53598-04-2

Upstream product

• 106-24-1 Geraniol 
• 100-52-7 benzaldehyde 
• 6138-90-5 trans-geranyl bromide 
• 7417-81-4 benzyl phenyl sulfoxide 
• 41273-34-1 (3,7-dimethyl-2,6-octadienyl)-triphenylphosphonium bromide 
• 114444-84-7 Acetatetributyl-((E)-3,7-dimethyl-octa-2,6-dienyl)-phosphonium; 
• 114444-86-9 Acetate((E)-3,7-dimethyl-octa-2,6-dienyl)-triphenyl-phosphonium; 
• 141-27-5 3,7-dimethyl-2,6-octadienal 
• 105-87-3 3,7-dimethyl-2E,6-octadien-1-yl acetate 

Relevant academic research and scientific papers

Weakening C-O bonds: Ti(III), a new reagent for alcohol deoxygenation and carbonyl coupling olefination

Investigations detailed herein, including density functional theory (DFT) calculations, demonstrate that the formation of either alkoxy- or hydroxy-Ti(III) complexes considerably decreases the energy of activation for C-O bond homolysis. As a consequence of this observation, we described two new synthetic applications of Nugent's reagent in organic chemistry. The first of these applications is an one-step methodology for deoxygenation-reduction of alcohols, including benzylic and allylic alcohols and 1,2-dihydroxy compounds. Additionally, we have also proved that Ti(III) is capable of mediating carbonyl coupling-olefination. In this sense, and despite the fact that for over 35 years it has been widely accepted that either Ti(II) or Ti(0) was the active species in the reductive process of the McMurry reaction, the mechanistic evidence presented proves the involvement of Ti(III) pinacolates in the deoxygenation step of the herein described Nugent's reagent-mediated McMurry olefination. This observation sheds some light on probably one of the mechanistically more complex transformations in organic chemistry. Finally, we have also proved that both of these processes can be performed catalytically in Cp 2TiCl2 by using trimethylsilyl chloride (TMSCl) as the final oxygen trap.

Stereoselective E and Z Olefin Formation by Wittig Olefination of Aldehydes with Allylic Phosphorus Ylides. Stereochemistry

Sterically crowded allylic tributylphosphorus ylides such as β-γ-disubstituted allylic ylides react with various aldehydes to afford E olefins with high stereoselectivity (E>92percent).As the steric demand of the ylides was decreased, bulky aldehydes were required to achieve high E selectivity.On the other hand, predominant or exclusive formation of Z olefins was achieved by using allylic triphenylphosphorus ylides and tertiary aldehydes like pivaldehyde, while the combination of allylic triphenylphosphorus ylides and such large secondary aldehydes as cyclohexanecarboxaldehyde led to E olefin formation under the lithium salt free conditions.The distinct lithium salt effect was observed in the reaction effected with triphenylphosphorus ylides.The origin of the observed E or Z selectivity can be reasonably explained according to Vedejs' rationale on the Wittig reaction stereochemistry.

Palladium-Catalyzed Allylidenation of Aldehyde. A Simple and Convenient Method for the Preparation of Conjugated Diene and Polyene Compounds

Allylic phenylcarbamates prepared from allylic alcohols and phenyl isocyanate in situ reacted with aldehydes to give conjugated dienes in good yields in the presence of tributylphosphine and a catalytic amount of Pd(PPh3)4.This method proved to be suitable for the preparation of polyene compounds such as carotenoids.

2-Allylisourea as a Starting Material for Palladium-Catalyzed Wittig-Type Allylidenation of Aldehydes

2-Allylic-substituted isoureas underwent Wittig-type allylidenation of aldehydes in the presence of triphenylphosphine and 2 molpercent of to give the corresponding conjugated olefins in tolerable to good yields.