17553-86-5

Usage

Uses

Used in Pharmaceutical Industry:
(S)-(+)-2,3,7,7A-TETRAHYDRO-7A-METHYL-1H is used as an intermediate for the preparation of Indenedione, which is a significant compound in the pharmaceutical industry.
Used in Total Synthesis:
In the field of organic chemistry, (S)-(+)-Hajos-Parrish diketone is used as a reactant in the total synthesis of steroidal alkaloids, such as cortistatins. This application is crucial for the development of novel bioactive compounds with potential pharmaceutical applications.
Used in Stereoselective Preparation:
(S)-(+)-2,3,7,7A-TETRAHYDRO-7A-METHYL-1H is employed in the stereoselective preparation of hydroanthracenol and related polycyclic compounds. This is achieved through Ti(Oi-Pr)4-promoted photoenolization and Diels-Alder reaction, which are essential techniques in organic synthesis for creating complex molecular structures with specific stereochemistry.
Used in Synthesis of Allyldiboron Compounds:
In the field of organometallic chemistry, (S)-(+)-2,3,7,7A-TETRAHYDRO-7A-METHYL-1H is used in the synthesis of γ,γ-disubstituted allyldiboron compounds. This is accomplished by reacting with allylic 1,1-diboronate reagents via Cu-catalyzed borylation and 1,2-addition reaction, which are important for the development of new materials and pharmaceuticals with unique properties.

InChI:InChI=1/C10H12O2/c1-10-5-4-8(11)6-7(10)2-3-9(10)12/h6H,2-5H2,1H3/t10-/m0/s1

Upstream product

• 16271-49-1 (1S,7aS)-1-hydroxy-7a-methyl-2,3,7,7a-tetrahydro-1H-inden-5(6H)-one 
• 765-69-5 2-Methylcyclopentane-1,3-dione 
• 78-94-4 methyl vinyl ketone 
• 35544-95-7 (3aR,7aR)-3a-hydroxy-7a-methylperhydroindene-1,5-dione 
• 33879-04-8 (+)-(3aS,7aS)-2,3,3a,4,7,7a-hexahydro-3a-hydroxy-7a-methyl-1H-indene-1,5(6H)-dione 
• 25112-78-1 2-methyl-2-(3-oxobutyl)-1,3-cyclopentanedione 
• 1120-72-5 2-Methylcyclopentanone 
• 19576-08-0 (+/-)-7a-methyl-2,3,7,7a,tetrahydro-1H-indene-1,5(6H)-dione 
• 147-85-3 L-proline 
• 17553-88-7 (1R,7aR)-3,6,7,7a-tetrahydro-1-hydroxy-7a-methyl-1H-inden-5(2H)-one 
• 4326-84-5 2-Methyl-2-(3-oxobutyl)cyclopentanone 
• 344-25-2 D-Prolin 
• 16271-49-1 1β-hydroxy-7aβ-methyl-2,3,7,7a-tetrahydro-1H-inden-5(6H)-one 
• 16271-45-7 rac.-7,7a-Dihydro-1β-hydroxy-7aβ-methyl-5(6H)-indanon-hydrogenphthalat 

Downstream Products

• 113726-22-0 7ξ-Hydroxy-3-methoxy-9,10-secoestra-1,3,5(10)-triene-9,17-dione 
• 61530-86-7 (3aS,4S,7aS)-2,3,3a,6,7,7a-Hexahydro-7a-methyl-4-<(phenylsulfonyl)methyl>-1H-inden-1,5(4H)-dion 
• 61530-85-6 (7aS)-2,3,7,7a-Tetrahydro-7a-methyl-4-<(phenylsulfonyl)methyl>-1H-inden-1,5(6H)-dion 
• 493021-13-9 (2Z,4E)-(R)-6-Acetoxy-7-[(1R,2S)-2-(tert-butyl-diphenyl-silanyloxymethyl)-1-methyl-5-oxo-cyclopentyl]-3-ethoxy-hepta-2,4-dienoic acid allyl ester 
• 144299-24-1 (1S,7aS)-1-(tosyloxy)-7a-methyl-7,7a-dihydro-5(6H)-indanone 
• 493021-04-8 (1S,7aR)-1-(tert-Butyl-diphenyl-silanyloxymethyl)-7a-methyl-1,2,3,6,7,7a-hexahydro-inden-5-one 
• 493021-11-7 Acetic acid (R)-2-[(1R,2S)-2-(tert-butyl-diphenyl-silanyloxymethyl)-1-methyl-5-oxo-cyclopentyl]-1-formyl-ethyl ester 
• 493021-05-9 acetic acid 3-(tert-butyl-diphenyl-silanyloxymethyl)-3a-methyl-6-oxo-2,3,3a,4,5,6-hexahydro-1H-inden-5-yl ester 
• 493021-10-6 (R)-2-Acetoxy-3-[(1R,2S)-2-(tert-butyl-diphenyl-silanyloxymethyl)-1-methyl-5-oxo-cyclopentyl]-propionic acid 
• 493021-06-0 Acetic acid (R)-2-[(1R,2S)-2-(tert-butyl-diphenyl-silanyloxymethyl)-1-methyl-5-oxo-cyclopentyl]-1-ethylsulfanylcarbonyl-ethyl ester 
• 493021-03-7 (E)-(R)-6-Acetoxy-7-[(1R,2S)-2-(tert-butyl-diphenyl-silanyloxymethyl)-1-methyl-5-oxo-cyclopentyl]-3-oxo-hept-4-enoic acid allyl ester 
• 493021-14-0 (1S,4aS,5S,8aS)-5-{(R)-1-Acetoxy-2-[(1R,2S)-2-(tert-butyl-diphenyl-silanyloxymethyl)-1-methyl-5-oxo-cyclopentyl]-ethyl}-1-(tert-butyl-diphenyl-silanyloxy)-4,7-dioxo-octahydro-naphthalene-4a-carboxylic acid methyl ester 
• 493021-08-2 (4S,5S,8R,9S,10R,11R,13R,14S,17S)-11-Acetoxy-4-(tert-butyl-diphenyl-silanyloxy)-17-(tert-butyl-diphenyl-silanyloxymethyl)-14-hydroxy-13-methyl-1,7-dioxo-hexadecahydro-cyclopenta[a]phenanthrene-10-carboxylic acid methyl ester 
• 493021-07-1 (4S,4aS,8S,8aS)-4-{(R)-1-Acetoxy-2-[(1R,2S)-2-(tert-butyl-diphenyl-silanyloxymethyl)-1-methyl-5-oxo-cyclopentyl]-ethyl}-8-(tert-butyl-diphenyl-silanyloxy)-2,5-dioxo-octahydro-naphthalene-1,4a-dicarboxylic acid 1-allyl ester 4a-methyl ester 

