25163-50-2

Upstream product

• 1071-73-4 5-Hydroxy-2-pentanone 
• 1575-67-3 2-(2-methyl-allyl)-malonic acid diethyl ester 
• 45081-67-2 2-(2-Methyl-allyl)-malonic acid monoethyl ester 
• 58715-25-6 1-acetoxy-4-methyl-4-pentene 
• 5185-97-7 4-oxopentyl acetate 
• 539-88-8 4-oxopentanoic acid ethyl ester 
• 4911-54-0 ethyl 4-methyl-4-pentenoate 

Downstream Products

• 154221-76-8 2-methyl-5-(phenylthio)pent-1-ene 
• 142077-87-0 2,7-dimethyl-4-(phenylthio)octa-1,7-diene 
• 154221-77-9 (1-Chloro-4-methyl-pent-4-enylsulfanyl)-benzene 
• 6709-39-3 2,6-dimethyl-hepta-1,5-diene 
• 10408-15-8 6-methylhept-6-en-2-one 
• 157367-96-9 4-methyl-N-(4-methylpent-4-en-1-yl)benzenesulfonamide 
• 1380332-36-4 C₁₅H₂₂O₂ 
• 1380332-33-1 C₁₅H₂₂O₃ 
• 1380332-32-0 C₁₅H₂₂O₃ 
• 1380332-22-8 C₁₄H₂₀O₂ 
• 1380332-26-2 C₁₃H₁₆O₂ 
• 1380332-24-0 C₁₄H₁₈O 
• 1380332-23-9 C₁₄H₁₈O 
• 1380332-48-8 C₁₅H₂₂O₄ 

Relevant academic research and scientific papers

Total synthesis of the terpenoid buddledone A: 11-membered ring-closing metathesis

The first total synthesis of buddledone A was accomplished in seven steps from methyl ethyl ketone (MEK). The key step in the sequence featured an 11-membered ring formation by ring-closing metathesis.

Intramolecular condensation via an o-quinone methide: Total synthesis of (±)-heliol

An acid-catalyzed intramolecular [4 + 2] cycloaddition of a non-natural bisabolene is reported. The key cyclocondensation was developed to access cyclic sesquiterpenes from linear phenolic precursors by generating a reactive o-quinone methide intermediate to initiate a cascade reaction. The new method was applied to the first total synthesis of (±)-heliol.

INHIBITION OF PPAR GAMMA EXPRESSION IN PREADIPOCYTE CELLS BY OXYSTEROLS

This invention relates, e.g., to methods and agents to inhibit peroxisome proliferator activated receptor expression (PPAR) in preadipocytes.

Ring reversal of a spirocyclic patchouli odorant: Molecular modeling, synthesis, and odor of 6-hydroxy-1,1,6-trimethylspiro[4.5]decan-7-one

Molecular modeling calculations on the recently discovered high-impact patchouli odorant (+)-(1S,4R,5R,9S)-1-hydroxy-1,4,7,7,9-pentamethylspiro[4.5] decan-2-one (1) indicated that ring reversal of the spirocyclic system should lead to molecules in which two of the five methyl substituents could be spared without significantly affecting the overall shape or conformational equilibrium. Intramolecular ene reactions promised simple access to the desired target compound, (5R*,6R*)-6-hydroxy-1,1,6-trimethylspiro[4.5]decan-7-one (2), but all attempts failed utterly. The elaborated alternative six-step synthesis of target structure 2 commenced with the addition of HCl gas to 5-bromo-2-methyl-2-pentene (16), giving 1-bromo-4-chloro-4-methylpentane (15). Spiroannulation of cyclohexanone with this building block by TiCl 4-mediated alkylation of the TMS enolate 14 and subsequent cyclization by means of tBuOK afforded 1,1-dimethylspiro[4.5]decan-6-one (12). The reaction of this spirocyclic ketone with MeLi furnished the corresponding tertiary alcohol 17, which was dehydrated by Appel-Lee bromination with concomitant dehydrohalogenation. The resulting alkene mixture containing 1,1,6-trimethylspiro[4.5]dec-6-ene (4) as the major component was subjected to the ketohydroxylation method developed by Plietker to provide, after repeated chromatography, target compound 2 in 33 % yield. To study the influence of the gem-dimethyl position on the olfactory properties, the analogous spirocyclic 2,2,6-trimethylketone 22 was also synthesized. Spiroannulation of cyclohexanone with 1,4-dibromo-2,2-dimethylbutane (18), with the use of 2.2 equiv. tBuOK as base, furnished 2,2-dimethylspiro[4.5]decan-6-one (19). The reaction of 19 with MeLi and subsequent Appel-Lee bromination/dehydrohalogenation led to an isomeric mixture containing 2,2,6-trimethylspiro[4.5]dec-6-ene (21) as the main component. The ketohydroxylation method according to the protocol of Plietker concluded the synthesis of the second target structure 22. In contrast to methyl carbinol 17, which has a typical woody-earthy patchouli odor, the odor of target molecule 2 was displaced towards the camphoraceous and minty side. The 2,2,6-trirnethylalcohol 20 emanated a camphoraceous and vetiver-type note, while the second target molecule, 22, was only weakly woody, cedar-like, and powdery in smell. Wiley-VCH Verlag GmbH & Co. KGaA, 2007.

