84363-86-0

Upstream product

• 104-53-0 3-phenyl-propionaldehyde 
• 4392-24-9 Cinnamyl bromide 
• 960-16-7 tributylphenylstannane 
• 147609-46-9 2-(2E)-(3-phenyl-2-propen-1-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane 
• 2687-12-9 cinnamyl chloride 
• 4407-36-7 (2E)-3-phenyl-2-propen-1-ol 
• 97-94-9 triethyl borane 
• 1313878-07-7 (E)-1-phenyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)allyl acetate 
• 370581-86-5 1,4-diphenyl-5-hexen-3-ol 
• 29000-10-0 (E)-cinnamyl(triphenyl)stannane 
• 21040-45-9 Cinnamyl acetate 

Relevant academic research and scientific papers

Nickel-Catalysed Allylboration of Aldehydes

A nickel catalyst for the allylboration of aldehydes is reported, facilitating the preparation of homoallylic alcohols in high diastereoselectivity. The observed diastereoselectivities and NMR experiments suggest that allylation occurs through a well-defined six-membered transition state, with nickel acting as a Lewis acid.

Nickel-Catalyzed Homo- And Cross-Coupling of Allyl Alcohols via Allyl Boronates

A nickel-catalyzed homo- and cross-coupling of allylic alcohols to 1,5-dienes in the presence of B2pin2 with excellent regioselectivity has been developed. Mechanistic studies indicate that the reaction proceeds via sequential nickel-catalyzed borylation of allyl alcohols followed by cross-coupling of the resulting allyl boronates with allyl alcohols. The method was effectively applied to nickel-catalyzed allylation of aldehydes using allylic alcohols directly.

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.

Controllable Stereoselective Synthesis of (Z)- and (E)-Homoallylic Alcohols Using a Palladium-Catalyzed Three-Component Reaction

Diastereoselective synthesis of (Z)- and (E)-homoallylic alcohols using a Pd-catalyzed three-component reaction of 3-(pinacolatoboryl)allyl benzoates, aldehydes, and aryl stannanes was developed, which provides an alternative method for the allylboration of aldehydes using α, γ-diaryl-substituted allylboronates. Both sets of reaction conditions enable access to either (Z)- or (E)-homoallylic alcohols with good to high alkene stereocontrol. The present method showed good functional group compatibility and generality. Efficient chirality transfer reactions to afford enantioenriched (Z)- and (E)-homoallylic alcohols were also achieved.

Pd-catalyzed three-component reaction of 3-(Pinacolatoboryl)ally acetates, aldehydes, and organoboranes: A new entry to stereoselective synthesis of (Z)- anti -homoallylic alcohols

The Pd-catalyzed three-component reaction of 3-(pinacolatoboryl)allyl acetates, aldehydes, and organoboranes is described. The reaction is initiated by the formation of an allylic gem-palladium/boryl intermediate, which then undergoes allylation of aldehydes by allylboronates followed by a coupling reaction of in situ generated (Z)-vinylpalladium acetates with organoboranes to provide the (Z)-anti-homoallylic alcohols with high levels of diastereoselectivity and alkene stereocontrol.

The first In(OTf)3-catalyzed conversion of kinetically formed homoallylic alcohols into the thermodynamically preferred regioisomers: Application to the synthesis of 22α-sterols

A retro-ene reaction that generates the parent aldehyde and a sigmatropic rearrangement are involved in the In(OTf)3-catalyzed conversion of homoallylic alcohols 1 into the thermodynamically favored regioisomers 2. This method can be used for the stereocontrolled synthesis of linear homoallylic 22α-sterols from their readily accessible branched 22β isomers.

Facile preparation of allylzinc species from allyl bromides and unactivated zinc induced by a catalytic amount of aluminum chloride and their reactions with carbonyl compounds and acetals

The effects of Lewis acids (ZnCl2, AlCl3, BF3, and TiCl4) on the generation of allylzinc species from allyl bromide and unactivated zinc powder in dry tetrahydrofuran (THF) were examined by trapping the organozinc compound with benzaldehyde, that is, Grignard-type allylation of the aldehyde. Among the Lewis acids employed, AlCl3 was found to be the promoter of choice. The allylzinc species preformed in the presence of a catalytic amount of AlCl3 effectively allylated carbonyl compounds. Various aromatic and aliphatic aldehydes as well as ketones were converted into homoallylic alcohols in good to excellent yields. Under the reaction conditions employed, ester, hydroxy, acetal, and aromatic nitro and halide groups were tolerated. In the case of α,β-unsaturated carbonyl compounds, selective 1,2-addition was observed. Substituted allyl bromides such as prenyl, crotyl, cinnamyl, and 2-cyclohexenyl bromides were smoothly converted to the corresponding allylzinc compounds, which reacted with carbonyl compounds to give substituted homoallylic alcohols in excellent yields. The diastereoselectivity in crotylation, cinnamylation, and 2-cyclohexenylation depended upon the structures of both the organic metals and the electrophiles. The origin of the observed selectivity is discussed. The allylation of dimethyl and cyclic acetals accompanied with carbon-oxygen bond cleavage also proceeded in excellent yields provided that two equivalents of AlCl3 was present.

STEREOSELECTIVE ACYCLIC SYNTHESIS VIA ALLYLMETALS: STRUCTURAL DEPENDENCE IN A LEWIS-ACID CATALYZED ADDITION OF ALLYLTINS TO ALDEHYDES

Lewis-acid catalyzed reaction of allyltins with aldehydes at -78 deg C provide homoallyl alcohols with high stereoselectivity; 2-alkenyltins in general provide erythro adducts preferentially with an erithro/threo ratio greater than 12/1, whereas only thre