaceutically promising drug candidates. This review provides a comprehensive overview of the construction of heterocycles using Kobayashi's silylaryl triflate aryne precursors. It is organized according to the type of heterocycle generated.

Use of benzynes for the synthesis of heterocycles

This is a compilation of ionization and appearance potentials of positive ions published from 1955 through June 1966. The compilation lists the ion formed, the parent species from which it was formed, the other products of the process, the threshold energy for the formation of this ion, and the method by which this data was obtained. Where feasible, the heat of formation at 298 K of the positive ion has been computed for each entry using auxiliary thermochemical data. From these computed values “best” values have been chosen.

Ionization Potentials, Appearance Potentials, and Heats of Formation of Gaseous Positive Ions

Author(s): Duttwyler, Simon; Douvris, Christos; Fackler, Nathanael LP; Tham, Fook S; Reed, Christopher A; Baldridge, Kim K; Siegel, Jay S | Abstract: Si(mply) rips it apart: C-F activation of fluorobenzene has been achieved using the extremely strong silyl Lewis acids [Et3Si(X)]+ (X=PhF or Et3SiH) and [(2,6-dixylyl-C6H 3)SiMe2] + paired with the anion CHB 11Cl11-. They abstract fluoride from unactivated fluorobenzene to give arylated products, consistent with phenyl-cation-like reactivity (see scheme). © 2010 Wiley-VCH Verlag GmbH a Co. KGaA.

/pdf/c-f-activation-of-fluorobenzene-by-silylium-carboranes-53ue4sk92i.pdf

C-F activation of fluorobenzene by silylium carboranes: evidence for incipient phenyl cation reactivity.

https://link.springer.com/content/pdf/10.1007%2FBFb0111403.pdf

Properties and preparations of Si-Si linkages

Oxidation‐Reduction and Related Reactions of Metal‐Metal Bonds

Bond dissociation energies in organosilicon compounds

367. The kinetics of the reactions of silicon compounds. Part I. The gas-phase thermal decomposition of 2,2-difluoroethyltrifluorosilane

Kinetics of the thermal decomposition of polyfluoroalkylsilicon compounds

The gas-phase thermal decomposition of 3,3,3-trifluoropropyltrifluorosilane proceeds by a complex radical-chain mechanism at temperatures from 550 to 640° and with initial pressures from 40 to 110 torr. The compounds SiF4, C2H4, CHF3, and CF3·CH:CH2 are major products; other primary products are H2, CH3·SiF3, CH2:CH·SiF3, CH2:CF2, CF3·CH3, and a compound believed to be CF2:CH·CH2·SiF3. The compounds CH4, C2H6, and CF3·CH2·CH3 were observed as secondary products. The decomposition is approximately of order 1·5 with respect to reactant in the initial stages, and the rate-constant is given by log10k1·5(cm. mole–½ min.–1)= 19·6 – 74 × 103/4·58T. The results are interpreted in terms of a complex radical-chain mechanism.

The kinetics of the reactions of silicon compounds. Part II. The gas-phase thermal decomposition of 3,3,3-trifluoropropyltrifluorosilane

The liquid-phase thermal decomposition of 2,2-difluoroethyltri-n-butoxysilane into vinyl fluoride and tri-n-butoxyfluorosilane has been studied using the silicone fluid MS 550 as the inert solvent. An experimental method has been devised in which the reaction is followed by the vinyl fluoride evolved. At 230–266° the reaction is first-order over a six-fold range of initial concentration, homogeneous, and unaffected by the addition of tri-n-butoxyfluorosilane or trans-stilbene. The first-order rate constant is given by: log10k(sec.–1)=(8·53 ± 0·22)–(30·30 ± 0·53)/0·004576T The reaction is probably unimolecular, proceeding by a four-centre β-fluorine elimination as for the gas-phase decomposition. The transition state appears to be more heavily solvated than the reactant molecule, and may thus be polar in character.

P. J. Robinson

Papers

Bond dissociation energies in organosilicon compounds

367. The kinetics of the reactions of silicon compounds. Part I. The gas-phase thermal decomposition of 2,2-difluoroethyltrifluorosilane

Kinetics of the thermal decomposition of polyfluoroalkylsilicon compounds

The kinetics of the reactions of silicon compounds. Part II. The gas-phase thermal decomposition of 3,3,3-trifluoropropyltrifluorosilane

The kinetics of the reactions of silicon compounds. Part V. Liquid-phase thermal decomposition of 2,2-difluoroethyltri-n-butoxysilane