1375111-56-0

Upstream product

• 591-50-4 iodobenzene 
• 1184937-21-0 4-(but-2-yn-1-yloxy)-4-methylcyclohexa-2,5-dien-1-one 
• 106-44-5 p-cresol 
• 1375111-55-9 4-methyl-4-(prop-2-yn-1-yloxy)cyclohexa-2,5-dienone 
• 1504-58-1 3-Phenyl-2-propyn-1-ol 

Relevant academic research and scientific papers

Lewis Acid-Driven Meyer-Schuster-Type Rearrangement of Yne-Dienone

Developed herein is a Cu(II)-catalyzed Meyer-Schuster-type rearrangement of alkyne-tethered cyclohexadienone for the construction of m-enone-substituted phenols. The reaction involves an uncommon 5-exo-trig 1,6-enyne cyclization of alkyne-tethered-cyclohexadienone, aromatization-triggered C-O bond cleavage, and an electrocyclic 4π-ring-opening of oxetene intermediate. This atom-efficient transformation provides access to a wide range of synthetically important α-(m-substituted phenol)-α,β-unsaturated ketones, featuring a broad scope with labile functional group tolerance. The gram-scale demonstration makes this transformation synthetically viable. The synthetic application of α,β-unsaturated ketones is also showcased.

Silver(I)-Catalyzed Enyne Cyclization/Aromatization of Alkyne-Tethered Cyclohexadienones to Access Meta-Substituted Phenols

Herein we report a highly regioselective silver(I)-catalyzed intramolecular annulation of alkyne-tethered cyclohexadienones to access meta-substituted phenols with enone functionality, which are difficult to synthesize from conventional methods. The reaction proceeds via intramolecular 1,6-enyne cyclization followed by aromatization and subsequent oxetene ring rearrangement. This strategy has also been compatible with a wide range of C-tethered cyclohexadienones to afford indanes in high yields. The unique functionality of products allows further transformations to expand the diversity.

Catalytic, Regioselective Hydrocarbofunctionalization of Unactivated Alkenes Triggered by trans-Acetoxypalladation of Alkynes

Herein we demonstrate a Pd(II)-catalyzed regioselective hydrocarbofunctionalization of unactivated alkenes. The σ-vinyl-palladium(II) intermediate generated by the trans-acetoxypalladation of alkynes was added across carbon-carbon double bond to realize an efficient hydroalkenylation protocol. Bidentate auxiliary 8-aminoquinoline controls the regioselectivity of the carbopalladation step and thereby controls the regioselectivity of the hydroalkenylation. Additionally, when alkynes containing a hydroxy group at the three- or four-position were employed, the cascade sequence led to 1,6-dicarbonyl compounds via hydroalkenylation followed by intramolecular acyl migration.

Mn-catalyzed radical initiated domino transformation of alkynylated cyclohexadienones with TMSN3 and O2 to bicyclic azido alcohols

An efficient Mn-catalyzed cascade azide radical addition/cyclization/oxygen insertion reaction of alkyne-tethered cyclohexadienones with TMSN3 under mild conditions is reported. This domino reaction presents good diastereoselectivity generating bicyclic azido alcohol scaffolds which can be transformed into useful building blocks in organic synthesis for medicinal chemistry.

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

Palladium-catalyzed highly diastereoselective cascade dihalogenation of alkyne-Tethered cyclohexadienones: Via Umpolung of palladium enolate

Herein, we report a highly diastereo-and regioselective dihalogenation of alkyne-Tethered cyclohexadienones for the synthesis of cis-hydrobenzofurans. One carbon-carbon and two carbon-halogen bonds were formed in an efficient manner and three contiguous s

Metal-free visible-light induced cyclization/substitution cascade reaction of alkyne-tethered cyclohexadienones and diselenides: Access to 5-hydroxy-3-selenyl-4a,8a-dihydro-2: H -chromen-6(5 H)-ones

A simple and efficient Se-radical triggered cyclization/substitution cascade reaction of alkyne-tethered cyclohexadienones to afford 5-hydroxy-3-selenyl-4a,8a-dihydro-2H-chromen-6(5H)-ones has been developed. This transformation via the 3,5-diselenyl-4a,8a-dihydro-2H-chromen-6(5H)-one intermediate followed by hydrolysis in the presence of CsOAc affords the desired product 3. The resulting products were tested for their in vitro anticancer activity using MTT assay, and compounds 3e and 3q showed potent cancer cell-growth inhibition activities.

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.

Sulfonylative and Azidosulfonylative Cyclizations by Visible-Light-Photosensitization of Sulfonyl Azides in THF

The generation of sulfonyl radicals from sulfonyl azides using visible light and a photoactive iridium complex in THF is described. This process was used to promote sulfonylative and azidosulfonylative cyclizations of enynes to give several classes of highly functionalized heterocycles. The use of THF as the solvent is critical for successful reactions. The proposed mechanism of radical initiation involves the photosensitized formation of a triplet sulfonyl nitrene, which abstracts a hydrogen atom from THF to give a tetrahydrofuran-2-yl radical, which then reacts with the sulfonyl azide to generate the sulfonyl radical.

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.