500-23-2Relevant academic research and scientific papers
A step toward polytwistane: Synthesis and characterization of C 2-symmetric tritwistane
Olbrich, Martin,Mayer, Peter,Trauner, Dirk
supporting information, p. 108 - 112 (2014/01/06)
Twistane is a classic hydrocarbon with fascinating stereochemical properties. Herein we describe a series of oligomers of twistane that converges on a chiral nanorod, which we term polytwistane. A member of this series, C 2-symmetric tritwistane, has been synthesized for the first time. This journal is The Royal Society of Chemistry.
Regio- and enantioselective linear cross-dimerizations between conjugated dienes and acrylates catalyzed by new Ru(0) complexes
Hiroi, Yuki,Komine, Nobuyuki,Komiya, Sanshiro,Hirano, Masafumi
, p. 6604 - 6613 (2015/02/19)
New naphthalene complexes of Ru(0) with various Ru(π6-naphthalene)(cyclic diene) (3) ligands catalyze linear cross-dimerization between conjugated dienes and acrylates. One of the noteworthy catalysts is the dibenzocyclooctatetraene complex 3d,
1-Benzenesulfonyl-2-trimethylsilylacetylene: a New Acetylene Equivalent for the Diels-Alder Reaction
Williams, Richard Vaughan,Chauhan, Kamlesh,Gadgil, Vijay R.
, p. 1739 - 1740 (2007/10/02)
1-Benzenesulfonyl-2-trimethylsilylacetylene has been shown to be an effective acetylene equivalent for the Diels-Alder reaction.
REACTION OF MERCURY SALTS WITH BICYCLOOCTA-2,5-DIENE
Kartashov, V. R.,Sokolova, T. N.,Timofeev, I. V.,Grishin, Yu. K.,Bazhenov, D. V.,Zefirov, N. S.
, p. 1838 - 1842 (2007/10/02)
It was established by 1H, 13C, and 199Hg NMR spectroscopy that the principal pathway in the reaction of mercury salts with bicyclooctadiene is the formation of products with an endo orientation of the mercury atom.On the whole, a mixture of cis adducts and a trans adduct is formed in the mercuration of bicyclooctadiene.
The Radical Cations of Bicyclohepta-2,5-diene (8,9,10-Trinorborna-2,5-diene) and Bicycloocta-2,5-diene (2,3-Dihydrobarrelene). An ESR and ENDOR Study
Gerson, Fabian,Qin, Xue-Zhi
, p. 383 - 390 (2007/10/02)
The radical cation of bicyclohepta-2,5-diene (8,9,10-trinorborna-2,5-diene; 1) in CF2ClCFCl2 and CF3CCl3 matrices and that of bicycloocta-2,5-diene (2,3-dihydrobarrelene; 2) in CFCl3 and CF3CCl3 matrices have been studied by ESR and ENDOR spectroscopy.For 1+., the coupling constants of the olefinic, methano-bridge, and bridgehead protons are -0.780 +/- 0.005, +0.304 +/- 0.002, and -0.049 +/- 0.002 mT, respectively.The hyperfine tensor for the methano-bridge protons is axial.A = +0.263 +/- 0.002 and A = +0.386 +/- 0.002 mT, while that for the olefinic protons is orthorhombic, Ax = -0.594 +/- 0.005, Ay = -0.913 +/-0.005, and Az = -0.834 +/- 0.005 mT (x parallel to C-H bond, z parallel to 2p? axis).For 2+., the coupling constants of the olefinic, ethano-bridge, and bridgehead protons are -0.68 +/- 0.01, +0.162 +/- 0.005, and -0.108 +/- 0.005 mT, respectively.The hyperfine data for 1+. and 2+. fully support the presentation of their singly occupied orbitals as antisymmetric combinations, b2(?), of the two bonding ethene ?-MO's.
Cyclic Olefins by Anodic Oxidation of β-(Trimethylsilyl)carboxylic Acids. - β-(Trimethylsilyl)acrylic Acid Derivatives as Acetylene Equivalents in Diels-Alder Reactions
Hermeling, Dieter,Schaefer, Hans J.
