Degradation of a-pinene

More recently, the degradation of a-pinene by Pseudomonas jluorescens NCIMB 11671 was described [97,98]. A novel pathway for the microbial breakdown of a-pinene (119) was proposed, Fig. (23). The attack is initiated by enzymatic oxygenation of the 1,2-double bond to form the epoxide (127). This epoxide then undergoes rapid rearrangement to produce a novel diunsaturated aldehyde, occurring as two isomeric forms. The primary product of the reaction (Z)-2-methyl-5-isopropylhexa-2,5-dien-l-al (trivial name isonovalal) (128) can undergo chemical isomerisation to the -form (novalal) (129). Isonovalal, the native form of... 

The negative values for the degradation of a-pinene and of A -carene at 6h-on-stream correspond to an increase of these terpenes in the products. After 30 h-on-stream all the main terpenes are degraded during the HDS treatment. It should be noted that the conversion of /3-pinene is higher in the turpentine oil than in the /3-pinene fraction. This is not due to a change in the terpene concentration in an experiment of HDS carried out with a mixture of a-pinene, /3-pinene and A -carene (in the same proportion as in the turpentine oil), the conversion of /3-pinene was 12%, very close to the conversion recorded... 

Gibbon, G.H., N.R Millis, and S.J. Pirt, 1972. Degradation of a-pinene by bacteria. Proc. IVIFS, Ferment. Technol. Today, pp. 609-612. 

Gibbon, G.H. and S.J. Pitt, 1971. The degradation of a-pinene by Pseudomonas PX 1. FEBS Lett., 18 103-105. Gondai, T., M. Shimoda, and T. Hirata, 1999. Asymmetric reduction of enone compounds by Chlorella miniata. Proc. 43rd TEAC, pp. 217-219. 

Chiral cyclopropanes, such as (9), have been obtained by degradation of (+)-a-pinene using a sequence of reactions that features a stereocontrolled ring contraction of a cyclobutanol derivative/ The iron carbonyl complex (10) has been resolved, and used to prepare the optically active cyclopropanes (11)."... 

Best DJ, NC Floyd, A Magalhaes, A Bnrfield, PM Rhodes (1987) Initial steps In the degradation of alpha-pinene by Pseudomonas fluorescens NCIMB 11671. Biocatalysis 1 147-159. 

Alcohols are oxidized to aldehydes by the liver enzyme alcohol dehydrogenase, and aldehydes to carboxylic acids by aldehyde dehydrogenase. In mammals, monooxygenases can be induced by plant secondary metabolites such as a-pinene, caffeine, or isobornyl acetate. Reduction is less common and plays a role with ketones that cannot be further oxidized. Hydrolysis, the degradation of a compound with addition of water, is also less common than oxidation. 

Ozonolysis of (—)-a-pinene 146 in pentane at — 35 °C or on polyethylene at —70°C affords only epoxide 147 and its degradation products 148 and 149 but no ozonide, perhaps due to steric hindrance caused by the two geminal methyl groups <1996T14813>. 

Earlier workers established the presence of a-pinene, (3-pinene, 1-a-phellandrene, dl-limonene, piperonal, dihydrocarveol, a compound melting at 161°C, P-caryophyllene and a piperidine complex from the essential oil obtained by steam distillation of ground Malabar pepper. The above compounds were identified by the classical methods of derivatization and degradation. They also reported the presence of epoxy dihydrocary-... 

Shukla, O.P., and P.K. Bhattacharyya, 1968. Microbiological transformations of terpenes Part XI—Pathways of degradation of a- P pinenes in a soil Pseudomonad (PL-strain). Indian J. Biochem., 5 92-101. Shukla, O.P., M.N. Moholay, and P.K. Bhattacharyya, 1968. Microbiological transformation of terpenes Part X—Fermentation of a- Ppinenes by a soil Pseudomonad (PL-strain). Indian J. Biochem., 5 79-91. Southwell, I.A. and T.M. Flynn, 1980. Metabolism of a- and p-pinene,/)-cymene and 1,8-cineole in the brush tail possum. XenobiotiM, 10 17-23. 

FIGURE 14.149 Metabolic pathways of degradation of a- and P-pinene by a soil Pseudomonad (PL strain) and Pseudomonas PIN 18. (Modified from Shukla, O.P., and P.K. Bhattacharyya, 1968. Indian J. Biochem., 5 92-101.)... 

This oil is produced exclusively in southern France and Algeria its major components are a-pinene and 3-carene. Degradation products of higher terpenoids are responsible for the typical ambergris note [470-473]. FCT 1978 (16) 699 [8013-86-3], [84696-07-1]. 

The same group has also isolated a strain of Pseudomonas putida-arvilla (PL-strain) from limonene and (+)-a-pinene as the sole carbon source that was capable of growing on (+)-limonene, (+)-a-pinene, (-)-a-pinene, / -pinene, 1-p-menthene, 3-p-menthene and p-cymene as substrates [75]. Limonene was degraded to perillyl alcohol, perillaldehyde and perillic acid. 

Metabolism, Biological Activity, Miscellaneous.—Camphene was converted into its 1,2-diol in rabbit,953 and the pathways from a- and p-pinenes and car-3-ene to hydroxylated, ring-opened, and decarboxylated compounds have been determined.954 The 9,10-oxide of THC was initially hydroxylated at C-8(p), and in the side-chain by rat 955 AU-THC was hydroxylated at C-8, C-10, and in the side-chain and subsequently epoxidized.956 The metabolism and degradation of various... 

---