491-09-8Relevant academic research and scientific papers
Chemoenzymatic Synthesis of the Intermediates in the Peppermint Monoterpenoid Biosynthetic Pathway
Cheallaigh, Aisling Ní,Mansell, David J.,Toogood, Helen S.,Tait, Shirley,Lygidakis, Antonios,Scrutton, Nigel S.,Gardiner, John M.
, p. 1546 - 1552 (2018/08/04)
A chemoenzymatic approach providing access to all four intermediates in the peppermint biosynthetic pathway between limonene and menthone/isomenthone, including noncommercially available intermediates (-)-trans-isopiperitenol (2), (-)-isopiperitenone (3), and (+)-cis-isopulegone (4), is described. Oxidation of (+)-isopulegol (13) followed by enolate selenation and oxidative elimination steps provides (-)-isopiperitenone (3). A chemical reduction and separation route from (3) provides both native (-)-trans-isopiperitenol (2) and isomer (-)-cis-isopiperitenol (18), while enzymatic conjugate reduction of (-)-isopiperitenone (3) with IPR [(-)-isopiperitenone reductase)] provides (+)-cis-isopulegone (4). This undergoes facile base-mediated chemical epimerization to (+)-pulegone (5), which is subsequently shown to be a substrate for NtDBR (Nicotiana tabacum double-bond reductase) to afford (-)-menthone (7) and (+)-isomenthone (8).
Method for producing 1-menthol
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Example 2, (2008/06/13)
Provided is a method for the production of 1-menthol, which comprises hydrogenation of piperitenone with a transition metal complex of a specified optically active phosphine to produce pulegone, hydrogenation of the obtained pulegone with a ruthenium-phosphine-amine complex in the presence of base to obtain pulegol, and further hydrogenation of the pulegol with a transition metal catalyst.
Method for producing 1-menthol
-
, (2008/06/13)
Provided is a method for the production of 1-menthol, which comprises hydrogenation of piperitenone with a transition metal complex of a specified optically active phosphine to produce pulegone, hydrogenation of the obtained pulegone with a ruthenium-phosphine-amine complex in the presence of base to obtain pulegol, and further hydrogenation of the pulegol with a transition metal catalyst.
α′-hydroxy-α,β-unsaturated tosylhydrazones: Preparation and use as intermediates for carbonyl and enone transpositions
Baptistella, Lucia H. B.,Aleixo, Adriana M.
, p. 2937 - 2950 (2007/10/03)
Regiospecifically generated α,β-unsaturated tosylhydrazones dianions are treated with molecular oxygen, yielding α′-hydroxy-α,β-unsaturated tosylhydrazones, versatile intermediates for organic synthesis. They proved to be useful for 1,2-carbonyl and 1,2-enone transpositions, and also permitted the preparation of α′-hydroxy enones in very high yields.
Thermal degradation of terpenes: Camphene, Δ3-carene, limonene, and α-terpinene
Mcgraw, Gerald W.,Hemingway, Richard W.,Ingram Jr., Leonard L.,Canady, Catherine S.,Mcgraw, William B.
, p. 4029 - 4033 (2007/10/03)
Emissions from wood dryers have been of some concern for a number of years, and recent policy changes by the Environmental Protection Agency have placed emphasis upon the gaseous emissions that lead to the formation of particulate matter as small as 2.5 μm diameter. In this qualitative study, camphene, Δ3-carene, limonene, and α-terpinene were thermally degraded in the presence of air to determine the number and kind of oxidative degradation products that might be expected under drying conditions used in processing wood products. Various chromatographic methods were used to isolate the products for proof of structure by NMR and/or GC-MS. The degradation products resulted from dehydrogenations, epoxidations, double bond cleavages, allylic oxidations, and rearrangements. A number of compounds not previously associated with the thermal degradation of these terpenes were identified. Emissions from wood dryers have been of some concern for a number of years, and recent policy changes by the Environmental Protection Agency have placed emphasis upon the gaseous emissions that lead to the formation of particulate matter as small as 2.5 μm diameter. In this qualitative study, camphene, Δ3-carene, limonene, and α-terpinene were thermally degraded in the presence of air to determine the number and kind of oxidative degradation products that might be expected under drying conditions used in processing wood products. Various chromatographic methods were used to isolate the products for proof of structure by NMR and/or GC-MS. The degradation products resulted from dehydrogenations, epoxidations, double bond cleavages, allylic oxidations, and rearrangements. A number of compounds not previously associated with the thermal degradation of these terpenes were identified.
Transformation of a monoterpene ketone, (R)-(+)-pulegone, a potent hepatotoxin, in Mucor piriformis
Madyastha,Thulasiram
, p. 1203 - 1207 (2007/10/03)
Biotransformation of a monoterpene ketone, (R)-(+)-pulegone (I), a potent hepatotoxin, was studied using a fungal strain, Mucor piriformis. Eight metabolites, namely, 5-hydroxypulegone (II), piperitenone (III), 6- hydroxypulegone (IV), 3-hydroxypulegone (V), 5-methyl-2-(1-hydroxy-1- methylethyl)-2-cyclohexene-1-one (VI), 3-hydroxyisopulegone (VII), 7- hydroxypiperitenone (VIII), and 7-hydroxypulegone (IX), have been isolated from the fermentation medium and identified. GC analysis of the metabolites indicated that II was the major metabolite formed. The organism initiates transformation either by hydroxylation at the C-5 position or by hydroxylation of the ring methylenes, the former being the major activity. On the basis of the identification of the metabolites, pathways for the biotransformation of (R)-(+)-pulegone have been proposed. The mode of transformation of (S)-(-)-pulegone by this organism was shown to be similar to that of its (R)-(+)-enantiomer. When isopulegone (X) was used as the substrate, the organism isomerized it to pulegone (I), which was then transformed to metabolites II-IX.
Biotransformation Products of (5R)-(+)-Pulegone and (2S,5R)-(-)-Menthone Produced by Cultured Cells of Catharanthus roseus
Williams, Howard J.,Moyna, Guillermo,Scott, A. Ian,Hamada, Hiroki,Lwin, War War,Tanaka, Toshinori,Furuya, Tsutomu
, p. 838 - 840 (2007/10/03)
Catharanthus roseus cultured cells produce several new oxidized products from (5R)-(+)-pulegone and (2S, 5R)-(-)-menthone, in some of which a double bond migration has occurred. Products were identified using NMR and mass spectrometry. The pleasant fragrances of some of the products suggest possible use as perfumery agents.
β-Pinene-6-one: A pivotal synthetic intermediate
Hebrault,Uguen
, p. 6699 - 6702 (2007/10/03)
Submitting the title ketone to either acetoxymercuration or basic conditions resulted in the formation of the acid β-5 and α-5, respectively, with an useful selectivity, related rearrangements being observed by using the corresponding alcohol and its epoxy derivative.
Biotransformation of terpenic compounds by fungi. I. Metabolism of R-(+)-pulegone
Ismaili-Alaoui,Benjilali,Buisson,Azerad
, p. 2349 - 2352 (2007/10/02)
R-(+)-Pulegone 1 is converted by several fungal strains to new regioselectively hydroxylated compounds. Epoxidation of the double bond does not seem to be responsible for the main observed hydroxylation pattern.
