41943-80-0Relevant academic research and scientific papers
Biotransformation of diterpenes and diterpene derivatives by Beauveria bassiana ATCC 7159
Buchanan, Greg O.,Reese, Paul B.
, p. 141 - 151 (2001)
The biohydroxylation of stemodin and stemodinone by Beauveria hassiana ATCC 7159 gave exclusively 2α,13,18-trihydroxystemodane and l3,18-dihydroxystemodan-2-one respectively. Stemarin was converted to the novel 1β,13,19-trihydroxystemarane and 13-hydroxys
Total synthesis of (±)-stemodinone
Tanaka, Tetsuaki,Murakami, Kazuo,Kanda, Atsushi,Patra, Debasis,Yamamoto, Sachiko,Satoh, Norifumi,Kim, Sang-Won,Ishida, Toshimasa,In, Yasuko,Iwata, Chuzo
, p. 1801 - 1804 (1997)
Starting from methyl-olefin (5), the total synthesis of (±)-stemodinone (2) was achieved through an efficient ring-exchange reaction to control the stereochemistry of C10 followed by A-ring construction and the introduction of three methyl groups.
Stemodin-derived analogues with lipid peroxidation, cyclooxygenase enzymes and human tumour cell proliferation inhibitory activities
Russell, Floyd A.,Mulabagal, Vanisree,Thompson, Dwayne R.,Singh-Wilmot, Marvadeen A.,Reynolds, William F.,Nair, Muraleedharan G.,Langer, Vratislav,Reese, Paul B.
, p. 2361 - 2368 (2011)
A series of analogues, derived from the antiviral and cytotoxic diterpene stemodin, were prepared and evaluated for their lipid peroxidation (LPO), cyclooxygenase enzyme-1 (COX-1) and -2 (COX-2), and tumour cell proliferation inhibitory activities. Oxidation of stemodin produced stemodinone, which was then converted to stemod-12-en-2-one. Reaction of the latter under Petrow conditions (bromine; silver acetate/pyridine) yielded mainly dibrominated abeo-stachanes. Solvolysis of the dibromo compounds gave products of hydrolysis, some with rearranged skeleta. In the lipid peroxidation inhibitory assay three of the compounds exhibited prominent activity. Interestingly, all the analogues showed higher COX-1 enzyme inhibition than COX-2. Although a few of the diterpenes limited the growth of some human tumour cell lines, most compounds induced proliferation of such cells.
The potential of Cyathus africanus for transformation of terpene substrates
McCook, Kayanne P.,Chen, Avril R.M.,Reynolds, William F.,Reese, Paul B.
, p. 61 - 66 (2012/11/07)
The insecticidal sesquiterpenes cadina-4,10(15)-dien-3-one and aromadendr-1(10)-en-9-one were administered to the fungus Cyathus africanus ATCC 35853. Biotransformation of the former produced (4R)-9α-hydroxycadin- 10(15)-en-3-one, while the latter gave 2β-hydroxyaromadendr-1(10)-en-9-one, 2α-hydroxyaromadendr-1(10)-en-9-one and 10α-hydroxy-1β, 2β-epoxyaromadendran-9-one. The bioconversion of santonin led to the production of two analogues, 11,13-dihydroxysantonin and the hitherto unreported 8α,13-dihydroxysantonin, while cedrol yielded 3β,8β- dihydroxycedrane and 3α,8β-dihydroxycedrane. Stemod-12-ene, a diterpene, was transformed to 2-oxostemar-13-ene, a hitherto unknown analogue with a rearranged carbon framework. When methyl betulonate, a triterpenoid belonging to the lupane family, was supplied to the fungus 18α-ursane and 18α-oleanane derivatives, namely 19β-hydroxy-3-oxo-18α-oleanan- 28-oic acid and 19α-hydroxy-3-oxo-18α-ursan-28-oic acids, were generated. There are no previous reports of fungal transformation of a triterpene in which a skeletal rearrangement occurred. All substrate administration experiments were done in the presence of the terpene cyclase inhibitor chlorocholine chloride (CCC), using the single phase - pulse feed method.
Bioconversion of Stemodia maritima diterpenes and derivatives by Cunninghamella echinulata var. elegans and Phanerochaete chrysosporium
Lamm, Andrew S.,Reynolds, William F.,Reese, Paul B.
, p. 1088 - 1093 (2008/02/10)
Stemodane and stemarane diterpenes isolated from the plant Stemodia maritima and their dimethylcarbamate derivatives were fed to growing cultures of the fungi Cunninghamella echinulata var. elegans ATCC 8688a and Phanerochaete chrysosporium ATCC 24725. C. echinulata transformed stemodin (1) to its 7α-hydroxy- (2), 7β-hydroxy- (3) and 3β-hydroxy- (4) analogues. 2α-(N,N-Dimethylcarbamoxy)-13-hydroxystemodane (6) gave 2α-(N,N-dimethylcarbamoxy)-6α,13-dihydroxystemodane (7) and 2α-(N,N-dimethylcarbamoxy)-7α,13-dihydroxystemodane (8). Stemodinone (9) yielded 14-hydroxy-(10) and 7β-hydroxy- (11) congeners along with 1, 2 and 3. Stemarin (13) was converted to the hitherto unreported 6α,13-dihydroxystemaran-19-oic acid (18). 19-(N,N-Dimethylcarbamoxy)-13-hydroxystemarane (14) yielded 13-hydroxystemaran-19-oic acid (17) along with the two metabolites: 19-(N,N-dimethylcarbamoxy)-2β,13-dihydroxystemarane (15) and 19-(N,N-dimethylcarbamoxy)-2β,8,13-trihydroxystemarane (16). P. chrysosporium converted 1 into 3, 4 and 2α,11β,13-trihydroxystemodane (5). The dimethylcarbamate (6) was not transformed by this microorganism. Stemodinone (9) was hydroxylated at C-19 to give 12. Both stemarin (13) and its dimethylcarbamate (14) were recovered unchanged after incubation with Phanerochaete.
Total synthesis of (+/-)-stemodinone via an efficient ring-exchange strategy.
Tanaka,Murakami,Kanda,Patra,Yamamoto,Satoh,Kim,Rahman,Ohno,Iwata
, p. 7107 - 7112 (2007/10/03)
A total synthesis of (+/-)-stemodinone, a tetracyclic stemodane diterpene, from the known tricyclic methyl olefin 11 is described. The key steps involve an efficient ring-exchange reaction and palladium(0)-catalyzed lactone migration. The ring-exchange strategy for controlling the stereochemistry was based on an initial Diels-Alder reaction to form a new ring followed by cleavage of the original ring. Cleavage of the original ring of the Diels-Alder adduct 9 was achieved by an initial regio- and chemoselective Baeyer-Villiger oxidation followed by the Pd(0)-catalyzed lactone-migration reaction reported by us.
