25112-78-1

Upstream product

• 765-69-5 2-Methylcyclopentane-1,3-dione 
• 78-94-4 methyl vinyl ketone 
• 60263-66-3 1-Phenylsulfinyl-3-buten-2-on 
• 5870-63-3 3-hydroxy-2-methyl-2-cyclopenten-1-one 
• 27132-81-6 2,4-dimethyl-penta-1,4-dien-3-one 

Downstream Products

• 17553-86-5 (S)-Halos-Parish ketone 
• 17553-86-5 (R)-7a-methyl-2,3,7,7a-tetrahydro-6H-indene-1,5-dione 
• 35544-95-7 (3aR,7aR)-3a-hydroxy-7a-methylperhydroindene-1,5-dione 
• 55790-72-2 3a-Hydroxy-7a-methyloctahydroindene-1,5-dione 
• 134005-25-7 1,3-bis(p-toluenesulfonyloxy)-2-(3,3-ethylenedioxybutyl)-2-methylcyclopentane 
• 33879-04-8 (+)-(3aS,7aS)-2,3,3a,4,7,7a-hexahydro-3a-hydroxy-7a-methyl-1H-indene-1,5(6H)-dione 
• 1173169-86-2 C₂₃H₂₄F₆N₂O₃ 
• 51065-67-9 C₁₀H₁₄O₃ 
• 42199-10-0 (3aR,5S,7aS)-5-(4-hydroxyphenyl)-7a-methyloctahydro-1H-inden-1-one 
• 55790-69-7 4β-hydroxy-1β,4α-dimethylbicyclo[3.2.1]octane-7,8-dione 
• 26831-64-1 (+/-)-2endo-hydroxy-2exo,5-dimethyl-bicyclo[3.2.1]octane-6,8-dione 
• 19576-08-0 (+/-)-7a-methyl-2,3,7,7a,tetrahydro-1H-indene-1,5(6H)-dione 
• 61530-85-6 (7aS)-2,3,7,7a-Tetrahydro-7a-methyl-4-<(phenylsulfonyl)methyl>-1H-inden-1,5(6H)-dion 
• 61530-86-7 (3aS,4S,7aS)-2,3,3a,6,7,7a-Hexahydro-7a-methyl-4-<(phenylsulfonyl)methyl>-1H-inden-1,5(4H)-dion 

Relevant academic research and scientific papers

Organic Reactions at High Pressure. A Robinson Annulation Sequence Initiated by Michael Addition of Activated Cycloalkanones with Hindered Enones

Activated cycloalkanones (ring size = five, six, seven) undergo Michael addition to β,β-disubstituted enones and subsequent aldol cyclization at 15 kbar (1.5 GPa) pressure in acetonitrile containing triethylamine or 1,5-diazabicyclonon-5-ene to aff

Construction of key building blocks towards the synthesis of cortistatins

This work reports the construction of key building blocks towards the synthesis of cortistatins; a family of steroidal alkaloids. Cortistatin A, being a primary target due to its superior biological properties over other congeners, has been prepared by two different synthetic routes. Synthesis of the precursor to the heavily substituted A-ring starting from d-glucose and construction of the DE-ring junction employing a Hajos-Parrish ketone as a chiral pool have been demonstrated. Efforts are underway to assemble these key fragments and build towards the total synthesis of cortistatin A.

Lipase-catalyzed domino Michael-aldol reaction of 2-methyl-1,3-cycloalkanedione and methyl vinyl ketone for the synthesis of bicyclic compounds

Synthesis of bicyclic compounds was achieved via a lipase-catalyzed, stereoselective, domino Michael-aldol reaction of 2-methyl-1,3-cycloalkanedione and methyl vinyl ketone. Appropriate reaction conditions, including the type of enzyme, solvent, and temperature, were determined. In addition, the effects of solvent polarity and addtives were investigated. The reaction proceeded in the presence of lipase AS in a solution of 20% acetone in dimethylsulfoxide (DMSO) at 10 °C for 8 days, followed by the addition of p-toluenesulfonic acid (TsOH) to afford bicyclic compounds in 51-83% yields with moderate stereoselectivity. Although this domino Michael-aldol reaction showed only moderate stereoselectivity, even with the acid-supported enhancement of the reaction, these results represent potential new applications for lipase.

