Synthesis, structure and pyrolysis of stabilised phosphonium ylides containing saturated oxygen heterocycles.

A range of twelve stabilised phosphonium ylides containing tetrahydrofuran, tetrahydropyran or 2,2-dimethyl-1,3-dioxolane rings have been prepared and fully characterised, including one X-ray structure determination of each type. The X-ray structures confirm the P=C and C=O functions to be syn and all the compounds undergo thermal extrusion of Ph3PO to give the corresponding alkynes. In some cases there is also competing loss of Ph3P to give different carbene-derived products and evidence has been obtained for the generation of 2-phenyloxete in this way. Raising the pyrolysis temperature leads in several cases to new secondary reactions of the alkyne products involving a sequence of alkyne to vinylidene isomerisation, intramolecular CH insertion, and retro Diels Alder reaction.

[1]  Natsumi Shimizu,et al.  Catalytic asymmetric synthesis of stable oxetenes via Lewis acid-promoted [2+2] cycloaddition. , 2011, Journal of the American Chemical Society.

[2]  Israel Fernández,et al.  Fascinating reactivity in gold catalysis: synthesis of oxetenes through rare 4-exo-dig allene cyclization and infrequent β-hydride elimination. , 2011, Chemical communications.

[3]  I. Lykakis,et al.  Functionalized 3(2H)-furanones via photooxygenation of (β-keto)-2-substituted furans: application to the biomimetic synthesis of merrekentrone C. , 2011, Organic & biomolecular chemistry.

[4]  R. C. Brown,et al.  Thermal rearrangements of alkynes under FVP conditions. the acetylene-methylenecarbene rearrangement , 2010 .

[5]  Daisuke Sato,et al.  Studies toward the total synthesis of armatol F: stereoselective construction of the C6 and C7 stereocenters and formation of the A-ring skeleton , 2010 .

[6]  R. Aitken,et al.  Cascade synthesis of new tetracyclic heteroaromatic thieno[2,3-b]pyridine-containing ring systems , 2009 .

[7]  R. Aitken,et al.  New gas-phase cascade reactions of stabilized phosphorus ylides leading to ring-fused indoles and to quinolines. , 2008, The Journal of organic chemistry.

[8]  R. Aitken,et al.  Flash vacuum pyrolysis of stabilised phosphorus ylides. Part 17. Preparation of aliphatic amino acid derived γ-alkoxycarbonylamino-β-oxo ylides and pyrolysis to give α,β-acetylenic γ-amino acid and GABA analogues , 2002 .

[9]  A. Hassner,et al.  Intermolecular [3+2] MIRC reactions with alkynoates. Asymmetric Michael addition leading to a nonracemic cyclopentene-annulated α,β-butenolide , 2000 .

[10]  J. Baldwin,et al.  Synthesis of novel C-nucleosides with potential applications in combinatorial and parallel synthesis , 2000 .

[11]  W. Shen,et al.  The Stille Reaction of 1,1-Dibromo-1-alkenes: Preparation of Trisubstituted Alkenes and Internal Alkynes. , 1999, The Journal of organic chemistry.

[12]  N. Priestley,et al.  Large Scale Synthesis of Cyclodiphospho-d-glycerate , 1996 .

[13]  T. Satoh,et al.  Palladium-Catalyzed Cross-Carbonylation of Aryl Iodides with Five-Membered Cyclic Olefins , 1995 .

[14]  R. Aitken,et al.  A new general synthesis of aliphatic and terminal alkynes: flash vacuum pyrolysis of β-oxoalkylidenetriphenylphosphoranes , 1985 .

[15]  Yaozeng Huang,et al.  APPLICATION OF ELEMENTO-ORGANIC COMPOUNDS OF THE FIFTH AND SIXTH GROUPS IN ORGANIC SYNTHESES. PART 35. A CONVENIENT SYNTHESIS OF TERMINAL PERFLUOROACYLACETYLENES AND PERFLUOROALKYNALS , 1985 .

[16]  J. Crandall,et al.  Cyclizations of .omega.-allenyl radicals , 1984 .

[17]  J. Tronchet,et al.  Préparation de dérivés de sucres acétyléniques terminaux et d'acides ynuroniques par réaction de Wittig. Note de laboratoire† , 1980 .

[18]  P. Shevlin,et al.  Oxetene: synthesis and energetics of electrocyclic ring opening , 1980 .

[19]  R. S. Vartanyan,et al.  Synthesis of ethyl Β-(2,2 -dimethyltetrahydro-4-pyranyl)-Β-oxopropionate , 1979 .

[20]  T. Otsuki.  The Photochemical Raction of 2-Alkoxy-1,4-naphthoquinones with Olefins. II. The Formation of Tetrahydropyran-ring Compounds , 1974 .

[21]  P. Chopard,et al.  The Reaction of Stable Phosphoranes with Acid Anhydrides. A New Synthesis of Acetylenic Ketones , 1965 .

[22]  G. Märkl.  Synthese von α.β-Acetylencarbonsäuren durch innermolekulare Wittig-Reaktion , 1961 .

[23]  R. Aitken,et al.  Recent Advances in the Synthesis of Heterocyclic Compounds Using Flash Vacuum Pyrolysis , 2015 .

[24]  J. Gervay-Hague,et al.  An efficient method for the preparation of peracetylated Neu5Ac2en by flash vacuum pyrolysis , 2015 .

[25]  P. Lightfoot,et al.  The solid state conformation of oxo stabilised ylides: X-ray structures of four new polyoxo phosphorus ylides , 2000 .

[26]  R. Aitken,et al.  Flash vacuum pyrolysis of stabilised phosphorus ylides. Part 11.1 Unexpected generation and rearrangement of acetyl benzotriazolyl carbene , 1997 .

[27]  R. Aitken,et al.  Flash vacuum pyrolysis of stabilised phosphorus ylides. Part 2. Two-step conversion of acid chlorides into acetylenic esters and terminal alkynes , 1994 .

[28]  R. Aitken,et al.  Flash vacuum pyrolysis of stabilised phosphorus ylides. Part 1. Preparation of aliphatic and terminal alkynes , 1994 .

[29]  R. Aitken,et al.  Unexpected generation and rearrangement of acetyl benzotriazolyl carbene , 1993 .

[30]  A. Katritzky,et al.  Addition of benzotriazole to vinyl ethers. Chemistry of the adducts , 1990 .

[31]  S. Ley,et al.  Substitution reactions of 2-benzenesulphonyl cyclic ethers with carbon nucleophiles , 1989 .

[32]  R. Weiss,et al.  Photolysis of benzoylmethylene(triphenyl)phosphorane , 1973 .

[33]  H. Bestmann.  Reaktionen mit Phosphin‐alkylenen, I. Intermolekulare Umylidierung zwischen Phosphoniumsalzen und Phosphin‐alkylenen , 1962 .

[34]  D. Walker,et al.  781. The reaction of witting reagents with phenyl isocyanate , 1959 .