Silver and Brønsted acid catalyzed nazarov-type cyclizations to generate benzofulvenes.

Benzofulvenes are valuable compounds that have found various applications in organometallic chemistry as precursors of indenyl ligands, and in materials science. Their preparations traditionally rely on the transformation of indane or indanone derivatives. Nevertheless, a few methods based on the direct formation of the benzofulvene framework from mono or acyclic precursors have been described. The exocyclic double bond of benzofulvenes may also be introduced directly using allenes or higher cumulenes. The allenic version of the 4p electrocyclization of arylprop-2-ene-1-yl cations by a Nazarov-type reaction, that is, the transformation of arylbuta-2,3-dienyl cations, would provide a direct route to benzofulvenes (Scheme 1). Early

[1]  R. Sarpong,et al.  An approach to the synthesis of dimeric resveratrol natural products via a palladium-catalyzed domino reaction. , 2009, Tetrahedron letters.

[2]  T. Fukuyama,et al.  Generation and trapping of cyclopentenylidene gold species: four pathways to polycyclic compounds. , 2009, Journal of the American Chemical Society.

[3]  S. Luo,et al.  Chiral primary-tertiary diamine catalysts derived from natural amino acids for syn-aldol reactions of hydroxy ketones. , 2009, The Journal of organic chemistry.

[4]  M. Shi,et al.  Lewis acid or Brønsted acid catalyzed reactions of vinylidene cyclopropanes with activated carbon-nitrogen, nitrogen-nitrogen, and iodine-nitrogen double-bond-containing compounds. , 2009, Chemistry.

[5]  E. Derat,et al.  Water dissociation on alpha1-hafnium and ytterbium substituted Dawson polyoxotungstates: a density functional theory study. , 2008, The journal of physical chemistry. A.

[6]  A. Togni,et al.  Ni(II)-catalyzed enantioselective Nazarov cyclizations. , 2008, Chemical communications.

[7]  N. Mizuno,et al.  Synthesis and catalysis of di- and tetranuclear metal sandwich-type silicotungstates [(gamma-SiW10O36)2M2(mu-OH)2]10- and [(gamma-SiW10O36)2M4(mu4-O)(mu-OH)6]8- (M = Zr or Hf). , 2008, Journal of the American Chemical Society.

[8]  A. S. Dudnik,et al.  Metal-catalyzed 1,2-shift of diverse migrating groups in allenyl systems as a new paradigm toward densely functionalized heterocycles. , 2008, Journal of the American Chemical Society.

[9]  H. Alt,et al.  The combination of mononuclear metallocene and phenoxyimine complexes to give trinuclear catalysts for the polymerization of ethylene , 2007 .

[10]  F. West,et al.  Interrupted nazarov reactions using dichlorocyclopropanes: a novel mode of arene trapping. , 2007, Organic letters.

[11]  Ming-Jung Wu,et al.  Synthesis of benzofulvenes by palladium-catalyzed cyclization of 1,2 -dialkynylbenzenes , 2007 .

[12]  B. Nachtsheim,et al.  Chiral Brønsted acids in the catalytic asymmetric Nazarov cyclization--the first enantioselective organocatalytic electrocyclic reaction. , 2007, Angewandte Chemie.

[13]  Magnus Rueping,et al.  Chirale Brønsted‐Säuren in der katalytischen asymmetrischen Nazarov‐Reaktion – die erste enantioselektive organokatalytische elektrocyclische Reaktion , 2007 .

[14]  Jun Hee Lee,et al.  Gold(I)-catalyzed synthesis of functionalized cyclopentadienes. , 2007, Angewandte Chemie.

[15]  S. Fujii,et al.  Domino Heck-C-H activation reaction of unsymmetrically substituted [3]cumulene. , 2006, Chemical communications.

[16]  M. Malacria,et al.  Lanthanide complexes of the monovacant Dawson polyoxotungstate [alpha1-P2W17O61]10- as selective and recoverable Lewis acid catalysts. , 2006, Angewandte Chemie.

