Synthetic Studies Directed Towards Various Homologues of Natural Sesquiterpene‐Coumarin Ethers: The Domino Approach

A domino-based strategy was used to construct analogues containing the basic skeleton of the monocyclic sesquiterpene-coumarin ethers galbanic acid (1) and secodrial (3), through conversion of the domino adduct 19 into 10 and 11, chosen as representative targets. 1 H NMR patterns, corroborated by X-ray crystallographic analysis for two of the four possible diastereomeric arrangements of the six-membered B-ring common to various A-seco terpenes, have been determined. The observed trends help in the design of substituent combinations that provide a tool for diastereomeric recognition, depending on the cis/trans arrangement of the adjacent methyl groups and the adopted conformations.

[1]  M. Perez,et al.  Natural and Unnatural A-seco Terpenes from Pulegone: Synthesis of Galbanic Acid and Marneral Revisited , 2009 .

[2]  C. Liaw,et al.  Influenza A (H(1)N(1)) Antiviral and Cytotoxic Agents from Ferula assa-foetida. , 2009, Journal of natural products.

[3]  A. Corbu,et al.  Microwave-assisted domino reactions: function-compatibility, modulation, and greening efforts , 2008 .

[4]  P. Retailleau,et al.  Total synthesis and structural confirmation of ent-galbanic acid and marneral. , 2008, Organic letters.

[5]  P. Retailleau,et al.  Enantioselective synthesis of iridal, the parent molecule of the iridal triterpenoid class. , 2008, Organic letters.

[6]  A. Corbu,et al.  A domino-based approach toward stereodefined heavily functionalized cyclohexanes: synthesis of iridal's core structure. , 2007, Organic letters.

[7]  S. Danishefsky,et al.  Total synthesis of (+)-suaveolindole: establishment of its absolute configuration. , 2007, Journal of the American Chemical Society.

[8]  G. Appendino,et al.  A meroterpenoid NF-kappaB inhibitor and drimane sesquiterpenoids from Asafetida. , 2006, Journal of natural products.

[9]  K C Nicolaou,et al.  Chasing molecules that were never there: misassigned natural products and the role of chemical synthesis in modern structure elucidation. , 2005, Angewandte Chemie.

[10]  M. O'Neil-Johnson,et al.  Suaveolindole, a new mass-limited antibacterial indolosesquiterpene from Greenwayodendron suaveolens obtained via high-throughput natural products chemistry methods. , 2005, Journal of natural products.

[11]  T. K. Khasanov,et al.  Structure and configuration of the coumarins mogoltadone and mogoltadin , 2004, Chemistry of Natural Compounds.

[12]  N. Birlirakis,et al.  An efficient one-pot approach to bridged bicyclic ring-systems through consecutive hetero-domino transformations: a mechanistic rationale and further rearrangements. , 2003, Chemistry.

[13]  J. Reymond,et al.  Synthesis and Evaluation of Chromogenic and Fluorogenic Analogs of Glycerol for Enzyme Assays , 2003 .

[14]  H. Schmickler,et al.  Determination of the Absolute Configuration of Hydroxyiridals by Chiroptical and NMR Spectroscopic Methods , 2003 .

[15]  S. Arseniyadis,et al.  Taxoid C-ring building blocks from Hajos–Parrish ketone. Practical synthesis of an enantiomerically pure taxoid ABC ring system , 1999 .

[16]  S. Ryu,et al.  Reinvestigation of the Structure of Galbanic Acid by 2D NMR Techniques Including 2D INADEQUATE. , 1998 .

[17]  L. Tietze.  Domino Reactions in Organic Synthesis. , 1996, Chemical reviews.

[18]  G. Appendino,et al.  Sesquiterpene coumarin ethers from asafetida , 1993 .

[19]  R. M. King,et al.  New diterpenes from and , 1986 .

[20]  F. Marner,et al.  Irigermanal and iridogermanal: two new triterpenoids from rhizomes of Iris germanica L , 1982 .

[21]  J. Bunnett,et al.  Thermolysis of arenediazonium salts in acidic methanol. Effects of substituents, atmospheres, and added substances on the competition between ionic and radical mechanisms , 1977 .

[22]  D. Olsen,et al.  Total stereoselective synthesis of .alpha.-atlantone , 1974 .

[23]  W. Lehnert.  Knoevenagel-kondensationen mit TiCl4/base—III : Umsetzungen von ketonen und α-halogenketonen mit malonester , 1973 .

[24]  G. Buchi,et al.  New synthesis of cyclopentenones. Methyl jasmonate and jasmone , 1971 .

[25]  F. Johnson.  Allylic strain in six-membered rings , 1968 .