25886-63-9Relevant academic research and scientific papers
Stereopermutation on the putative structure of the marine natural product mucosin
Antonsen, Simen G.,Gallantree-Smith, Harrison,G?rbitz, Carl Henrik,Hansen, Trond Vidar,Stenstr?m, Yngve H.,Nols?e, Jens M.J.
, (2017)
A stereodivergent total synthesis has been executed based on the plausibly misassigned structure of the unusual marine hydrindane mucosin (1). The topological connectivity of the four contiguous all-carbon stereocenters has been examined by selective permutation on the highlighted core. Thus, capitalizing on an unprecedented stereofacial preference of the cis-fused bicycle[4.3.0]non-3-ene system when a Michael acceptor motif is incorporated, copper-mediated conjugate addition furnished a single diastereomer. Cued by the relative relationship reported for the appendices in the natural product, the resulting anti-adduct was elaborated into a probative target structure 1?.
Microbial Baeyer-Villiger oxidation of ketones by cyclohexanone and cyclopentanone monooxygenase - A computational rational for biocatalyst performance
Mihovilovic, Marko D.,Mueller, Bernhard,Spina, Markus,Durrani, Arjumand I.,Stanetty, Peter,Dazinger, Georg,Kirchner, Karl
, p. 785 - 794 (2006)
Recombinant Escherichia coli overexpressing Pseudomonas sp. NCIMB 9872 cyclopentanone monooxygenase (CPMO, EC 1.14.13.16) and Acinetobacter sp. NCIMB 9871 cyclohexanone monooxygenase (CHMO, EC 1.14.13.22) have been utilized in whole-cell Baeyer-Villiger biotransformations of prochiral bicycloketones. A significant difference in substrate acceptance and stereoselectivity was observed for bicyclo[3.3.0] and bicyclo[4.3.0] substrates. A plausible mechanism of these transformations was established by means of high level DFT/B3LYP calculations suggesting an essential difference in electronic requirements for a successful enzymatic conversion, which was similarly encountered in recombinant whole-cell mediated biooxidations. Some of the lactones produced in the biocatalytic Baeyer-Villiger oxidation represent key intermediates for the synthesis of indole alkaloids. Springer-Verlag 2006.
Total synthesis based on the originally claimed structure of mucosin
Gallantree-Smith, Harrison C.,Antonsen, Simen G.,G?rbitz, Carl H.,Hansen, Trond V.,Nols?e, Jens M. J.,Stenstr?m, Yngve H.
supporting information, p. 8433 - 8437 (2016/09/28)
The first total synthesis aimed at the naturally occurring eicosanoid bicycle mucosin is reported. A practical route has been devised allowing the issues relating to the previous assignment of stereochemistry to be examined. X-ray crystallography was performed on a late stage intermediate to pinpoint the topological relationship displayed by the featured bicyclo[4.3.0]non-3-ene scaffold.
Synthesis of 1,3-Cycloalkadienes from Cycloalkenes: Unprecedented Reactivity of Oxoammonium Salts
Nagasawa, Shota,Sasano, Yusuke,Iwabuchi, Yoshiharu
, p. 13189 - 13194 (2016/10/30)
Few methods allow for the direct conversion of cycloalkenes into cycloalkadienes with high chemo- and regioselectivity. Herein, we report a convenient one-pot process for this transformation that involves the unprecedented N-preferential group transfer of N-oxoammonium salts to cycloalkenes, followed by Cope elimination, to afford cycloalkadienes at room temperature and pressure.
