87383-87-7

Upstream product

• 40595-35-5 (Z)-1-phenyl-3-(trimethylsilyl)-1-propene 
• 630-19-3 pivalaldehyde 
• 40595-34-4 (E)-trimethyl(3-phenylallyl)silane 
• 101306-31-4 benzyl cinnamyl ether 
• 4407-36-7 (2E)-3-phenyl-2-propen-1-ol 
• 588-73-8 (Z)-β-bromostyrene 
• 588-72-7 [(E)-2-bromoethenyl]benzene 
• 74785-32-3 (E)-cinnamyl(tributyl)tin 
• 590-86-3 isovaleraldehyde 
• 21040-45-9 Cinnamyl acetate 

Downstream Products

• 33398-52-6 erythro-3-Hydroxy-4,4-dimethyl-2-phenylvaleriansaeure 
• 33398-52-6 α-(1-Hydroxy-2,2-dimethylpropyl)benzenessigsaeure 

Relevant academic research and scientific papers

Catalytic Nucleophilic Allylation Driven by the Water-Gas Shift Reaction

The ruthenium-catalyzed allylation of aldehydes with allylic pro-nucleophiles has been demonstrated to be an efficient means to form carbon-carbon bonds under mild conditions. The evolution of this reaction from the initial serendipitous discovery to its general synthetic scope is detailed, highlighting the roles of water, CO, and amine in the generation of a more complete catalytic cycle. The use of unsymmetrical allylic pro-nucleophiles was shown to give preferential product formation through the modulation of reaction conditions. Both (E)-cinnamyl acetate and vinyl oxirane were efficiently used to form the anti-branched products (up to >20:1 anti/syn) and E-linear products (up to >20:1 E/Z) in high selectivity with aromatic, α,β-unsaturated, and aliphatic aldehydes, respectively. Attempts to render the reaction enantioselective are highlighted and include enantioenrichment of up to 75:25 for benzaldehyde.

Pd-catalyzed nucleophilic allylic alkylation of aliphatic aldehydes by the use of allyl alcohols

Under catalysis of Pd(OAc)2-(P-n-Bu)3, Et 2Zn promotes a variety of allyl alcohols to undergo nucleophilic allylation of aliphatic aldehydes and ketones at room temperature and provides homoallyl alcohols in 60-90 and ca. 60% isolated yield, respectively. The reaction is irreversible and kinetically controlled, and unique regio- and stereoselectivities observed for the allylation with unsymmetrically substituted allyl alcohols are discussed.

Regio- and Stereochemistry on the Electrophilic Trapping of Allylic Samariums Generated by Reductive Cleavage of Allylic Ethers with (C5Me5)2Sm(thf)n

The C-O bond of allylic benzyl ethers was selectively cleaved with Cp*2Sm(thf)n to give allylic samarium complexes in good yields. Facility of their bond fission has been found to be comparable to that of the corresponding propargylic ethers intermolecularly, but lower intramolecularly. Regio-and stereochemistry on the electrophilic trapping of the allylic complexes thus generated remarkably depended on the nature of the electrophiles. They reacted with carbonyl compounds exclusively from the most substituted terminus of the allylic moieties to yield blanched homoallylic alcohols with anti diasteroselectivity. On the other hand, trapping with silyl chlorides produced linear allylic silanes. Here, a plausible mechanism to account for the difference is proposed.

On the Transmetallation of (E)-1-Phenyl-3-(tributylstannyl)propene and 3-Phenyl-3-(tributylstannyl)propene with BuSnCl3

Transmetallation of (E)-1-phenyl-3-(tributylstannyl)propene and 3-phenyl-3-(tributylstannyl)propene with BuSnCl3, and the isomerization of the transmetallated product are described.The application of the reactions to stereoselective (Z)-3-phenyl-2-propenylation and threo-1-phenyl-2-propenylation of aldehydes is also described.

ERYTHROSELECTIVITY IN ADDITION OF γ-SUBSTITUTED ALLYLSILANES TO ALDEHYDES IN THE PRESENCE OF TITANIUM CHLORIDE

(E)-Crotyltrimethylsilane and (E)-cinnamyltrimethylsilane were allowed to react with aldehydes (RCHO: t-Bu, i-Pr, Et, Me) in the presence of titanium chloride to give erythro homoallyl alcohols with over 93percent selectivity.Lower erythroselectivity was observed in the reaction of (Z)-allylsilanes.