5206-83-7

Upstream product

• 3858-43-3 (1R,2R,4R)-(-)-carvomenthol 
• 33375-08-5 (R)-5-isopropyl-2-methylcyclohex-2-enone 
• 6485-40-1 (R)-Carvone 
• 3858-49-9 (1R,2S,4R)-(+)-neocarvomenthol 
• 2102-62-7 p-Menthadiene-<1(7),8>-trans-ol-(2) 
• 18383-51-2 (-)-trans-carveol 
• 1946-00-5 (1S,2S,4R)-limonene-1,2-diol 
• 499-69-4 (2R,5R)-2-methyl-5-(isopropyl)cyclohexan-1-ol 
• 74006-76-1 (R)-(+)-3-(1-methylethyl)cyclohexanone 
• 74-88-4 methyl iodide 
• 4031-57-6 (1RS,2RS,4RS)-p-menthane-1,2-diol 
• 4031-57-6 (1RS,2RS,4SR)-p-menthane-1,2-diol 
• 4031-57-6 (1RS,2SR,4RS)-p-menthane-1,2-diol 
• 4031-57-6 (1RS,2SR,4SR)-p-menthane-1,2-diol 

Downstream Products

• 3858-49-9 (1R,2S,4R)-(+)-neocarvomenthol 
• 3858-43-3 (1R,2R,4R)-(-)-carvomenthol 
• 59060-39-8 hydroxymethylenecarvomenthone 
• 899420-99-6 [(2R,5R)-5-Isopropyl-2-methyl-cyclohex-(E)-ylidene]-acetic acid methyl ester 
• 606490-81-7 (4R,7R)-(-)-7-methyl-4-isopropyl-2-oxo-oxepanone 
• 141538-91-2 (3R,6S)-(-)-3-methyl-6-iso-propenyl-2-oxo-oxepanone 
• 1575700-69-4 N-[{(1S,4R,E)-4-isopropyl-2-(methoxyimino)cyclohexyl}methyl]-4-methylbenzenesulfonamide 
• 1575699-78-3 (2R,5R,E)-5-isopropyl-2-methylcyclohexanone O-methyl oxime 
• 134178-39-5 3-ethyl-2,5-dimethylcyclohex-2-en-1-one 
• 499-69-4 5-isopropyl-2-methylcyclohexan-1-ol 
• 499-69-4 5-isoprpyl-2-methylcyclohexan-1-ol 
• 69770-96-3 4-Isobutyl-2-methyl-cyclopentanone 
• 640296-44-2 (1R)-trans-p-menthan-2-one semicarbazone 
• 2157-46-2 (+)-carvomenthone oxime of mp: 100 degree 

Relevant academic research and scientific papers

Selective C-C Bond Cleavage of Cycloalkanones by NaNO2/HCl

A novel selective fragmentation of cycloalkanones by NaNO2/HCl has been established. The C-C bond cleavage reaction proceeds smoothly under mild conditions, selectively affording versatile keto acids or oxime acids. The methodology can streamline the synthesis of valuable chiral molecules and isocoumarins from readily available feedstocks.

Bidentate Nitrogen-Ligated I(V) Reagents, Bi(N)-HVIs: Preparation, Stability, Structure, and Reactivity

Hypervalent iodine(V) reagents are a powerful class of organic oxidants. While the use of I(V) compounds Dess-Martin periodinane and IBX is widespread, this reagent class has long been plagued by issues of solubility and stability. Extensive effort has been made for derivatizing these scaffolds to modulate reactivity and physical properties but considerable room for innovation still exists. Herein, we describe the preparation, thermal stability, optimized geometries, and synthetic utility of an emerging class of I(V) reagents, Bi(N)-HVIs, possessing datively bound bidentate nitrogen ligands on the iodine center. Bi(N)-HVIs display favorable safety profiles, improved solubility, and comparable to superior oxidative reactivity relative to common I(V) reagents. The highly modular synthesis and in situ generation of Bi(N)-HVIs provides a novel and convenient screening platform for I(V) reagent and reaction development.

Environmentally responsible, safe, and chemoselective catalytic hydrogenation of olefins: ppm level Pd catalysis in recyclable water at room temperature

Textbook catalytic hydrogenations are typically presented as reactions done in organic solvents and oftentimes under varying pressures of hydrogen using specialized equipment. Catalysts new and old are all used under similar conditions that no longer reflect the times. By definition, such reactions are both environmentally irresponsible and dangerous, especially at industrial scales. We now report on a general method for chemoselective and safe hydrogenation of olefins in water using ppm loadings of palladium from commercially available, inexpensive, and recyclable Pd/C, together with hydrogen gas utilized at 1 atmosphere. A variety of alkenes is amenable to reduction, including terminal, highly substituted internal, and variously conjugated arrays. In most cases, only 500 ppm of heterogeneous Pd/C is sufficient, enabled by micellar catalysis used in recyclable water at room temperature. Comparison with several newly introduced catalysts featuring base metals illustrates the superiority of chemistry in water.

Natural-Product-Derived Transient Receptor Potential Melastatin 8 (TRPM8) Channel Modulators

A library of novel structural hybrids of menthol and cubebol was tested for each derivative's ability to interact with the transient receptor potential subfamily melastatin member 8 (TRPM8) channel. This structure-activity relationship study revealed three potent modulators of the TRPM8 ion channel: a novel agonist (4) with an EC50 value of 11 ± 1 μM, an antagonist (15) with an IC50 value of 2 ± 1 μM, and an allosteric modulator (21) that minimized channel desensitization toward menthol. Each of these novel exocyclic olefin analogues of menthol is readily accessible by synthesis and was tested using Ca2+ assays and electrophysiology.

