1375111-57-1

Upstream product

• 764-01-2 methyl propargyl alcohol 
• 92-69-3 4-Phenylphenol 

Downstream Products

• 1375111-58-2 (Z)-1-((3αR,7αR)-5-oxo-7α-phenyl-4,5-dihydrobenzofuran-3(2H,3αH,7αH)-ylidene)ethyl acetate 
• 1448451-20-4 (3aS,7aS,Z)-7a-phenyl-3-(1-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)ethylidene)-2,3,3a,4-tetrahydrobenzofuran-5(7aH)-one 

Relevant academic research and scientific papers

Asymmetric Synthesis of a Fused Tricyclic Hydronaphthofuran Scaffold by Desymmetric [2+2+2] Cycloaddition

A rhodium(I)-BINAP-catalyzed highly enantioselective [2+2+2] cycloaddition of enynes with alkynes has been developed. Diverse fused tricyclic hydronaphthofuran scaffolds with three consecutive stereogenic centers were constructed in one step from easily a

Highly Enantioselective Rhodium-Catalyzed Cross-Addition of Silylacetylenes to Cyclohexadienone-Tethered Internal Alkynes

The first highly enantioselective rhodium-catalyzed cross-addition of silylacetylenes to cyclohexadienone-tethered internal alkynes has been achieved via a tandem process: regioselective alkynylation of the internal alkynes and subsequent intramolecular conjugate addition to the cyclohexadienones, affording the cis-hydrobenzofuran frameworks with good yields (up to 88% yield) and excellent enantioselectivities (90%-96% ee). This mild reaction showed perfect atom economy and broad functional group tolerance. Furthermore, a gram-scale experiment and diverse further conversions of the cyclization products were also presented.

Palladium enolate umpolung: Cyclative diacetoxylation of alkynyl cyclohexadienones promoted by a Pd/SPRIX catalyst

A novel palladium-catalyzed reaction involving an unusual nucleophilic attack on a palladium enolate was developed using a spiro-bis(isoxazoline) (SPRIX) ligand. Treatment of alkynyl cyclohexadienone substrates with a Pd/SPRIX catalyst in acetic acid under an oxygen atmosphere furnished diacetoxylated benzofuranone derivatives in good yields. This cyclative diacetoxylation proceeded enantioselectively in the presence of an optically pure SPRIX ligand. In a SPRIX: A new palladium-catalyzed reaction involving an unusual nucleophilic attack on a palladium enolate was developed using the SPRIX ligand. Treatment of alkynyl cyclohexadienone substrates with Pd/SPRIX in acetic acid under an oxygen atmosphere furnished diacetoxylated benzofuranone derivatives in good yields and with high enantioselectivity.

Rhodium-catalyzed asymmetric arylative cyclization of meso-1,6-dienynes leading to enantioenriched cis-hydrobenzofurans

In tandem: The title reaction of cyclohexadienone-containing meso-1,6-dienynes with arylboronic acids through a tandem arylrhodation/ conjugate addition sequence has been realized, and provides a novel approach to the enantioenriched cis-hydrobenzofurans with both excellent yields and enantioselectivities. binap=2,2′-bis(diphenylphosphanyl)-1,1′- binaphthyl, Boc=tert-butoxycarbonyl. Copyright

Cu-catalyzed asymmetric borylative cyclization of cyclohexadienone- containing 1,6-enynes

The first Cu-catalyzed asymmetric borylative cyclization of cyclohexadienone-containing 1,6-enynes is achieved through a tandem process: selective β-borylation of propargylic ether and subsequent conjugate addition to cyclohexadienone. The reaction proceeds with excellent regioselectivity and enantioselectivity to afford an optically pure cis-hydrobenzofuran framework bearing alkenylboronate and enone substructures. Furthermore, the resulting bicyclic products could be converted to bridged and tricyclic ring structures. This method extends the realm of Cu-catalyzed asymmetric tandem reactions using bis(pinacolato)diboron (B2pin 2).

Ligand and substrate effects during Pd-catalyzed cyclizations of alkyne-tethered cyclohexadienones

The effects of ligand and substrate choice on the Pd-catalyzed cyclization of alkyne-tethered cyclohexadienones were examined. In the presence of a chiral ligand, the enantioselectivity of the desymmetrization is remarkably sensitive to structural changes in both the ligand and the substrate. Additionally, the regioselectivity of the reaction (5- vs. 6-membered ring formation) is dependent on the proximity of heteroatoms to the alkyne.

Bicyclic cyclohexenones as inhibitors of NF-κB signaling

A series of structurally simplified cryptocaryone analogues were synthesized by a facile Pd-catalyzed acetoxylation of alkyne-tethered cyclohexadienones and evaluated as inhibitors of NF-κB signaling. Compounds 10 and 11 were found to possess low micromolar inhibitory properties toward induced NF-κB activity by blocking p50/p65 nuclear protein through a covalent inhibition mechanism. Both compounds were able to inhibit NF-κB-induced IL-8 expression and exhibited antiproliferative activity against two model cancer cell lines. These analogues constitute a promising new scaffold for the development of novel NF-κB inhibitors and anticancer agents.