Organic compounds -- part of the class 532-570 series – Organic compounds – Carboxylic acid esters
Patent
1996-02-07
1998-03-17
Lambkin, Deborah
Organic compounds -- part of the class 532-570 series
Organic compounds
Carboxylic acid esters
560115, 562504, C07C 6974, C07C 6106
Patent
active
057288666
DESCRIPTION:
BRIEF SUMMARY
This application is a 371 of PCT/IB1995/00505 filed Jun. 21, 1995.
TECHNICAL FIELD AND PRIOR ART
The present invention relates to the field of organic synthesis and, more particularly, to that of the stereoselective and enantioselective synthesis of optically active compounds. It concerns in particular the preparation of (+)-(1R)-cis-3-oxo-2-pentyl-1-cyclopentaneacetic acid, or (+)-(1R,2S)-3-oxo-2-pentyl-1-cyclopentaneacetic acid, in a pure optically active form, as well as its methyl ester.
The structure of (+)-(1R)-cis-3-oxo-2-pentyl-1-cyclopentaneacetic acid is known. It has in fact been described by O. Miersch et al. in Phytochem. 26, 1037 (1987). According to these authors, the above-mentioned acid was extracted from a culture of Botryodiplodia theobromae isolated from Cuban origin oranges. However, to our knowledge, there is no prior art description of any synthetic method for preparing this acid which is susceptible of convenient industrial application.
The present invention brings precisely a solution to this problem. It provides the above-mentioned acid with excellent optical purity and essentially in the form of its (+)-(1R)-cis configuration isomer. This is all the more important in that (+)-(1R)-cis-3-oxo-2-pentyl-1-cyclopentaneacetic acid is a useful product for the preparation of methyl (+)-(1R)-cis-3-oxo-2-pentyl-1-cyclopentaneacetate, the preferred isomer, from an olfactive point of view, of methyl dihydrojasmonate, also known under the tradename of Hedione.RTM. (origin: Firmenich SA, Geneva, Switzerland), a much appreciated ingredient of vast use in perfumery.
Amongst the four optically active isomers of methyl dihydrojasmonate or Hedione.RTM., it is in fact known that methyl (+)-(1R)-cis-3-oxo-2-pentyl-1-cyclopentaneacetate possesses at best the sought-after Hedione.RTM. odor characters, and namely its jasmine note. Thus, obtaining optically pure methyl (+)-(1R)-cis-3-oxo-2-pentyl-1-cyclopentaneacetate is of capital importance in perfumery. If one considers, in addition, that to this day there is no synthesis of this compound that can be exploited on an industrial scale, the value of the present invention becomes quite understandable, since the latter renders it possible to industrially produce a starting product that can be converted on a large scale and in a profitable manner into methyl (+)-(1R)-cis-3-oxo-2-pentyl-1-cyclopentaneacetate.
DESCRIPTION OF THE INVENTION
An object of the invention is therefore a process for the preparation of 3-oxo-2-pentyl-1-cyclopentaneacetic acid, or of methyl 3-oxo-2-pentyl-1-cyclopentaneacetate, essentially in the form of their (+)-(1R)-cis configuration isomer, characterized in that it comprises the following steps: presence of a catalyst composed of a Ru (II) complex comprising chiral ligands which contain a 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl (BINAP) type ligand or a 1,2-bis(2,5-dialkylphospholano)benzenyl (DuPHOS) type ligand, wherein the alkyl is a C.sub.2 or C.sub.3 radical, of a compound of formula ##STR3## wherein M represents a hydrogen atom, an atom of an alkaline or alkaline-earth metal, or a NR.sub.4 group, R representing hydrogen or a lower alkyl radical, to obtain a compound of formula ##STR4## wherein M has the meaning indicated above, essentially in the form of an isomer of (+)-(1R)-cis configuration; compound of formula (II) wherein M represents an atom of an alkaline or alkaline-earth metal or a NR.sub.4 group, R representing hydrogen or a lower alkyl radical, to obtain (+)-(1R)-cis-3-oxo-2-pentyl-1-cyclopentaneacetic acid; and (+)-(1R)-cis-3-oxo-2-pentyl-1-cyclopentaneacetic acid thus obtained to form methyl (+)-(1R)-cis-3-oxo-2-pentyl-1-cyclopentaneacetate.
By alkaline or alkaline-earth metal, it is understood here any one of the elements in group I, or respectively II, of Mendelejev's Periodic Table. In this context, there can be cited more particularly sodium, potassium, lithium, cesium, calcium and magnesium.
On the other hand, the lower alkyl radicals represented by symbol R, typically include linear or branched alk
REFERENCES:
patent: 3158644 (1964-11-01), Demole et al.
patent: 3754016 (1973-08-01), Oberhansli
patent: 3954834 (1976-05-01), Cohen
patent: 3978108 (1976-08-01), Teisseire et al.
patent: 4014919 (1977-03-01), Johnson et al.
patent: 4039563 (1977-08-01), Tanaka et al.
patent: 4045489 (1977-08-01), Wiegers et al.
patent: 4072755 (1978-02-01), Buendia et al.
patent: 4237308 (1980-12-01), Torii et al.
patent: 4280934 (1981-07-01), Schulte-Elte
patent: 4294863 (1981-10-01), Mookherjee et al.
patent: 5300489 (1994-04-01), Boden et al.
patent: 5302745 (1994-04-01), Winter
patent: 5372994 (1994-12-01), Yamada et al.
patent: 5436226 (1995-07-01), Lulai et al.
B. Heiser et al., "New Efficient Methods for the Synthesis and In-Situ Preparation of Ruthenium(II) Complexes of Atropisomeric Diphosphines and Their Application in Asymmetric Catalytic Hydrogenations," Tetrahedron: Asymmetry vol. 2, No. 1, (1991) pp. 51-62.
E. Demole et al., "Isolement et determination de la structure du jasmonate de methyle, constituant odorant caracteristique de l'essence de jasmin," Helvetica Chimica ACTA (1962), pp. 675-685.
O. Miersch et al., "(+)-7-ISO-Jasmonic Acid and Related Compounds From Botryodiplodia Theobromae," Phytochemistry , vol. 26, No. 4 (1987) pp. 1037-1039.
K. Wan et al., "Asymmetric Hydrogenation in Water by a Rhodium Complex of Sulfonated 2,2'-Bis(diphenylphosphino)-1,1'-binaphthyl (binap)," J. Chem. Soc. (1993) pp. 1262-1264.
M.J. Burk, "C.sub.2 -Symmetric Bis(phospholanes) and Their Use in Highly Enantioselective Hydrogenation Reactions," J. Am. Chem. Soc. , vol. 113, No. 22 (Oct. 1991) pp. 8518-8519.
Rautenstrauch Valentin
Riedhauser Jean-Jacques
Firmenich SA
Lambkin Deborah
LandOfFree
Process for the preparation of (+)-(1R) -cis-3-oxo-2-pentyl-1-cy does not yet have a rating. At this time, there are no reviews or comments for this patent.
If you have personal experience with Process for the preparation of (+)-(1R) -cis-3-oxo-2-pentyl-1-cy, we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Process for the preparation of (+)-(1R) -cis-3-oxo-2-pentyl-1-cy will most certainly appreciate the feedback.
Profile ID: LFUS-PAI-O-959064