131111-08-5

Upstream product

• 136559-11-0 4-Phenyl-1-vinyl-cyclohexanol 
• 7486-35-3 tri-n-butyl(vinyl)tin 
• 122948-47-4 4-phenylcyclohex-1-enyl trifluoromethanesulfonate 

Downstream Products

• 138624-02-9 (4-Ethyl-cyclohex-3-enyl)-benzene 

Relevant academic research and scientific papers

Significant enhancement of the Stille reaction with a new combination of reagents-copper(I) iodide with cesium fluoride

A systematic investigation for enhancement of Stille reaction using the combination of copper(I) iodide and cesium fluoride was described. Initial route to the target compound involved a double Stille coupling in the carbon-carbon bond formation of the key intermediate 1. Homocoupling has often been observed in this reaction especially when electron-withdrawing substituents are present in conjugation with tin. After extensive optimization, a variety of electronically unfavourable and sterically hindered substrates were coupled in very high yields under mild conditions.

Stille coupling made easier - The synergic effect of copper(I) salts and the fluoride ion

CsF and Cul do the trick: Stille coupling reactions of aryl/vinyl iodides, triflates, and bromides with aryl/vinyl stannanes are greatly enhanced by the inclusion of CsF and Cul in the reaction mixture (see scheme; Conditions A: [Pd(PPh3)4]/CsF/ Cul/DW/45 °C; Conditions B: PdCl 2/ PtBu3/CsF/Cul/DMF/45 °C).

Rearrangement of allylic and propargylic alcohols catalyzed by the combined use of tetrabutylammonium perrhenate(VII) and p-toluenesulfonic acid

Allylic rearrangement and/or dehydration reaction of allylic alcohols proceeds smoothly by the use of catalytic amounts of tetrabutylammonium perrhenate and p-toluenesulfonic acid hydrate. Treatment of propargylic alcohols with the catalysts at room temperature affords the rearranged products, α,β-unsaturated carbonyl compounds, while β,γ-unsaturated ketones are obtained as main products by the reaction in refluxing 1,2-dichloroethane. The application of this catalytic system is also described for the preparation of some synthetic intermediates.

Rearrangement of Allylic and Propargylic Alcohols Catalyzed by the Combined Use of Tetrabutylammonium Perrhenate(VII) and p-Toluenesulfonic Acid

Allylic rearrangement and/or dehydration of allylic alcohols proceed by the use of a catalytic amount of tetrabutylammonium perrhenate and p-toluenesulfonic acid.Treatment of propargylic alcohols with the above reagents affords the rearranged products, α,β-unsaturated carbonyl compounds.

Large rate accelerations in the stille reaction with tri-2-furylphosphine and triphenylarsine as palladium ligands: mechanistic and synthetic implications

The effect changing the palladium ligands on the rates of typical Stille cross-coupling reactions was studied. Large rate enhancements (typically 102-103 over triphenylphosphine-based catalysts) were observed with tri-2-furylphosphine (TFP) and triphenylarsine, which are recommended as the new ligands of choice in the palladium-catalyzed coupling between olefinic stannanes and electrophiles. On the basis of the evidence presented, the transmetalation, which is the rate-determining step in the catalytic cycle, is postulated to involve a π-complex between the metal and the stannane double bond. In general, ligands that readily dissociate from Pd(II) and allow ready formation of this π-complex are the ones that produce the fastest coupling rates. The utility of the new ligands is demonstrated with several synthetic examples.

Palladium in Cephalosporin Chemistry: Mild Triflate Couplings in the Absence of Phosphines and Halide Donors

Palladium catalyzed triflate-organostannane couplings are shown to proceed in a very mild manner in the absence of added phosphine and halide reagents.This protocol has been demonstrated for 3-trifloxycephems and vinyltriflates.