Stereoselective synthesis of conjugated α-Z/γ-E and α-Z/γ-Z dienoic acids. Kinetic torquoselectivity versus thermodynamic control

The stereoselective synthesis of conjugated (α-Z/γ-E)-(α-Z/γ-Z)-dienoic acids 4 and 4′ is described. It is based on the regio- and stereoselective addition of Grignard reagents to methylcoumalate. The origin of the stereocontrol is discussed.

[1]  K. Houk,et al.  Stereoselective synthesis of dienyl-carboxylate building blocks: formal synthesis of inthomycin C. , 2013, Organic letters.

[2]  B. Schmidt,et al.  One‐Flask Tethered Ring Closing Metathesis–Electrocyclic Ring Opening for the Highly Stereoselective Synthesis of Conjugated Z/E‐Dienes , 2012 .

[3]  R. J. Fox,et al.  (+)-Sorangicin A: evolution of a viable synthetic strategy. , 2011, Tetrahedron.

[4]  A. Fürstner,et al.  Gram-scale synthesis of iejimalide B. , 2011, Chemistry.

[5]  A. Fürstner,et al.  Stereoselective synthesis of E,Z-configured 1,3-dienes by ring-closing metathesis. Application to the total synthesis of lactimidomycin. , 2011, Journal of the American Chemical Society.

[6]  R. Goldstein,et al.  Chemoselective 1,3-dipolar cycloadditions of azomethine ylide with conjugated dienes , 2011 .

[7]  A. Goel,et al.  Natural and synthetic 2H-pyran-2-ones and their versatility in organic synthesis☆ , 2009 .

[8]  R. J. Fox,et al.  Total synthesis of (+)-sorangicin A. , 2009, Journal of the American Chemical Society.

[9]  K. Houk,et al.  Thermodynamic control of the electrocyclic ring opening of cyclobutenes: C=X substituents at C-3 mask the kinetic torquoselectivity. , 2009, Journal of the American Chemical Society.

[10]  I. V. Mineeva,et al.  Synthesis of methyl 3-bromomethylbut-3-enoate and its reactions with aldehydes and tributylchlorostannane in the presence of zinc , 2008 .

[11]  F. Castiglione,et al.  Synthesis and preliminary biological characterization of new semisynthetic derivatives of ramoplanin. , 2007, Journal of medicinal chemistry.

[12]  K. Houk,et al.  DFT study of pericyclic reaction cascades in the synthesis of antibiotic TAN-1085. , 2004, Organic letters.

[13]  Ó. Delgado,et al.  Total synthesis and configurational assignment of (-)-dictyostatin, a microtubule-stabilizing macrolide of marine sponge origin. , 2004, Angewandte Chemie.

[14]  J. Parrain,et al.  Efficient preparation of β-trifluoromethyl acrylates and derivatives via palladium cross-coupling reactions , 2003 .

[15]  Dae-Whang Kim,et al.  A New and Facile Synthesis of 2-Pyridones , 2002 .

[16]  J. Poirier,et al.  A general synthesis of (2Z)-terpenoic acids , 2000 .

[17]  J. Rodríguez-Otero.  Study of the Electrocyclization of (Z)-Hexa-1,3,5-triene and Its Heterosubstituted Analogues Based on Ab Initio and DFT Calculations. , 1999, The Journal of organic chemistry.

[18]  E. Carreira,et al.  Total Synthesis of Macrolactin A with Versatile Catalytic, Enantioselective Dienolate Aldol Addition Reactions. , 1998, Angewandte Chemie.

[19]  J. Cintrat,et al.  Efficient Synthesis of Conjugated (2E)- or (2Z)-En-4-ynoic Acids and (2E,4E)- or (2Z,4E)-Dienoic Acids via Palladium-Catalysed Cross Coupling , 1996 .

[20]  D. Spellmeyer,et al.  Transition Structures of Thermally Allowed Disrotatory Electrocyclizations. The Prediction of Stereoselective Substituent Effects in Six-Electron Pericyclic Reactions , 1995 .

[21]  Robert S. H. Liu,et al.  Stereospecific thermal rearrangement of the four labile isomers of retinal. Activation parameters and FT-IR data , 1992 .

[22]  Grety Rihs,et al.  UBER DIE REAKTION EINIGER 2H-PYRAN-2-ON-DERIVATE MIT PRIMAREN AMINEN , 1991 .

[23]  V. Kvita.  Synthese von 2(1 H )-Pyridonen aus 2 H -Pyran-2-onen , 1991 .

[24]  Grety Rihs,et al.  Eine neue Azepinring‐Synthese , 1989 .

[25]  M. Constantino,et al.  A novel synthesis of (±)-abscisic acid , 1989 .

[26]  V. Kvita,et al.  Reaktionen des Cumalinsäure-methylesters und Cumalinaldehyds mit ambidenten Nucleophilen , 1988 .

[27]  M. Nantz,et al.  Cycloaromatization Reactions of Methyl 4-Carbomethoxy-5-Methoxy-Penta-2,4-Dienoate , 1987 .

[28]  John K. Stille,et al.  The Palladium‐Catalyzed Cross‐Coupling Reactions of Organotin Reagents with Organic Electrophiles [New Synthetic Methods (58)] , 1986 .

[29]  Philip L. Fuchs,et al.  Laboratory automation. 1: syntheses via vinyl sulfones. 14. Robotic orchestration of organic reactions: yield optimization via an automated system with operator-specified reaction sequences , 1984 .

[30]  V. Kvita,et al.  Chemie der Cumalinsäurederivate. I. Synthese und Diels-Alder-Reaktionen von 1-Arylamino-2-methoxycarbonylbutadienen , 1983 .

[31]  W. C. Still,et al.  Direct synthesis of Z-unsaturated esters. A useful modification of the horner-emmons olefination. , 1983 .

[32]  A. Spada,et al.  Enantio- and stereoselective syntheses of the dihydroxyoctadienoic acid framents of the roridins and trichoverrins , 1982 .

[33]  E. Corey,et al.  Studies on the total synthesis of rifamycin. A method for the stereospecific synthesis of the carbonyl-conjugated 1,3-diene unit [C(15) to C(20)] , 1979 .

[34]  G. Cardillo,et al.  Synthesis of compounds containing the isoprene unit : A stereospecific synthesis of dehydronerol isovalerate, a component of anthemis Montana L , 1976 .

[35]  T. Gosink.  Valence isomers. Substituent effects on the equilibrium between 2H-pyrans and cis-dienones , 1974 .

[36]  A. Kluge,et al.  Mechanism of photoisomerization of 3,5-heptadienone , 1971 .

[37]  A. Kluge,et al.  Molecular spectra and conformations of conjugated dienones , 1971 .

[38]  G. Vogel.  Reaction of 2-Pyrones with Cyanide Ion1 , 1965 .

[39]  R. Gompper,et al.  Pyrane, II. Neue Synthese aromatischer Kohlenwasserstoffe , 1961 .

[40]  R. Gompper,et al.  Pyrane, I. a- und ?-Pyrane , 1961 .

[41]  R. H. Wiley,et al.  2-Pyrones. VII. 2-Pyridones from 2-Pyrones , 1954 .

[42]  W. T. Caldwell,et al.  Substituted 2-Sulfonamido-5-aminopyridines. II , 1942 .