, p. 1151 - 1158 (2007/10/02)
Trimethylsilyl-substituted dienophiles 1, 2, and 4 react with dienes 6-14 in 66-100percent yields to give β-trimethylsilyl-substituted carboxylic acids 15-25, some of which are hydrogenated to 26-31.These are decarboxylated-desilylated to cyclic olefins 35-47 by Non-Kolbe electrolysis in 45-91percent yields.The dienophiles 1, 2, and 4 are thus suitable acetylene equivalents for Diels-Alder reactions.
(Z)- and (E)-1,2-Bis(phenylsulfonyl)ethylenes as Synthetic Equivalents to Acetylene as Dienophile
Lucchi, Ottorino De,Lucchini, Vittorio,Pasquato, Lucia,Modena, Giorgio
, p. 596 - 604 (2007/10/02)
A new method for introducing an ethylenic bridge via a cycloaddition reaction has been developed.It makes use of either (Z)- or (E)-1,2-bis(phenylsulfonyl)ethylene (5 or 6) as synthetic equivalents of acetylene.The high activation due to the two sulfonyl groups promotes cycloaddition even to very unreactive dienes.The removal of the two sulfonyl groups for the required formation of the carbon-carbon double bond is promoted by reduction with metal amalgams in high yields.These properties, associated with the stability of the reagents and the ease of performance of the reactions, make this method a very useful synthetic tool for the preparation of polycyclic dienes and a valid alternative to the commonly available reagents that largely depend upon oxidative methods.
SYNTHESIS OF TETRACYCLO2,4.03,6>OCT-7-ENE AND SOME OF ITS DERIVATIVES
Stapersma, J.,Rood, I. D. C.,Klumpp, G. W.
, p. 191 - 199 (2007/10/02)
A full account is given of the synthesis of the title compound, its 7,8-dihydro-analogue and of some of its derivatives.
cis-1,2-Bis(phenylsulfonyl)ethylene: a Novel, Convenient Acetylene Synthon in Diels-Alder Reactions
Lucchi, Ottorino De,Modena, Giorgio
, p. 914 - 915 (2007/10/02)
cis-1,2-Bis(phenylsulfonyl)ethylene (5) is found to be a reactive acetylene synthon in Diels-Alder reactions since, after cycloaddition to cyclopentadiene, cyclohexadiene, and cycloheptatriene, and reduction with sodium amalgam, the corresponding bicyclodienes (6)-(8) are obtained in good yields.
Electronic Structure of Symmetric Homocojugated Dienes. Circular Dichroism of (1S)-2-Deuterio- and 2-Methylnorbornadiene and (1S)-2-Deuterio- and 2-Methylbicyclooctadiene
Lightner, David A.,Gawronski, Jacek K.,Bouman, Thomas D.
, p. 5749 - 5754 (2007/10/02)
(1S)-Bicyclohepta-2,5-diene (1), (1S)-2-methylbicyclohepta-2,5-diene (3), (1S)-bicycloocta-2,5-diene (4), and (1S)-2-methylbicyclooctadiene (6) were prepared by reaction of the corresponding chiral β,γ-unsaturated ketone tosylhydrazone with CH3Li followed by either D2O or CH3I quenching.The circular dichroism Cotton effects of 1 (Δε237 = -0.032, Δε216 = +0.14, Δε205 = -0.37) and 4 (Δε222 = -0.027) are the first examples obtained from deuterated olefins or dienes whose chirality is due only to isotopic substitution.Both the deuterated and the methylated dienes exhibited multiple Cotton effects (3, Δε249 = +2.38, Δε222 = -0.25, Δε219 = -0.54, Δε214 = +0.62, Δε204 = -0.94; 6, Δε231 = +0.90, Δε211 = +0.48, Δε200 = -0.24), demonstrating the existence of interchromophoric interaction and electronic transitions that are only difficulty seen in their ultraviolet spectra.We present ab initio localized orbital RPA calculations on 1 that allow a consistent assignment of norbornadiene transitions.