Relevant academic research and scientific papers

One carbon elongation of the Hajos-Parrish ketone. Synthesis of (+)-(3aS,7aR)-octahydro-3a-hydroxy-7a-methyl-1-methylene-5H-indene-5-o ne

The difficulties encountered for the C-1 methylenation of Hajos-Parrish (1) and Hajos-Wiechert (2) ketones, were overcome by the use of Conia reaction on their C-5 dithiane derivatives.

β-Homoamino acids as catalysts in enantioselective intra- and intermolecular aldol reactions

β3-Homoamino acids catalyze the intra- (cf. the Hajos-Parrish-Eder-Sauer-Wiechert reaction) as well as the intermolecular aldol reaction. The stereochemical outcome with selectivities of up to 83% ee is reversed in the intramolecular reaction,

Synthesis of ent-Cholesterol, the Unnatural Enantiomer

Cholesterol is ubiquitious in mammals and plays an important role in human health.The unique relationship between enantiomers make ent-cholesterol, the unnatural enantiomer of cholesterol, a valuable new probe of cholesterol function in biochemical systems.We report the first enantioselective total synthesis of ent-cholesterol.

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.

Inotropic activity of hydroindene amidinohydrazones

Several hydroindenic derivatives (7a-methyl-2,3,5,6,7,7a-hexahydro-1H-indenes), bearing an amidinohydrazone at C-5 and different moieties at C-1, have been synthesized and evaluated for their inotropic and chronotropic effects on right- and left-guinea-pig-atria activity. Three of them showed the same profile as digoxin, although with lower potency. The effect on Na+,K+ ATPase (NKA) was also evaluated for these three compounds, observing that two of them, with the same absolute configuration as natural cardenolides, are also NKA inhibitors, while the compound with the opposite configuration lacks such an effect. More interestingly, both active compounds act without affecting the cardiac rhythm. This could be related to the selective inhibition of the human α2β1 isozyme (associated with the inotropic effect) with respect to the α1β1 isozyme (associated with the maintenance of basal ionic levels in the cell and the toxic effect of cardenolides).

Synthesis of Optically Active trans-Cyclononenes. A Possible Approach to Xenicanes

Two optically active substituted trans-cyclononenes (13a, 13b) were synthesized from the (-)-Hajos-Parrish diketone.This procedure provides a possible approach for the total synthesis of xenicanes, biologically active compounds isolated from marine organi

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.

Desymmetrisation of: Meso -diones promoted by a highly recyclable polymer-supported chiral phosphoric acid catalyst

A polystyrene-supported BINOL-derived chiral phosphoric acid has been applied to the desymmetrisation of meso-diones to produce enantioenriched cyclohexenones. The catalytic resin has proven highly active and robust, giving rise to Hajos-Parrish or Wieland-Miescher type products in good yields and enantioselectivities, while allowing for extended recycling.

A Highly Active Polymer-Supported Catalyst for Asymmetric Robinson Annulations in Continuous Flow

The preparation through Robinson annulation of enantiopure building blocks with both academic and industrial relevance, such as the Wieland-Miescher and Hajos-Parrish ketones, has suffered from important drawbacks, such as the need for high catalyst loading or extremely long reaction times. Here we report a heterogenized organocatalyst based on Luo's diamine for fast and broad-scope enantioselective Robinson annulation reactions. The polystyrene-supported diamine 19a enables the high-yield, highly enantioselective preparation of a wide range of chiral bicyclic enones under mild conditions, with reaction times as short as 60 min (batch) or residence times of 10 min (flow). In contrast with its homogeneous counterpart 19b, the catalytic resin 19a experiences a notable increase in catalytic activity with temperature in 2-MeTHF (a 10-fold decrease in reaction times without erosion in enantioselectivity is observed from room temperature to 55 °C). The scope of the transformation in batch mode has been illustrated with 14 examples, including examples only reported in poorly enantioenriched (22n) or in racemic form (22k). Enantiopure 22k has been used as the starting material for a straightforward formal synthesis of the antibiotic and antifeedant sesquiterpene (-)-isovelleral (24). The heterogenized catalyst 19a admits extended recycling (10 cycles) and has been used to develop the first asymmetric Robinson annulations in continuous flow. The potential of the flow process is illustrated by the large-scale preparation of the Wieland-Miescher ketone (65 mmol in 24 h of operation, TON of 117) and by a sequential flow experiment leading to a library of eight enantioenriched diketone compounds.

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.