Microbial Baeyer-Villiger oxidation of bicyclo[4.3.0]ketones by two recombinant E. coli strains. A novel access to indole alkaloids
Mihovilovic, Marko D.,Müller, Bernhard,Kayser, Margaret M.,Stanetty, Peter
, p. 700 - 702 (2007/10/03)
Recombinant Escherichia coli overexpressing Pseudomonas sp. NCIMB 9872 cyclopentanone monooxygenase (CPMO; E.C. 1.14.13.16) and Acinetobacter sp. NCIMB 9871 cyclohexanone monooxygenase (CHMO; E.C. 1.14.13.22) have been utilized in whole-cell biotransforma
Symmetry-driven synthesis of indole alkaloids: Asymmetric total synthesis of (+)-yohimbine, (-)-yohimbone, (-)-yohimbane, and (+)-alloyohimbane
Aube,Ghosh,Tanol
, p. 9009 - 9018 (2007/10/02)
Total asymmetric syntheses of the target alkaloids are reported. The syntheses involve the preparation of enantiomerically pure (S,S)-1,3,3a,4,7,7a-hexahydro-2(H)-inden-2-one 7 and its meso isomer 5. Each ketone is then converted into a ring-expanded lactam using an oxaziridine synthesis/rearrangement protocol. The applications of Bischler-Napieralski ring constructions along with appropriate functional group transformations afford enantiomerically enriched alloyohimbane or yohimbane from the meso-or C2-symmetric ketones, respectively. A cis-5,6-diacetoxy compound (18) derived from the (S,S)-ketone served as the starting material for the total syntheses of the more highly functionalized alkaloids. Accordingly, a site-specific insertion of the indole-containing side chain was accomplished via stereoselective formation of an oxaziridine followed by its stereospecific rearrangement. The selectivity of this sequence allowed for the differentiation of alcohols at C-17 and C-18 (yohimbine numbering) and the synthesis of Δ18,19-yohimbone. This α,β-unsaturated ketone was converted into either (-)-yohimbone or (+)-yohimbine using standard chemistry.
EFFICIENT PREPARATION OF NEW CHIRAL SYNTHONS USEFUL FOR (+)-CARBACYCLIN SYNTHESIS BY UTILIZING ENZYMATIC HYDROLYSIS OF PROCHIRAL ?-SYMMETRIC DIESTERS
Nagao, Yoshimitsu,Kume, Masaharu,Wakabayashi, Robin Chikako,Nakamura, Takeshi,Ochiai, Masahito
, p. 239 - 242 (2007/10/02)
Enzymatic hydrolyses of some prochiral ?-symmetric dimethyl esters employing porcine liver esterase and porcine pancreatic lipase were investigated, resulting in the enantioselective preparation of the corresponding new monoesters useful for (+)-carbacycl
ISOMERIC CIS-BICYCLONONADIENES
Gevorkyan, G. G.,Belikova, N. A.,Bobyleva, A. A.,Pekhk, T. I.,Anfilogova, S. N.,et al.
, p. 1583 - 1588 (2007/10/02)
cis-Bicyclonona-2,7-dienes and the corresponding 2,8-dienes were obtained by the isomerization of cis-bicyclonona-3,7-diene and dehydration of the cis-bicyclonon-7(8)-en-3-ols.The 13C and PMR spectra of the isomeric dienes were investigated, and their retention times in GLC analysis were determined.The reaction of cis-bicyclonona-3,7-diene with N-bromosuccinimide in aqueous DMSO and the reaction of cis-bicyclonona-2,7-diene with acetic acid were studied.
ADDITION OF HYDROGEN BROMIDE TO CIS-BICYCLONONA-3,7-DIENE. SYNTHESIS OF 5-BROMOBREXANE AND BREXAN-5-ONE
Dubitskaya, N. F.,Khaibullina, E. A.,Pekhk, T. I.,Grishin, Yu. K.,Belikova, N. A.,Bobyleva, A. A.
, p. 1589 - 1593 (2007/10/02)
The addition of hydrogen bromide to cis-bicyclonona-3,7-diene takes place preferentially but not selectively at the double bond of the six-membered ring.In the case of gaseous hydrogen bromide only bromobicyclononenes are formed, but with 48percent aqueous hydrobromic acid the reaction is accompanied by transannular cyclization and by the formation of endo- and exo-5-bromobrexanes (16-20percent).A method is proposed for the production of brexan-5-one.
TRANSANNULAR CYCLIZATION OF 3-METHYL-cis-BICYCLONONA-2,7-DIENE AND 3-METHYL- AND 3,4-DIMETHYL-cis-BICYCLONONA-3,7-DIENES. SYNTHESIS OF 5-SUBSTITUTED BREXANES
Anfilogova, S. N.,Nigmatova, V. B.,Pekhk, T. I.,Belikova, N. A.,Koptev, D. A.
, p. 1708 - 1713 (2007/10/02)
The reaction of formic acid and acetic acid with 3-methyl-cis-bicyclonona-2,7-diene, 3-methyl- and 3,4-dimethyl-cis-bicyclonona-3,7-dienes, and 3-methyl-cis-bicyclonon-7-en-3-ol leads to the exclusive formation of esters of 1-methyl- or 1,9-dimethyl-exo-brexan-5-ol with yields of 80-90percent.The reaction can be used as a convenient preparative method for the synthesis of 5-substituted brexanes.
