66334-32-5

Upstream product

• 130633-07-7 4-methyl-4-(4-methylphenyl)-hex-5-en-2-one 
• 144272-12-8 triisopropyl(prop-2-yn-1-yl)silane 
• 624-31-7 4-tolyl iodide 
• 122-00-9 para-methylacetophenone 
• 51431-59-5 2-(p-tolyl)but-3-en-2-ol 
• 1311260-43-1 (S)-1-(3,5-dimethylhexa-1,5-dien-3-yl)-4-methylbenzene 
• 1311260-04-4 tert-butyl (2-(p-tolyl)but-3-en-2-yl) carbonate 
• 795277-33-7 1-[(E)-(S)-3-Isopropenyloxy-3-((1R,2S,5R)-2-isopropyl-5-methyl-cyclohexyl)-1-methyl-propenyl]-4-methyl-benzene 
• 795278-37-4 Acetic acid (E)-(S)-1-((1R,2S,5R)-2-isopropyl-5-methyl-cyclohexyl)-3-p-tolyl-but-2-enyl ester 
• 795280-30-7 (E)-(S)-1-((1R,2S,5R)-2-Isopropyl-5-methyl-cyclohexyl)-3-p-tolyl-but-2-en-1-ol 
• 795277-39-3 (E)-(S)-6-((1S,2S,5R)-2-Isopropyl-5-methyl-cyclohexyl)-4-methyl-4-p-tolyl-hex-5-en-2-one 
• 133678-92-9 (2R)-2-methyl-2-(4-methylphenyl)pentane-1,4-diol 
• 887641-60-3 benzyl 2-(4-methylphenyl)-2-oxoacetate 
• 5524-56-1 ethyl 2-p-tolyl-2-oxoacetate 

Downstream Products

• 101693-57-6 (R)-(+)-4-methyl-4-(4-methylphenyl)cyclopent-2-enone 
• 123930-76-7 (S)-(-)-4-methyl-4-(4-methylphenyl)cyclopent-2-enone 
• 74567-38-7 4-methyl-4-(p-tolyl)-2-cyclopenten-1-one 

Relevant academic research and scientific papers

Synthesis of Cyclopentenones with C4-Quaternary Stereocenters via Stereospecific [3,3]-Sigmatropic Rearrangement and Applications in Total Synthesis of Sesquiterpenoids

A cationic gold(I)-catalyzed asymmetric [3,3]-sigmatropic rearrangement of sulfonium leads after cyclization to cyclopentenones with a C4-quaternary stereocenter. Starting with simple vinyl sulfoxides and propargyl silane, numerous compounds were isolated

Highly chemo-, enantio-, and regioselective synthesis of α,α-disubstituted furanones by Cu-catalyzed conjugate addition

A highly chemo-, enantio-, and regioselective synthesis of furanones bearing an α,α-disubstituted quaternary stereogenic center is reported. The Cu-catalyzed enantioselective conjugate addition of organoaluminum reagents to unsaturated ketoesters at room temperature and subsequent lactonization took place. Synthetic transformations of furanones represent facile approaches to various cyclic or acyclic compounds bearing a quaternary stereogenic center. Selective chemistry: A highly chemo-, enantio-, and regioselective synthesis of furanones bearing an α,α-disubstituted quaternary stereogenic center is reported (see scheme). Cu-catalyzed enantioselective conjugate addition of organoaluminum reagents to unsaturated ketoesters at room temperature and subsequent lactonization took place.

Enantioselective construction of all-carbon quaternary centers by branch-selective Pd-catalyzed allyl-allyl cross-coupling

The Pd-catalyzed cross-coupling of racemic tertiary allylic carbonates and allylboronates is described. This reaction generates all-carbon quaternary centers in a highly regioselective and enantioselective fashion. The outcome of these reactions is consistent with a process that proceeds by way of 3,3′-reductive elimination of bis(η1-allyl)palladium intermediates. Strategies for distinguishing the product alkenes and application to the synthesis of (+)-α-cuparenone are also described.

p-menthane-3-carboxaldehyde: A useful chiral auxiliary for the synthesis of chiral quaternary carbons of high enantiomeric purity

(+)- or (-)-p-Menthane-S-carboxaldehyde is made in two easy steps from (+)- or (-)-menthone, respectively. This auxiliary allows for the synthesis of carbonyl compounds bearing a α-chiral quaternary carbon. The flexibility, efficiency, and ease of use of

An expedient protocol for cyclopentenone annulation

A convenient and general protocol for the cyclopentenone annulation process is described.

An efficient synthesis of α-Cuparenone

Synthesis of α-Cuparenone is described. The key step involved are photorearrangement of α-halo arylketone (4) to 1-methyl-1-(p-tolyl)acetic acid (5) and extremely mild, essentially neutral, room temperature/3-aza-claisen reaction of N-allylamide (6).

Asymmetric Construction of Quaternary Carbons from Chiral Malonates: Selective and Versatile Total Syntheses of the Enantiomers of α- and β-Cuparenones from a Common Optically Active Precursor

From a single chiron (R)-4, available with high enantiomeric purity (96percent) by simple enzymatic hydrolysis (PLE) of a prochiral malonate, were prepared convenient precursors of the two enantiomers of α- and β-cuparenones (1a,b and 2a,b).This versatile

Geminal Acylation-Alkylation at a Carbonyl Carbon via Regiospecifically Generated Metalloenamines

A useful procedure for effecting geminal disubstitution at the carbonyl carbon atom of aldehydes and ketones has been developed in which the sequence of reactions results in the replacement of the two carbon-oxygen bonds of the carbonyl function with an acyl group and an alkyl or hydroxyalkyl group.Of particular importance is the facile application of these procedures to the efficient construction of quaternary carbon atoms that bear alkyl appendages containing differentiated functionality.This novel methodology features the initial conversion of carbonyl compounds 1 into the substituted 2-azadienes 10 or 11 by Wittig-Horner reaction.Subsequent reaction of these 2-azadienes produced in situ with n-butyllithium results in the formation of the metalloenamines 12 and 13 (R4 = n-Bu) which undergo reactions with a wide variety of electrophiles to give, after hydrolysis of the intermediate imines, the α-substituted aldehydes 14 or the α-substituted ketones 15 in good of excellent overall yields.New procedures for the annelation of cyclopentenones such as 22 and cyclohexenones 26 at the carbonyl carbon of ketones are described as is an important variant of a directed aldol reaction, 1 --> 28.Although a number of individual manipulations are necessary to effect the geminal disubstitution of a carbonyl functional group, it is generally feasible to execute the entire sequence of reactions in single flask, thereby rendering this methodology very convenient to implement in practice.