Highly Selective Hydrogenation of Aromatic Ketones and Phenols Enabled by Cyclic (Amino)(alkyl)carbene Rhodium Complexes

Air-stable Rh complexes ligated by strongly σ-donating cyclic (amino)(alkyl)carbenes (CAACs) show unique catalytic activity for the selective hydrogenation of aromatic ketones and phenols by reducing the aryl groups. The use of CAAC ligands is essential for achieving high selectivity and conversion. This method is characterized by its good compatibility with unsaturated ketones, esters, carboxylic acids, amides, and amino acids and is scalable without detriment to its efficiency.

Diverting Hydrogenations with Wilkinson's Catalyst towards Highly Reactive Rhodium(I) Species

The addition of Barton's base has a dramatic effect on the classic rhodium(III)-mediated hydrogenations promoted by Wilkinson′s catalyst. Following the initial oxidative addition, a barrierless reductive elimination of HCl from the traditional rhodium(III) intermediates instantly produces a rhodium(I) monohydride species, which is remarkably reactive in the hydrogenation of several internal alkynes and functionalized trisubstituted alkenes. The direct formation of this species is unprecedented upon addition of molecular hydrogen and its catalytic potential has been hitherto barely explored.

Organocatalytic oxidation of secondary alcohols using 1,2-Di(1-naphthyl)-1,2-ethanediamine (NEDA)

Diamine, 1,2-di(1-naphthyl)-1,2-ethanediamine (NEDA), efficiently catalyzes the oxidation of alcohols by using TBHP as an oxidant. Notably, secondary benzyl alcohols are oxidized in almost quantitative yields, and the catalyst also displays high activity towards even hindered cycloaliphatic secondary alcohols. With enantiopure (R,R)-NEDA, oxidative kinetic resolution can be realized and depending on the alcohol ee up to 99% are achieved.

Tetrabutylammonium prolinate-based ionic liquids: A combined asymmetric catalysis, antimicrobial toxicity and biodegradation assessment

Chiral ionic liquids (CILs) tetrabutylammonium-(S)-prolinate, tetrabutylammonium-(R)-prolinate and tetrabutylammonium trans-4-hydroxy-(S)- prolinate were investigated as chiral additives in the Pd-catalyzed enantioselective hydrogenation of α,β-unsaturated ketones. These CILs were easily prepared in one step from the aminoacid and tetrabutylammonium hydroxide and characterized (NMR, IR, optical rotation, elemental analysis, DSC, viscosity, decomposition temperature). The research strategy was to assess the antimicrobial toxicity (>20 strains) and biodegradability (OECD 301D) of the CILs at the same time as undertaking the asymmetric catalysis study. The Pd-catalyzed enantioselective hydrogenation of the carbon-carbon double bond of α,β-unsaturated ketones under mild conditions (room temperature, 1 atm of H2) in different solvents with CILs present. The best results were obtained in i-PrOH after 18 hours of reaction with a i-PrOH/IL ratio of 5. While all three CILs have low antimicrobial toxicity to a wide range of bacteria and fungi, tetrabutylammonium-(S)-prolinate, tetrabutylammonium-(R)-prolinate and tetrabutylammonium trans-4-hydroxy-(S)-prolinate did not pass the Closed Bottle biodegradation test.

Site-saturation mutagenesis of tryptophan 116 of saccharomyces pastorianus old yellow enzyme uncovers stereocomplementary variants

Site-saturation mutagenesis was used to generate all possible replacements for Trp 116 of Saccharomyces pastorianus (formerly Saccharomyces carlsbergensis) old yellow enzyme (OYE). Our original hypothesissthat smaller amino acids at position 116 would allow better acceptance of bulky 3-alkylsubstituted 2-cyclohexenonessproved incorrect. Instead, Phe and Ile replacements favored the binding of some substrates in an opposite orientation, which yielded reversed stereochemical outcomes compared to that of the wild-type OYE. For example, W116I OYE reduced (R)- and (S)-carvone to enantiomeric products, rather than the diastereomers produced by the wild-type OYE. Deuterium labeling revealed that (S)-carvone reduction by the W116I OYE occurred by the same pathway as that by the wild type (net trans-addition of H2), proving that different substrate binding orientations were responsible for the divergent products. Trp 116 mutants also afforded different stereochemical outcomes for reductions of (R)- perillaldehyde and neral. Preliminary studies of an OYE family member whosenative sequence contains Ile at position 116 (Pichia stipitis OYE 2.6) revealed that this enzyme's stereoselectivity matched that of the wild-t ype S. pastorianus OYE, showing that the identity of the residue at position 116 does not solely determine the substrate binding orientation. Computational docking studies using an induced fit methodology successfully reproduced the majority of the experimental outcomes. These computational tools will allow preliminary in silico screening of additional residues to identify those most likely to control the substrate binding orientation and provide some guidance to future experimental studies.

Microbial Baeyer-Villiger oxidation of terpenones by recombinant whole-cell biocatalysts - Formation of enantiocomplementary regioisomeric lactones

Recombinant whole-cell expression systems for Baeyer-Villiger monooxygenases of various bacterial origin were utilized in the regiodivergent biooxidation of cyclic terpenones enabling access to enantio- and regioisomeric lactones on preparative scale. This journal is The Royal Society of Chemistry.