Regioselective Oxidation of (+)-.ALPHA.-Longipinene by Aspergillus niger

Abstract

A Agilent-technologies 5973N gas chromatograph equipped with a split injector HP-5MS capillary column (30 m length, 0.25 mm i.d.) was combined by direct coupling to a Agilent-technologys 5973N mass spectrometer. The same temperature program as just described for GC was used. Helium at 1 mL/min was used as a carrier gas. The elec- Journal of Oleo ScienceCopyright ©2010 by Japan Oil Chemists ' Society J. Oleo Sci. 59,(5) 261-265 (2010) Regioselective Oxidation of (+)-a-Longipinene by Aspergillus niger Kazuki Sakata and Mitsuo MiyazawaAbstract: The regioselective oxidation of (+)-a-longipinene (1) with sesquiterpen hydrocarbon was investigated using Aspergillus niger (NBRC 4414) as a biocatalyst. Compound 1 was converted to three new terpenoids, (+)-(5S)-5,12-dihydroxy-a-longipinene (2), (-)-(5R)-5,12-dihydroxy-a-longipinene (3), and (+)-12-hydroxy-a-longipinen-5-one (4). These structures were determined by NMR, IR, specific rotation and mass spectral studies.

Improvement of a P450-Based Recombinant Escherichia coli Whole-Cell System for the Production of Oxygenated Sesquiterpene Derivatives

“…(+)-α-Longipinene was converted into only one product at a retention time of 13.85 min (Figure 1A). The major ions with their intensities (in parentheses) in the mass spectrum of this product were as follows: 41 (1), 55 (3), 69 (10), 77 (16), 93 (46), 105 (85), 121 (53), 135 (100), 149 (84), 159 (49), 175 (25), 189 (82), 202 (201), and 220 (38) (Figure 1B). (−)-Isolongifolene was converted into a major product (73%) at a retention time of 13.57 min and two minor products at retention times of 14.75 and 16.07 min, respectively (Figure 1C).…”

“…To date, transformations of (+)-α-longipinene, (−)-isolongifolene, and α-humulene have received remarkable attention from researchers because they are major constituents of plant essential oils, which have interesting biological properties. (+)-α-Longipinene is one of the major components of essential oils from many herbs and plants, such as Cedrus atlantica and Monticalia andicola with antioxidant and antibacterial activities. , Biotransformation of (+)-α-longipinene by Aspergillus niger was performed to investigate its derivatives . So far, 12-hydroxy-α-longipinene has been found in the heartwood of Juniperus chinensis Linn.…”

“…47,48 Biotransformation of (+)-α-longipinene by Aspergillus niger was performed to investigate its derivatives. 49 So far, 12hydroxy-α-longipinene has been found in the heartwood of Juniperus chinensis Linn. var.…”

Production of a new terpenoid from biotransformation of (-)-isolongifolanol byAspergillus nigerand suppression of SOS-inducing activity

“…Longifolenes exist in the essential oil of conifer species and have antioxidant and anti-infl ammatory activity and a unique fl avour (Orav et al 1996, Singh et al 2005, Awad 2002). Previously we have investigated the biotransformation of the longifolenes ( ϩ )-cycloisolongifolol, (-)-isolongifolol, ( ϩ )-α -longipinene, (-)-isolongifolene and ( ϩ )-longicyclene by microorganisms (Miyazawa and Sakata 2007, Sakata and Miyazawa 2010a, Sakata and Miyazawa 2010b. The metabolites showed a suppressive effect on the SOS response, which is induced by an alteration in DNA synthesis, either directly by agents blocking the replication fork or indirectly by antibiotics, such as novobiocin, that inhibit DNA synthesis.…”

Biotransformation of 4-Chromanol, 4-Flavanol, Xanthydrol, and their Analogs by Tissue Cultured Cells

“…Many types of biocatalysts have been examined, such as fungi, microorganisms, and insects [1][2][3][4][5][6][7][8][9][10][11]. Furthermore, the Hamada group at the Okayama University of Science has investigated organic synthesis methods using tissue culture cells of higher plants as biocatalysts for reactions such as the glycosylation of terpenes [12][13][14][15][16].…”