150765-78-9

Upstream product

• 37595-74-7 N,N-phenylbistrifluoromethane-sulfonimide 
• 1193-55-1 2-methylcyclohexane-1,3-dione 
• 358-23-6 trifluoromethylsulfonic anhydride 
• 32774-63-3 3-hydroxy-2-methyl-cyclohex-2-enone 
• 456-64-4 phenyl trifluoromethanesulfonamide 

Downstream Products

• 124267-38-5 2-methyl-3-propenyl-2-cyclohexenone 

Relevant academic research and scientific papers

Enantioselective Synthesis of γ-Functionalized Cyclopentenones and δ-Functionalized Cycloheptenones Utilizing a Redox-Relay Heck Strategy

In this report, the desymmetrization of cyclic enones under relay Heck conditions with an array of aryl boronic acids, alkenyl triflates and indole derivatives is described. This method grants facile access to diverse γ-functionalized cyclopentenones and δ-functionalized cycloheptenones. Using this approach, a formal synthesis of (S)-baclofen was completed in high yield and excellent enantioselectivity. (Figure presented.).

Studies Targeting Ryanodol Result in an Annulation Reaction for the Synthesis of a Variety of Fused Carbocycles

An annulation reaction is described to access a range of polycyclic and highly oxygenated carbocycles. First developed in an approach to the synthesis of ryanodol, metallacycle-mediated annulative diketone-alkyne coupling defines a framework for realization of new retrosynthetic relationships for complex molecule synthesis. In addition to demonstrating this reaction in the context of forging distinct carbocyclic systems, including those featuring a seven-membered ring, the choice of quenching reagent leads to unique reaction outcomes.

Stereodivergent Photoelectrocyclization Reactions of Bis-aryl Cycloalkenones: Intercepting Photoelectrocyclization Intermediates with Acid

Described here are tandem photoelectrocyclization and [1,5]-hydride shift reactions of heteroaryl-containing bis-aryl cyclohexenone derivatives that give heteroaryl-substituted dihydrophenanthrenes. This Letter demonstrates that electrocyclization intermediates can be trapped with acid when the [1,5]-hydride shift is relatively slow. From a practical perspective, the observation that the acid-mediated reaction gives a divergent stereochemical outcome when compared with the reaction run under neutral conditions makes these transformations powerful.

Vinylogous acyl triflates as an entry point to α,β-disubstituted cyclic enones via Suzuki-Miyaura cross-coupling

An alternative protocol for the B-alkyl Suzuki-Miyaura reaction to produce cyclic α,β-disubstituted enones is reported. The use of β-triflyl enones as coupling partners in lieu of their halogenated analogs provides enhanced substrate stability to light and chromatography without adversely affecting reactivity. This protocol allows efficient access to the synthetically challenging α,β-disubstituted enone motif under mild conditions.

Enantioselective Conia-Ene-Type Cyclizations of Alkynyl Ketones through Cooperative Action of B(C6F5)3, N-Alkylamine and a Zn-Based Catalyst

An efficient and highly enantioselective Conia-ene-type process has been developed. Reactions are catalyzed by a combination of B(C6F5)3, an N-alkylamine and a BOX-ZnI2 complex. Specifically, through cooperative

Multimetallic Ni- and Pd-Catalyzed Cross-Electrophile Coupling to Form Highly Substituted 1,3-Dienes

The synthesis of highly substituted 1,3-dienes from the coupling of vinyl bromides with vinyl triflates is reported for the first time. The coupling is catalyzed by a combination of (5,5′-bis(trifluoromethyl)-2,2′-bipyridine)NiBr2 and (1,3-bis(diphenylphosphino)propane)PdCl2 in the presence of a zinc reductant. This method affords tetra- and penta-substituted 1,3-dienes that would otherwise be difficult to access and tolerates electron-rich and -poor substituents, heterocycles, an aryl bromide, and a pinacol boronate ester. Mechanistically, the reaction appears to proceed by an unusual zinc-mediated transfer of a vinyl group between the nickel and palladium centers.

Control of the Chemoselectivity of Metal N-Aryl Nitrene Reactivity: C-H Bond Amination versus Electrocyclization

A mechanism study to identify the elements that control the chemoselectivity of metal-catalyzed N-atom transfer reactions of styryl azides is presented. Our studies show that the proclivity of the metal N-aryl nitrene to participate in sp3-C-H bond amination or electrocyclization reactions can be controlled by either the substrate or the catalyst. Electrocyclization is favored for mono-β-substituted and sterically noncongested styryl azides, whereas sp3-C-H bond amination through an H-atom abstraction-radical recombination mechanism is preferred when a tertiary allylic reaction center is present. Even when a weakened allylic C-H bond is present, our data suggest that the indole is still formed through an electrocyclization instead of a common allyl radical intermediate. The site selectivity of metal N-aryl nitrenes was found to be controlled by the choice of catalyst: Ir(I)-alkene complexes trigger electrocyclization processes while Fe(III) porphyrin complexes catalyze sp3-C-H bond amination in substrates where Rh2(II) carboxylate catalysts provide both products.

Formal synthesis of palmerolide A, featuring alkynogenic fragmentation and syn-selective vinylogous aldol chemistry

An enantioselective route to palmerolide A is described. The approach features original syntheses of three subunits, which are then assembled to produce a known late-stage intermediate and formally provide the highest overall yield of the natural product

Synthesis of high-value 1,6-enynes by tandem fragmentation/olefination

A tandem process provides high-value 1,6-enynes that are otherwise difficult to prepare. Two base-mediated reactions - fragmentation and olefination - are executed in a coordinated manner that is overall more efficient than either reaction on its own. The