Structure-Elucidating Total Synthesis of the (Polyenoyl)tetramic Acid Militarinone C§.

The (polyenoyl)tetramic acid militarinone C (1) heads a family of seven members. Before our work, the configuration of C-5 was unknown whereas the configurations of C-8' and C-10' were either (R,R) or (S,S). We synthesized the four stereoisomers of constitution 1, which conform with these insights. This included cross-coupling both enantiomers of the western building block (8) with both enantiomers of the eastern building block (9). The specific rotations of the resulting 1 isomers suggested that natural 1 is configured like the coupling partners (S)-8 and (R,R)-9. This conclusion was corroborated by degrading natural 1 to alcohol 35 and by proving its configurational identity with synthetic (R,R)-35.

[1]  R. Schobert,et al.  Synthesis of the Entomopathogenic Fungus Metabolites Militarinone C and Fumosorinone A. , 2018, The Journal of organic chemistry.

[2]  Wen‐Ju Bai,et al.  Recent Advances in the Total Synthesis of Tetramic Acid-Containing Natural Products , 2016 .

[3]  Chengshu Wang,et al.  Structure and biosynthesis of fumosorinone, a new protein tyrosine phosphatase 1B inhibitor firstly isolated from the entomogenous fungus Isaria fumosorosea. , 2015, Fungal genetics and biology : FG & B.

[4]  T. Sim,et al.  A Concise and Efficient Total Synthesis of Militarinone D , 2015 .

[5]  Max L. Hofferberth,et al.  α- und β-Lipomycin: Totalsynthesen auf der Grundlage sequentieller Stille-Kupplungen und Zuordnung der absoluten Konfiguration aller stereogenen Zentren† , 2014 .

[6]  R. Brückner,et al.  α- and β-Lipomycin: total syntheses by sequential stille couplings and assignment of the absolute configuration of all stereogenic centers. , 2014, Angewandte Chemie.

[7]  H. W. Lam,et al.  Enantioselective synthesis of allylboronates and allylic alcohols by copper-catalyzed 1,6-boration. , 2014, Angewandte Chemie.

[8]  Xue‐Wei Liu,et al.  Directed orthometalation and the asymmetric total synthesis of N-deoxymilitarinone A and torrubiellone B. , 2014, Organic letters.

[9]  A. Schumacher,et al.  Ein einheitlicher Ansatz zur stereoselektiven Totalsynthese von Pyridonalkaloiden und deren neuritogene Aktivität , 2011 .

[10]  K. Gademann,et al.  A unified approach for the stereoselective total synthesis of pyridone alkaloids and their neuritogenic activity. , 2011, Angewandte Chemie.

[11]  O. Piva,et al.  Application of the diastereoselective photodeconjugation of α,β-unsaturated esters to the synthesis of gymnastatin H , 2011, Beilstein journal of organic chemistry.

[12]  Xingzhong Liu,et al.  N-hydroxypyridones, phenylhydrazones, and a quinazolinone from Isaria farinosa. , 2011, Journal of natural products.

[13]  M. Moloney,et al.  Synthesis of and tautomerism in 3-acyltetramic acids. , 2011, The Journal of organic chemistry.

[14]  K. Mori,et al.  Pheromone synthesis. Part 245: Synthesis and chromatographic analysis of the four stereoisomers of 4,8-dimethyldecanal, the male aggregation pheromone of the red flour beetle, Tribolium castaneum , 2011 .

[15]  L. Dubost,et al.  Total Synthesis of Tyrosine‐Derived Tetramic Acid Pigments from a Slime Mould , 2010 .

[16]  R. Schobert,et al.  Toward the macrocidins: macrocyclization via Williamson etherification of a phenolate. , 2010, The Journal of organic chemistry.

[17]  K. Gademann,et al.  4-Hydroxy-2-pyridone alkaloids: structures and synthetic approaches. , 2010, Natural product reports.

[18]  Hiromitsu Sogawa,et al.  Tyrosine-based poly(m-phenyleneethynylene-p-phenyleneethynylene)s. Helix folding and responsiveness to a base , 2010 .

[19]  Alan H. Cherney,et al.  Stereoretentive Suzuki-Miyaura coupling of haloallenes enables fully stereocontrolled access to (-)-peridinin. , 2010, Journal of the American Chemical Society.

[20]  B. Breit,et al.  Direct assignment of the relative configuration in 1,3,n-methyl-branched carbon chains by (1)H NMR spectroscopy. , 2010, Organic letters.

[21]  V. Sepe,et al.  Synthetic studies on homophymine A: stereoselective synthesis of (2R,3R,4R,6R)-3-hydroxy-2,4,6-trimethyloctanoic acid , 2009 .

[22]  R. Schobert,et al.  Tetramic and tetronic acids: an update on new derivatives and biological aspects. , 2008, Bioorganic & medicinal chemistry.

[23]  R. Schobert.  Domino syntheses of bioactive tetronic and tetramic acids , 2006, Naturwissenschaften.

[24]  R. K. Boeckman,et al.  Toward the development of a general chiral auxiliary. Enantioselective alkylation and a new catalytic asymmetric addition of silyloxyfurans: application to a total synthesis of (-)-rasfonin. , 2006, Journal of the American Chemical Society.

[25]  B. Schneider,et al.  (+)-N-Deoxymilitarinone A, a neuritogenic pyridone alkaloid from the insect pathogenic fungus Paecilomyces farinosus. , 2006, Journal of natural products.

[26]  Reinhard Brückner,et al.  Totalsynthese von Xerulinsäure , 2004 .

[27]  R. Brückner,et al.  Total synthesis of xerulinic acid. , 2004, Angewandte Chemie.

[28]  M. Hamburger,et al.  Novel tetramic acids and pyridone alkaloids, militarinones B, C, and D, from the insect pathogenic fungus Paecilomyces militaris. , 2003, Journal of natural products.

[29]  J. A. Marshall,et al.  Total synthesis of (-)-callystatin A. , 2002, The Journal of organic chemistry.

[30]  W. Günther,et al.  Militarinone A, a neurotrophic pyridone alkaloid from Paecilomyces militaris. , 2002, Organic letters.

[31]  Andrew Kopecky,et al.  Pseudoephedrine as a Practical Chiral Auxiliary for the Synthesis of Highly Enantiomerically Enriched Carboxylic Acids, Alcohols, Aldehydes, and Ketones , 1997 .

[32]  R. W. Hoffmann,et al.  Assignment of Relative Configuration to Acyclic Compounds Based on (13)C NMR Shifts. A Density Functional and Molecular Mechanics Study. , 1996, The Journal of organic chemistry.

[33]  K. Mori,et al.  Synthesis of the three stereoisomers of auxin-glutaric acid to confirm the non-existence of Kögl's auxin-a and -b , 1991 .

[34]  D. Norbeck,et al.  Application of the Swern oxidation to the manipulation of highly reactive carbonyl compounds , 1985 .