115580-35-3

Upstream product

• 21087-29-6 trans-3-phenylprop-2-enyl chloride 
• 675-10-5 4-hydroxy-6-methyl-2-pyron 
• 21040-45-9 Cinnamyl acetate 
• 103-54-8 cinnamyl acetate 
• 125486-63-7 methyl 2-cinnamyl-3,5-dioxopentanoate 
• 673-32-5 1-Phenylprop-1-yne 

Downstream Products

• 116504-04-2 3-cinnamyl-4-methoxy-6-methyl-2-pyrone 
• 115580-42-2 4-hydroxy-6-methyl-3-(3-phenylpropyl)-2-pyrone 
• 115580-44-4 3-cyclohexyl-4-hydroxy-6-methyl-2-pyrone 

Relevant academic research and scientific papers

In(OTf)3-catalysed easy access to dihydropyranocoumarin and dihydropyranochromone derivatives

We developed an easy, In(OTf)3-catalysed, regioselective and generalizable method, for allylation/cyclization of β-ketolactone-type heterocyclic compounds. This reaction is proposed to proceed one-pot, through a Friedel-Crafts C-allylation followed by cyclization. This process represents a green synthetic method, as AcOH is the only isolated byproduct. We propose here, a protocol applicable for the construction of biologically active dihydropyranocoumarin and dihydropyranochromone derivatives.

Palladium-catalyzed allylic alkylation with internal alkynes to construct C-C and C-N bonds in water

A palladium-catalyzed system enabled efficient allylic alkylation with alkynes in water has been developed. This reaction presents an environmentally friendly strategy for constructing lots of allylic compounds with indolinones, ketones, amines as well as electron-rich aromatic compounds as nucleophiles. Moreover, the in situ formed arylallene intermediate adopting alkynes as starting materials omits the need for leaving groups and extra oxidants, showing high atom economy. The versatility of the developed reaction also lends itself to the incorporation of deuteriums by simply replacing H2O with D2O.

Large rate accelerations in the stille reaction with tri-2-furylphosphine and triphenylarsine as palladium ligands: mechanistic and synthetic implications

The effect changing the palladium ligands on the rates of typical Stille cross-coupling reactions was studied. Large rate enhancements (typically 102-103 over triphenylphosphine-based catalysts) were observed with tri-2-furylphosphine (TFP) and triphenylarsine, which are recommended as the new ligands of choice in the palladium-catalyzed coupling between olefinic stannanes and electrophiles. On the basis of the evidence presented, the transmetalation, which is the rate-determining step in the catalytic cycle, is postulated to involve a π-complex between the metal and the stannane double bond. In general, ligands that readily dissociate from Pd(II) and allow ready formation of this π-complex are the ones that produce the fastest coupling rates. The utility of the new ligands is demonstrated with several synthetic examples.

COPPER PROTECTION IN THE PALLADIUM CATALYZED REGIOSELECTIVE ALLYLATION OF A MODEL POLYKETIDE: METHYL 3,5-DIOXOHEXANOATE

Regioselective allylation of the model polyketide system methyl 3,5-dioxohexanoate at the C-2 position can be accomplished even with secondary and tertiary radicals by palladium catalyzed allylation of its copper(II) complex, 1a.Initial results indicate that the cobalt(II) complex, 1b, can also be useful.Cyclizations of the resulting diketoesters, 3, afford triacetic acid lactone derivatives, 5, regioselectively allylated at C-3.

PALLADIUM CATALYZED ALLYLIC C-ALKYLATION OF HIGHLY ACIDIC AND ENOLIC HETEROCYCLIC SUBSTRATES: TETRONIC ACID AND TRIACETIC ACID LACTONE

Tetronic acid (pKa 3.76) and triacetic acid lactone (pKa 4.94) have been alkylated at their active carbon atoms by means of thermodinamically controlled palladium catalyzed allylic alkylations.

Palladium-Catalyzed C-Alkylations of the Highly Acidic and Enolic Triacetic Acid Lactone. Mechanism and Stereochemistry

4-Hydroxy-6-methyl-2-pyrone (triacetic acid lactone) (1) is efficiently alkylated at C-3 with primary and secondary allylic substrates under thermodynamic control by using palladium(0) catalysts.Controlled hydrogenation of the resulting allylated derivatives affords pyrones with saturated chains at C-3.Allylic alkylations occur with retention of configuration at the allylic center, probably through a reversible kinetically favored O-alkylation.