121725-72-2

Upstream product

• 87802-71-9 (E)-methyl cinnamyl carbonate 
• 105-45-3 acetoacetic acid methyl ester 
• 4407-36-7 (2E)-3-phenyl-2-propen-1-ol 
• 7217-71-2 1-phenyl-2-propenyl acetate 
• 34284-28-1 methyl acetoacetate, monosodium salt 
• 106625-70-1 ethyl (1-phenylallyl) carbonate 
• 673-32-5 1-Phenylprop-1-yne 
• 2687-12-9 cinnamyl chloride 
• 100-52-7 benzaldehyde 
• 15768-07-7 methyl 2-benzylidene-3-oxobutanoate 
• 106625-69-8 ethyl (E)-3-phenyl-2-propenyl carbonate 
• 21040-45-9 Cinnamyl acetate 

Downstream Products

• 50552-30-2 4-phenyl-5-hexen-2-one 
• 17168-38-6 2,5-dimethyl-4-phenylfuran-3-carboxylic acid methylester 

Relevant academic research and scientific papers

Regioselective Rhodium-Catalyzed Addition of β-Keto Esters, β-Keto Amides, and 1,3-Diketones to Internal Alkynes

The first rhodium-catalyzed regioselective addition of 1,3-dicarbonyl compounds, including β-keto esters, β-keto amides, and 1,3-diketones, to internal alkynes furnishes branched allylic compounds. By applying RhI/DPEphos/TFA as the catalytic system, aliphatic as well as aromatic internal methyl-substituted alkynes act as suitable substrates to yield valuable branched α-allylated 1,3-dicarbonyl compounds regioselectively in good to excellent yields. A simple basic saponification–decarboxylation procedure provides access to valuable γ,δ-unsaturated ketones. The reaction shows a broad functional-group tolerance, and numerous structural variations on both reaction partners highlight the synthetic potential and flexibility of this method.

Rhodium/Lewis Acid Catalyzed Regioselective Addition of 1,3-Dicarbonyl Compounds to Internal Alkynes

Herein we describe an efficient protocol for the regioselective addition of 1,3-dicarbonyl compounds to internal alkynes catalyzed by rhodium/Lewis acid catalysts. The corresponding branched/linear allylic alkylation products could be selectively obtained in good yields. Rh-H species were considered to be generated by direct C-H oxidative addition of 1,3-dicarbonyl compounds with rhodium catalyst with the assistance of Lewis acid. Moreover, a retro-allylic alkylation process was observed in this transformation.

New 1,2,4,5-tetrakis-(N-imidazoliniummethyl)benzene and 1,2,4,5-tetrakis-(N-benzimidazoliummethyl)benzene salts as N-heterocyclic tetracarbene precursors: synthesis and involvement in ruthenium-catalyzed allylation reactions

New tetraimidazolinium and tetrabenzimidazolium salts have been prepared. Upon reaction with tBuOK, they generate carbene ligands, which were associated in situ to [RuCp*(MeCN)3]PF6 to produce new ruthenium catalysts that

Ruthenium-bisimine: A new catalytic precursor for regioselective allylic alkylation

New complexes [Cp*Ru(bisimine)Cl] are active catalysts for the regioselective alkylation of allylic carbonates by soft carbonucleophiles, in favour of the branched isomers. The catalysts can be conveniently prepared in situ from [Cp*Ru(cod)Cl] and a bulky aromatic bisimine.

A new route to 2-alkenyl-1,3-dicarbonyl compounds, intermediates in the synthesis of dihydrofurans

A two step synthetic strategy for obtaining 2-alkenyl-1,3-dicarbonyl compounds from the corresponding 1,3-dicarbonyl compounds is reported. The method is based on a Knoevenagel condensation and a Michael addition using a high order organocuprate procedure, and proves to be of general value. Obtained compounds are useful starting materials for the synthesis of furan derivatives.

Regiocontrol in palladium-catalysed allylic alkylation by addition of lithium iodide

Regioselectivity in the palladium-catalysed allylic alkylation of 1-arylprop-2-enyl acetates [ArCH(OAc)CH=CH2] or (E)-3-phenylprop-2-enyI acetate (PhCH=CHCH2OAc) with sodium enolates of soft carbon nucleophiles is controlled by addition of a catalytic amount of lithium iodide to give lienar products [(E)-ArCH=CHCH2Nu] exclusively; their branch isomers [ArCH(Nu)CH=CH2] were not detected.

Iodoenolcyclization. III. A General Approach to Tetrasubstituted Furans from 2-Alkenyl-1,3-Dicarbonyl Compounds.

2,3,4,5-tetrasubstituted furans were easily obtained from of 2-alkenyl-1,3-dicarbonyl compounds by an efficient three steps synthesis.

Ruthenium complex-catalyzed allylic alkylation of carbonucleophiles with allylic carbonates

Allylic carbonates except for allyl methyl carbonate reacted with carbonucleophiles such as ethyl acetoacetate in the presence of a catalytic amount of Ru(cod)(cot) in N-methylpiperidine at 80 deg C to give the corresponding monoallylated carbonucleophiles in high yields with high regioselectivity.The regioselectivity was quite different from that in the palladium-catalyzed reactions.The allylation of carbonucleophiles using allyl methyl carbonate selectively gave the diallylated carbonucleophiles in high yields.

Copper(I) promoted C-C bond forming reactions: direct activation of allyl alcohols

Allylic alcohols, acetates, carbonates and chlorides can be activated by copper(I) salts towards nucleophilic substitution by carbon nucleophiles under relatively mild conditions.