01812nas a2200169 4500008004100000022001400041245011800055210006900173260011000242300001400352490000700366520106400373100001901437700002101456700003701477856012801514 2013 eng d a1463-926200aBiocatalysis: fungi mediated novel and selective 12 beta- or 17 beta-hydroxylation on the basic limonoid skeleton0 aBiocatalysis fungi mediated novel and selective 12 beta or 17 be aTHOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLANDbROYAL SOC CHEMISTRYcMAR a1311-13170 v153 a

Basic limonoids carrying a 4,4,8-trimethyl-17-furanylsteroid skeleton are a class of triterpenoids and well-known for their insecticidal as well as a vast array of pharmacological activities. Rare and synthetically challenging 12 beta- and 17 beta-hydroxylation was achieved on the basic limonoid skeleton to produce a novel series of hydroxylated limonoids using fungi-mediated biocatalysis. The fungal system belonging to the genera of Mucor efficiently converted azadiradione, epoxyazadiradione, gedunin and their derivatives into corresponding 12 beta- and/or 17 beta-hydroxy derivatives. The position and stereochemistry of hydroxylation was determined by rigorous spectroscopic and crystallographic studies. This fungi-mediated stereo- and regio-selective hydroxylation process was highly efficient and mild enough to sustain chemically sensitive functional groups around the basic limonoid skeleton. Modifications of specific functional groups and variation in biocatalyst were shown to bring selectivity among 12 beta- or 17 beta-hydroxylation.

1 aHaldar, Saikat1 aKolet, Swati, P.1 aThulasiram, Hirekodathakallu, V. uhttps://library.ncl.res.in/content/biocatalysis-fungi-mediated-novel-and-selective-12-beta-or-17-beta-hydroxylation-basic-001870nas a2200229 4500008004100000022001400041245010100055210006900156260007900225300001400304490000700318520099500325653002501320653002201345653001401367100002101381700002701402700001901429700002401448700003701472856013101509 2013 eng d a0039-128X00aBiocatalyst mediated production of 6 beta,11 alpha-dihydroxy derivatives of 4-ene-3-one steroids0 aBiocatalyst mediated production of 6 beta11 alphadihydroxy deriv a360 PARK AVE SOUTH, NEW YORK, NY 10010-1710 USAbELSEVIER SCIENCE INCcNOV a1152-11580 v783 a

Biotransformation of steroids with 4-ene-3-one functionality such as progesterone (I), testosterone (II), 17 alpha-methyltestosterone (III), 4-androstene-3,17-dione (IV) and 19-nortestosterone (V) were studied by using a fungal system belonging to the genera of Mucor (M881). The fungal system efficiently and quantitatively converted these steroids in regio- and stereo-selective manner into corresponding 6 beta,11 alpha-dihydroxy compounds. Time course experiments suggested that the transformation was initiated by hydroxylation at 6 beta- or 11 alpha-(10 beta-hydroxy in case of V) to form monohydroxy derivatives which upon prolonged incubation were converted into corresponding 613,11oc-dihydroxy derivatives. The fermentation studies carried out using 5 L table-top fermentor with substrates (I and II) clearly indicates that 6 beta,11 alpha-dihydroxy derivatives of steroids with 4-ene-3-one functionality can be produced in large scale by using M881. (C) 2013 Elsevier Ltd.

10a4-Ene-3-one steroids10aBiotransformation10aMucor sp.1 aKolet, Swati, P.1 aNiloferjahan, Siddiqui1 aHaldar, Saikat1 aGonnade, Rajesh, G.1 aThulasiram, Hirekodathakallu, V. uhttps://library.ncl.res.in/content/biocatalyst-mediated-production-6-beta11-alpha-dihydroxy-derivatives-4-ene-3-one-steroids-001282nas a2200205 4500008004100000022001400041245008100055210006900136260011000205300001600315490000600331520047900337100001900816700002100835700002700856700002100883700002400904700003700928856011100965 2014 eng d a2046-206900aBiocatalyst mediated functionalization of salannin, an insecticidal limonoid0 aBiocatalyst mediated functionalization of salannin an insecticid aTHOMAS GRAHAM HOUSE, SCIENCE PARK, MILTON RD, CAMBRIDGE CB4 0WF, CAMBS, ENGLANDbROYAL SOC CHEMISTRYcJUN a27661-276640 v43 a

Transformation of salannin, an insecticidal C-seco limonoid was investigated using a fungal system, Cunninghamella echinulata. Salannin was efficiently converted into two metabolites, where the C-17 furan moiety was transformed into gamma-hydroxybutenolide (salanninolide) and N-(2-hydroxyethyl)-alpha,beta-unsaturated-gamma-lactam (salanninactam) analogues. Present studies have indicated salanninolide to be a metabolite in the C-seco limonoid biosynthetic pathway.

1 aHaldar, Saikat1 aKolet, Swati, P.1 aDandekar, Devdutta, S.1 aKale, Balaji, S.1 aGonnade, Rajesh, G.1 aThulasiram, Hirekodathakallu, V. uhttps://library.ncl.res.in/content/biocatalyst-mediated-functionalization-salannin-insecticidal-limonoid-0