83542-41-0

Upstream product

• 100-52-7 benzaldehyde 
• 3102-33-8 trans-3-penten-2-one 
• 74-88-4 methyl iodide 
• 917-54-4 methyllithium 
• 625-33-2 3-penten-2-one 
• 143023-64-7 ((1E,3E)-4-nitropenta-1,3-dien-1-yl)benzene 
• 75-24-1 trimethylaluminum 
• 75-16-1 methylmagnesium bromide 
• 585533-41-1 C₁₁H₁₃NO₃ 
• 544-97-8 dimethyl zinc(II) 
• 14371-10-9 (E)-3-phenylpropenal 
• 67646-68-8 3-methyl-5-phenylpent-1-yne-3-ol 
• 75343-87-2 (E)-3-Methyl-1-phenyl-pent-3-ene-1,2-diol 
• 821775-44-4 tricarbonyl(3-methyl-5-phenyl-1-oxapenta-1,2,4-triene)iron⁽⁰⁾ 

Relevant academic research and scientific papers

Nickel-Catalyzed Reductive Cross-Coupling of Oxalates Derived from α-Hydroxy Carbonyls with Vinyl Bromides

nickel-catalyzed cross-electrophile coupling is disclosed in which a range of vinyl bromides were utilized as electrophiles with oxalates derived from α-hydroxy carbonyls as precursors to carbonyl radical coupling partners. This method is compatible with a broad range of functional groups, providing a complementary solution for the construction of β,γ-unsaturated carbonyl compounds.

α-Branched Ketone Dienolates: Base-Catalysed Generation and Regio- and Enantioselective Addition Reactions

In this study, the unique capacity of bifunctional Br?nsted bases to generate α-branched ketone dienolates and control both site- and stereoselectivity of their addition reactions to representative classes of carbon electrophiles (i.e., vinyl sulfones, nitroolefins, formaldehyde) is documented. We demonstrate that by using selected chiral tertiary amine/squaramide catalysts, the reactions of β,γ-unsaturated cycloalkanones proceed through the dienolate Cα almost exclusively and provide all-carbon quaternary cyclic ketone adducts in good yields with very high enantioselectivities. A minor amount (5 %) of γ-addition is observed when nitroolefins are used as electrophiles. The parent acyclic ketone dienolates proved to be less reactive under these conditions, and thus still constitute a challenging class of substrates. Quantum chemical calculations correctly predict these differences in reactivity and explain the observed site-specificity and enantioselectivity.

Alkenes as chelating groups in diastereoselective additions of organometallics to ketones

Alkenes have been discovered to be chelating groups to Zn(II), enforcing highly stereoselective additions of organozincs to β,γ-unsaturated ketones. 1H NMR studies and DFT calculations provide support for this surprising chelation mode. The results expand the range of coordinating groups for chelation-controlled carbonyl additions from heteroatom Lewis bases to simple C-C double bonds, broadening the 60 year old paradigm.

Mild conversion of propargylic alcohols to α,β-unsaturated enones in ionic liquids (ILs); A new 'metal free' life for the Rupe rearrangement

A mild and selective transition metal free protocol for the conversion of propargylic alcohols to cyclic and acyclic α,β-unsaturated enones via the Rupe rearrangement is reported. The method utilizes the Br?nsted acidic ionic liquid [BMIM-SO3H][OTf] as catalyst and [BMIM][PF 6] as solvent and offers the potential for recycling and reuse of the IL solvent. The feasibility to synthesize bicyclic fused cyclopentenone derivatives via a Rupe → Aldol → Nazarov sequence utilizing this protocol has also been demonstrated.

Enantio- and regioselective conjugate addition of organometallic reagents to linear polyconjugated nitroolefins

The copper-catalysed conjugate addition of trialkylaluminium and dialkylzinc reagents to polyconjugated nitroolefins (nitrodiene and nitroenyne derivatives) is reported. A reversed Josiphos ligand L7 allows for the selective 1,4- or 1,6-addition with high enantioselectivities. Copyright

Synthesis and olfactory evaluation of bulky moiety-modified analogues to the sandalwood odorant polysantol

Five new bulky moiety-modified analogues of the sandalwood odorant Polysantol have been synthesized by aldol condensation of appropriate aldehydes with butanone, deconjugative α-methylation of the resulting α,β-unsaturated ketones, and reduction of the co

One-carbon homologation of unsymmetrical ketones through magnesium β-oxido carbenoid rearrangement and trapping the enolate intermediates with electrophiles

A procedure for one-carbon homologation of unsymmetrical ketones, including one-carbon ring-expansion of 2-substituted cyclohexanones, through magnesium β-oxido carbenoid rearrangement as the key reaction is described. Addition of the α-sulfinyl carbanion of 1-chloroethyl p-tolyl sulfoxide to an unsymmetrical ketone gave two diastereomers as adducts in good yields. The adducts were treated with a base to give alkoxides, which were treated with a Grignard reagent to give magnesium β-oxido carbenoids. The β-oxido carbenoid rearrangement then took place to afford one-carbon homologated ketones having a methyl group at the α-position. Remarkable specificity or selectivity was observed in the rearrangement. The magnesium enolate intermediates of this reaction were found to be able to get trapped with several electrophiles to give one-carbon homologated α,α-disubstituted ketones. Origin of the specificity and selectivity is also discussed.

Indium-catalyzed cross-coupling reactions between α,β -unsaturated carbonyl compounds and aromatic aldehydes

Cross-coupling reactions between α,β-unsaturated carbonyl compounds and aromatic aldehydes have been achieved in tetrahydrofuran (THF) at 25 °C under N2 using a catalytic amount of InCl3 (0. 05 molar amount to the substrate) in the presence of both chlorotrimethylsilane (TMSCl) and aluminum foil (Al). These reactions provide the corresponding β,γ-unsaturated ketones in moderate yields, together with pinacol-coupling products of aldehydes as side products. Chlorides other than TMSCl and AlCl3, such as LiCl, CaCl2, MgCl2, and SOCl2, are not effective at all. Without either TMSCl or Al, no reaction proceeds even in the presence of the catalyst.

Nickel-catalyzed electrochemical couplings of vinyl halides: Synthetic and stereochemical aspects

Homo- and cross-coupling involving alkenyl halides have been performed efficiently using an electroassisted nickel-complex catalysis. Valuable product such as conjugated dienes, β,γ- or γ,δunsaturated esters, ketones, or nitriles, as well as alkenylated aryl compounds are thus prepared with high yields and high stereoselectivity. Partial isomerization is only observed in a few cases, when the alkenyl halide is involved in a late step of the catalytic cycle. This is the case in the preparation of (Z,Z)-1,3-diene.

Carbon-carbon bond forming reactions of η3-allyl iron tricarbonyl anions with carbon electrophiles

Reaction of the η3-allyl iron tricarbonyl anion, 1, with alkyl halides (RX, R = -CH3, -CH2Ph, -(CH2)3CH3, -CH(CH3)2,-CH2CH=CH2) followed by treat