[17]  A. Guarna,et al.  The Lewis acid-catalyzed nazarov reaction of 2-(n-methoxycarbonylamino)-1,4-pentadien-3-ones. , 2006, Organic letters.

[18]  Christina G. Collison,et al.  The Nazarov Cyclization in Organic Synthesis. Recent Advances , 2005 .

[19]  M. Tius.  Some New Nazarov Chemistry , 2005 .

[20]  S. V. Kovalenko,et al.  Synthesis of selectively deuterated fulvenes and indenes from enediynes. , 2005, Organic & biomolecular chemistry.

[21]  D. Trauner,et al.  Enantioselective Nazarov reactions through catalytic asymmetric proton transfer. , 2004, Journal of the American Chemical Society.

[22]  M. Manoharan,et al.  5-Exo-dig radical cyclization of enediynes: the first synthesis of tin-substituted benzofulvenes. , 2004, Organic letters.

[23]  R. Eisenberg,et al.  Efficient catalysis of Nazarov cyclization using a cationic iridium complex possessing adjacent labile coordination sites. , 2004, Journal of the American Chemical Society.

[24]  V. Aggarwal,et al.  Catalytic asymmetric Nazarov reactions promoted by chiral Lewis acid complexes. , 2003, Organic letters.

[25]  P. Schreiner,et al.  Fulvenes from enediynes: regioselective electrophilic domino and tandem cyclizations of enynes and oligoynes. , 2003, Angewandte Chemie.

[26]  P. Schreiner,et al.  Fulvene aus Endiinen: Regioselektive elektrophile Domino‐ und Tandemcyclisierungen von Eninen und Oligoinen , 2003 .

[27]  M. Casolaro,et al.  Synthesis and characterization of a new benzofulvene polymer showing a thermoreversible polymerization behavior. , 2003, The Journal of organic chemistry.

[28]  T. Nakano,et al.  Dibenzofulvene, a 1,1-diphenylethylene analogue, gives a pi-stacked polymer by anionic, free-radical, and cationic catalysts. , 2001, Journal of the American Chemical Society.

[29]  M. Döring,et al.  Direct transformation of silyl enol ethers into functionalized allenes. , 2001, Chemistry.

[30]  P. Gaede.  Syntheses and crystal structures of ferrocene substituted indenyl complexes , 2000 .

[31]  Peter G. Jones,et al.  Palladium-catalyzed arylation of butadiynes , 2000 .

[32]  G. Bazan,et al.  FULVENE TO CYCLOPENTADIENYL CONVERSION WITH HOMOLEPTIC COMPLEXES OF ZIRCONIUM AND HAFNIUM , 1999 .

[33]  J. A. Marshall,et al.  Observations Regarding the Ag(I)-Catalyzed Conversion of Allenones to Furans , 1994 .

[34]  J. A. Marshall,et al.  Stereoselective synthesis of 2,5-dihydrofurans by sequential SN2' cleavage of alkynyloxiranes and silver(I)-catalyzed cyclization of the allenylcarbinol products , 1993 .

[35]  F. Toda,et al.  The Solvent Effect on the Reaction of 1,1,4,4-Tetraphenyl-2-halobuta-2,3-dien-1-ol with Mercuric Halide , 1971 .

[36]  N. Krause,et al.  Stereoselective Synthesis of Conjugated Bisallenols as Precursors of Novel Bis(2,5‐dihydrofuran) Derivatives , 2009 .

[37]  P. Langer.  Synthesis and domino reactions of 1,1-bis(hydroxymethyl)allenes , 1999 .

[38]  M. Ishikura,et al.  A novel one-pot route to cyclopenta [b]indole via the palladium-catalysed carbonylative cross-coupling reaction of indolylborate with prop-2-ynyl carbonate , 1996 .

[39]  L. Olsson,et al.  Synthesis of 2,5-Dihydrofurans and 5,6-Dihydro-2H-pyrans by Silver(I)-Catalyzed Cyclization of Allenic Alcohols , 1979 .