Total syntheses of epothilones B and D

A convergent, total synthesis of epothilones B (2) and D (4) is described. The key steps are Normant coupling to establish the desired (Z)-stereochemistry at C12-C13, Wadsworth-Emmons olefination of methyl ketone 28 with the phosphonate ester 8, diastereoselective aldol condensation of aldehyde 5 with the enolate of keto acid derivatives to form the C6-C7 bond, selective deprotection of acid 52, and macrolactonization.

Synthesis and biological activity of isopentenyl diphosphate analogues

A series of analogues of isopentenyl diphosphate (IPP) having a dicarboxylate moiety in place of the diphosphate were synthesized and investigated as inhibitors of undecaprenyl diphosphate (UPP) synthase and protein farnesyltransferase (PFTase). PFTase is involved in control of cell proliferation and is known to be inhibited by certain maleic acid derivatives bearing long alkyl substituents (≥12 carbons, e.g., chaetomellic acid). UPP synthase is a potential target for antimicrobial agents and utilizes isopentenyl diphosphate (IPP) as a substrate. A number of dicarboxylate- containing IPP analogues were prepared in 2-5 steps from commercially available starting materials with good overall yield (20-78%). These syntheses involved the conjugate addition of an organocuprate to dimethyl acetylenedicarboxylate (DMAD) followed by basic ester hydrolysis. The E-pentenylbutanedioic acid 32 showed inhibition of UPP synthase with an IC50 of 135 μM. Compound 30 displays competitive inhibition of PFTase with a Ki of 287 μM.

Total synthesis of (±)-dysidiolide

The total synthesis of (±)-dysidiolide was accomplished with a high level of intramolecular stereo-induction. Methylation of 6-carboethoxy-3-chloro-5-methyl-cyclohex-2-enone provided 33 bearing the 6,7-trans-dimethyl substitution of the C6-C11 B-ring. Diastereoselective conjugate addition upon enone 34 installed the C11 stereogenic center. Annulation then provided an A-ring enone (23), a substrate for a challenging conjugate addition of the branched pentenyl side chain. The combination of tri-n-butylphosphine, boron trifluoride etherate, and a dialkylcuprate uniquely effected conjugate addition to yield 58. Incorporation of the hydroxybutenolide-containing side chain completed the total synthesis and established the viability of a general approach for the preparation of the isolabdanoid terpene system.

Synthesis of pyrrolidines and piperidines via palladium-catalyzed coupling of vinylic halides and olefinic sulfonamides

The palladium-catalyzed coupling of vinylic halides and olefinic sulfonamides affords good yields of 2-(1-alkenyl)pyrrolidine and -piperidine sulfonamides via vinylpalladium addition to the olefin, regioselective rearrangement to a π-allylpalladium intermediate, and subsequent intramolecular nucleophilic displacement of palladium.

Synthesis of 5-, 6-, 7- and 18-mono-13C-labelled retinals

Four retinals labelled at positions 5,6,7 and 18 with 13C were obtained via simple schemes involving only a few steps with >98percent chemical purity and 92percent 13C incorporation. (5-13C)Retinal was obtained in 26percent yield from K13CN. (6-13C)- and (7-13C)Retinal were obtained in 37percent yield from (2-13C)- and (1-13C)acetonitrile, respectively, while (18-13C)retinal was obtained in 8 steps and 4percent yield starting from 13CH3I.Their 13C - 1H and 13C - i142213C NMR coupling constants were determined.