Evolution of a Unified Strategy for Complex Sesterterpenoids: Progress toward Astellatol and the Total Synthesis of (-)-Nitidasin

Astellatol and nitidasin belong to a subset of sesterterpenoids that share a sterically encumbered trans-hydrindane motif with an isopropyl substituent. In addition, these natural products feature intriguing polycyclic ring systems, posing significant challenges for chemical synthesis. Herein, the evolution of our stereoselective strategy for isopropyl trans-hydrindane sesterterpenoids is detailed. These endeavors included the synthesis of several building blocks, enabling studies toward all molecules of this terpenoid subclass, and of advanced intermediates of our initial route toward a biomimetic synthesis of astellatol. These findings provided the basis for a second-generation and a third-generation approach toward astellatol that eventually culminated in the enantioselective total synthesis of (-)-nitidasin. In particular, a series of substrate-controlled transformations to install the ten stereogenic centers of the target molecule was orchestrated and the carbocyclic backbone was forged in a convergent fashion. Furthermore, the progress toward the synthesis of astellatol is disclosed and insights into some observed yet unexpected diastereoselectivities by detailed quantum-mechanical calculations are provided. Two and a half molecules: Astellatol and nitidasin are polycyclic sesterterpenoids, posing considerable challenges for synthetic chemists. In this full account, the evolution of a synthetic strategy for these and structurally related natural products is given (see scheme). The presented work includes efforts toward a biomimetic synthesis of astellatol, a successful route for the first total synthesis of (-)-nitidasin, and quantum-mechanical investigations into unexpected diastereosectivities.

Protecting-group-free total synthesis of aplykurodinone-1

A concise, stereoselective, and protecting-group-free total synthesis of aplykurodinone-1 from Hajos-Parrish ketone was described. The synthetic approach features a sequence of aerobic allylic oxidation and elimination of alcohol 9. The key intermediate for this synthesis was formed by a stereoselective intramolecular radical cyclization.

Novel supported and unsupported prolinamides as organocatalysts for enantioselective cyclization of triketones

A novel prolylsulfonamide derived from ethylene diamine and its supported counterpart has been prepared and tested as enantioselective intramolecular aldol reaction of cyclic and acyclic triketones. Good to excellent yields and enantioselectivities have been obtained in water and under solvent free conditions.

The A-CD analogue of 16β,17α-estriol is a potent and highly selective estrogen receptor β agonist

Selective estrogen receptor β (ERβ) agonists display neuroprotective properties in animal models and hold promise in the treatment of neurodegenerative diseases. In our quest to design, synthesize and evaluate potent and safe ERβ agonists, we focused on m

Asymmetric synthesis of Wieland-Miescher and Hajos-Parrish ketones catalyzed by an amino-acid-derived chiral primary amine

This paper describes a simple chiral primary amine-catalyzed highly efficient and practical protocol for the synthesis of both Wieland-Miescher ketone and Hajos-Parrish ketone as well as their analogues. The reaction can be conducted in gram scale with 1%

STEROID ANALOGUES FOR NEUROPROTECTION

Provided are steroid analogues functionalized with polar substituents at the C3 and/or C20 positions of the steroid ring system that exhibit improved water solubility. Also provided are pharmaceutical compositions comprising the steroid analogues and methods using the novel steroid analogues for the treatment and prevention of neurodegeneration in a patient following injury to the central nervous system.

Combining multi-catalysis and multi-component systems for the development of one-pot asymmetric reactions: Stereoselective synthesis of highly functionalized bicyclo[4.4.0]decane-1,6-diones

We have developed a direct amine/acid-catalyzed stereoselective hydrogenation of a variety of Wieland-Miescher (W-M) ketones, Hajos-Parrish (H-P) ketones and their analogs with organic hydrides (Hantzsch esters) as the hydrogen source. This astonishingly simple and biomimetic approach was used to construct highly functionalized chiral bicyclo[4.4.0]decane-1,6-diones 6 in a diastereoselective fashion. This is an example of the development of a new technology by the combination of multiple catalysts and components in one pot to deliver highly functionalized chiral molecules. The Royal Society of Chemistry 2008.