106046-45-1

Upstream product

• 123-72-8 butyraldehyde 
• 97515-98-5 Triphenyl-((E)-3-phenyl-allylidene)-λ⁵-arsane 
• 100-52-7 benzaldehyde 
• 74676-14-5 (Z)-hex-2-enyltrimethylsilane 
• 14371-10-9 (E)-3-phenylpropenal 
• 1779-51-7 n-butyl(triphenyl)phosphonium bromide 
• 925-90-6 ethylmagnesium bromide 
• 109529-98-8 ((1E,3E)-5-bromopenta-1,3-dien-1-yl)benzene 

Relevant academic research and scientific papers

The regioselectivity of 1,3-disubstituted allylmetal species towards electrophiles: 1-(Trimethylsilyl)alk-2-enylpotassium compounds

1-(Trimethylsilyl)alk-2-enylpotassium species are readily generated by deprotonation of (alk-2-enyl)trimethylsilanes with the superbasic mixture of butyllithium and potassium tert-butoxide. Like the parent compound 1- (trimethylsilyl)allylpotassium, they too react with a variety of electrophiles preferentially, if not exclusively, at the silyl-distant terminus of the allyl moiety, thus producing branched enesilanes. The opposite regioselectivity previously observed with iodomethane hence appears to be an exception.

Palladium-Catalyzed Regio- A nd Enantioselective Hydrosulfonylation of 1,3-Dienes with Sulfinic Acids: Scope, Mechanism, and Origin of Selectivity

Chiral sulfones are important structural motifs in organic synthesis because of their widespread use in pharmaceutical chemistry. In particular, chiral allylic sulfones have drawn particular interest because of their synthetic utility. However, enantioselective synthesis of 1,3-disubstituted unsymmetrical chiral allylic sulfones remains a challenge. In this article, we report a protocol for (R)-DTBM-Segphos/Pd-catalyzed regio- A nd enantioselective hydrosulfonylation of 1,3-dienes with sulfinic acids, which provides atom- A nd step-economical access to 1,3-disubstituted chiral allylic sulfones. The reaction occurs under mild conditions and has a broad substrate scope. Combined experimental and computational studies suggest that the reaction is initiated by a ligand-to-ligand hydrogen transfer followed by a C-S bond reductive elimination via a six-membered transition state. Steric repulsion between the olefinic C-H of the substrate and the tert-butyl group of (R)-DTBM-Segphos was found to be a key factor in the enantiocontrol.

A biosynthetically inspired route to substituted furans using the Appel reaction: Total synthesis of the furan fatty acid F5

Appel reaction conditions have been harnessed to affect a mild biosynthetically inspired dehydration of endoperoxides to deliver multi-substituted electron rich furans. Unlike traditional dehydrative procedures, this method is metal and acid free, and can be achieved under redox neutral conditions. It is general for a range of aryl and alkyl substituted endoperoxides, and is functional group tolerant. Furthermore, this procedure has been used to deliver an effective total synthesis of the furan fatty acid (FFA) F5.

Bidentate hydroxyalkyl NHC ligands for the copper-catalyzed asymmetric allylic substitution of allyl phosphates with grignard reagents

Demonstrating their potential: Bidentate alkoxy NHC ligands have been used in the copper-catalyzed asymmetric allylic alkylation of allyl phosphates with Grignard reagents (see scheme). The method provides access to tertiary and quaternary chiral centers with high regio- and enantioselectivity. The system is also applied to the synthesis of chiral E,E-dienes, a key structural motif prevalent in natural products. Copyright

Chemoselectivity in the ruthenium-catalyzed redox isomerization of allyl alcohols

Adjustment of oxidation level by internal hydrogen reorganization represents a highly efficient synthetic protocol. Cyclopentadienylbis(triphenylphosphine)ruthenium chloride in the presence of triethylammonium hexafluorophosphate catalyzes the redox isomerization of allyl alcohols to their saturated aldehydes or ketones. High chemoselectivity is observed since simple primary and secondary alcohols and isolated double bonds are not affected by this catalyst. The reaction is sensitive to the degree of substitution on the double bond and requires relatively unhindered olefins. Switching to indenylbis(triphenylphosphine)ruthenium chloride in the presence of triethylammonium hexafluorophosphate significantly expands the scope of the reaction to substrates bearing more substituted olefinic linkages and to cyclic substrates of rings containing eight or more members. The mechanism is probed by deuterium labeling, which shows that the metal catalyzes an intramolecular 1,3-hydrogen shift of the carbinol hydrogen to the terminal olefinic position.

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.

Chemical process

Novel 2,4-dihydrocarbylspiro[5.5]undeca-1,4,8-trien-3-one compounds are prepared by reacting an N,N-dihydrocarbyl,2,6-dihydrocarbyl-4-aminomethylphenol with a conjugated diene and an alkyl halide in a liquid solvent medium.