689221-29-2

Upstream product

• 1655-07-8 ethyl 2-oxocyclohexane carboxylate 
• 4407-36-7 (2E)-3-phenyl-2-propen-1-ol 
• 6651-36-1 1-(Trimethylsilyloxy)cyclohexene 
• 117969-61-6 [(1E)-3-fluoroprop-1-en-1-yl]benzene 
• 673-32-5 1-Phenylprop-1-yne 
• 108-94-1 cyclohexanone 
• 13652-41-0 Cyclohexylidene-(2-methoxy-ethyl)-amine 
• 124517-47-1 cinnamyl tert-butyl carbonate 

Relevant academic research and scientific papers

Rhodium-Catalyzed Branched and Enantioselective Direct α-Allylic Alkylation of Simple Ketones with Alkynes

Herein, we report the first direct branched-selective α-allylic alkylation of simple ketones with alkynes under rhodium and secondary amine cooperative catalysis. Through a rhodium-hydride-catalyzed allylic substitution pathway, a series of valuable γ,δ-unsaturated ketones are obtained with excellent regioselectivity in an atom-economic and byproduct-free manner. With a chiral BIPHEP ligand, high enantioselectivity has been achieved for this transformation.

Gamma-alkenyl ketone and synthesis method thereof

The invention discloses gamma-alkenyl ketone and a preparation method thereof. Simple cyclic ketones or non-cyclic methyl ketones such as cyclopentanone and 1-phenyl-1-propyne are used as raw materials, and a target product is obtained with high yield, high regioselectivity and high enantioselectivity in the presence of an organic solvent, a catalyst, an additive and a ligand. The gamma-alkenyl ketone has the advantages of atom economy, high regioselectivity, high enantioselectivity and the like, and efficient conversion from cheap basic organic chemicals to high-added-value gamma-alkenyl ketone can be realized. The synthesized gamma-alkenyl ketone is a potential synthesis intermediate, and has potential application prospects in fine chemical synthesis and drug intermediate synthesis.

Chemo- and regioselectivity-tunable Pd-catalyzed allylic alkylation of imines

α-Carbanions of cyclic and acyclic imines have been successfully applied as nucleophiles in the Pd-catalyzed allylic alkylation reaction. Tuning of chemo- and regioselectivity has been realized by using t-BuOK/THF and LDA/toluene to give branched and line

Lewis acid/CpRu dual catalysis in the enantioselective decarboxylative allylation of ketone enolates

The addition of a Lewis acidic metal triflate salt Mg(OTf)2 as co-catalyst in the CpRu-catalyzed decarboxylative allylation of in situ-generated ketone enolates allows the reaction to proceed at lower temperature with higher regio- and enantios

Enantioselective CpRu-catalyzed carroll rearrangement - Ligand and metal source importance

The addition of unstabilized carbonyl nucleophiles to unsymmetrical allyl-metal fragments still represents a challenge to generate stereogenic centers enantio- and regioselectively. In this context, the decarboxylative Carroll rearrangement of allyl β-keto esters is particularly interesting, since chiral γ,δ-unsaturated ketones are obtained. Herein, we show that CpRu half-sandwich complexes can, with selected enantio-pure pyridine-monooxazoline ligands, catalyze this transformation and afford complete conversions along with good levels of regioselectivity and enantioselectivity. Even more challenging (electron-poor) substrates react (up to 86% ee, branched/linear ratio ≥ 97:03). In addition, the use of an air-stable metal precursor, namely [CpRu(η6-naphthalene)][PF6], allows the reaction to be carried out reproducibly even in non-anhydrous THF with a catalyst loading as low as 2 mol-%. Wiley-VCH Verlag GmbH & Co. KGaA, 2008.

Mechanistic analysis of the photocycloaddition of silyl-tethered alkenes

(Chemical Equation Presented) The photochemistry of substituted cinnamyloxy silanes has been examined in both cyclohexane and acetonitrile solvents. Alkene isomerization occurs in addition to cycloaddition. Fluorescence quantum yields and excited singlet state lifetimes have been determined for each compound. We have used the information in order to better understand the regio- and stereoselectivity of photocycloaddition between silyl-tethered cinnamyl groups. This study allows us to conclude that the 2 + 2 photocycloaddition between alkenes is not a Woodward-Hoffmann orbital symmetry controlled event. The most consistent explanation for the excellent regio- and stereoselectivity is that the photocycloaddition is conformationally controlled.

Boron trifluoride-catalyzed reaction of alkyl fluoride with silyl enolate, allylsilane, and hydrosilane

Alkylation of silyl enolates with tert-alkyl or allylic fluorides proceeds smoothly in the presence of a catalytic amount of boron trifluoride to afford the corresponding carbonyl compounds. Allylation and reduction of alkyl fluorides with allylsilane and hydrosilane, respectively, occur under BF 3 catalysis.

Ruthenium-catalyzed decarboxylative allylation of nonstabilized ketone enolates

(Matrix Presented) Bipyridyl(pentamethylcyclopentadienyl)ruthenium chloride is an efficient catalyst for the formal [3,3] rearrangement of allyl β-ketoesters. The mechanism of the transformation involves formation of π-allyl ruthenium intermediates, which