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131.
Laurence Miesch Dr. Tania Welsch Vincent Rietsch Michel Miesch Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(17):4394-4401
Selecting the ring : tert‐Butyldimethylsilyltriflate (TBSOTf)/NEt3 treatment of alkynyl esters tethered to bicycloalkanones leads to the formation of tricyclic allenoates with total diasteroselectivity at the ring junction. An intramolecular alkynylogous Mukaiyama aldol reaction promoted by a TBSOTf/NEt3 dual activation is involved. This novel methodology was illustrated by a formal total synthesis of (±)‐hamigeran B.
132.
In a previous contribution, we have reported on a convenient and high yield synthesis of the disilene trans-[(TMS)(2)N(η(1)-Me(5)C(5))Si═Si(η(1)-Me(5)C(5))N(TMS)(2)] (2). Herein, we show the reactions of 2 with N(2)O and S(8). The former reaction affords two isomeric (cis- and trans-) dioxadisiletane ring compounds. To the best of our knowledge, this is the first report where both cis-and trans-isomers are isolated from the same disilene precursor and characterized structurally by single-crystal X-ray diffraction (XRD) studies. The reaction of 2 with elemental sulfur yields only the trans-isomer. To investigate this dissimilar reaction pattern exhibited by 2, computational studies were performed. Density functional theory (DFT) calculations showed that the two dioxadisiletane ring isomers are isoenergetic, with the trans isomer being slightly more stable than the cis counterpart, by 3.3 kcal/mol, while that is not the case with sulfur. All the isolated compounds are characterized by single-crystal XRD studies, multinuclear NMR spectroscopy, and electron ionization-mass spectrometry (EI-MS). 相似文献
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134.
Stanković S Catak S D'hooghe M Goossens H Abbaspour Tehrani K Bogaert P Waroquier M Van Speybroeck V De Kimpe N 《The Journal of organic chemistry》2011,76(7):2157-2167
The synthetic utility of N-alkylidene-(2,3-dibromo-2-methylpropyl)amines and N-(2,3-dibromo-2-methylpropylidene)benzylamines was demonstrated by the unexpected synthesis of 3-methoxy-3-methylazetidines upon treatment with sodium borohydride in methanol under reflux through a rare aziridine to azetidine rearrangement. These findings stand in contrast to the known reactivity of the closely related N-alkylidene-(2,3-dibromopropyl)amines, which are easily converted into 2-(bromomethyl)aziridines under the same reaction conditions. A thorough insight into the reaction mechanism was provided by both experimental study and theoretical rationalization. 相似文献
135.
F. Peypoux M. Guinand G. Michel L. Delcambe B.C. Das P. Varenne E. Lederer 《Tetrahedron》1973,29(21):3455-3459
lturin, a peptide antibiotic from Bacillus subtilis, was separated into three iturins: A, B, C by thin-layer chromatography. Iturin A, which has an antifungal activity, contains Asp, Glu, Tyr, Ser, Pro in a molar ratio 3:1:1:1:1 and a lipid moiety AL. The latter was shown to be a mixture of C14 (40%) and C15, (60%) amino-acids. The structure of these was determined by combined gas chromatography-mass spectrometry of the N-acetylmethyl esters. Strong peaks at m/e = 144 and m/e = 102 indicate a β-amino group. Identification of acetone and methylethylketone after chromic acid oxidation indicates an iso and anteiso structure. After comparison of the natural amino-acids with synthetic 3-amino pentadecanoic acid it is concluded that the lipid AL is a mixture of 3-amino 12- methyltetradecanoic acid and 3-amino 12-methyltridecanoic acid. 相似文献
136.
Bin Lin Frej Mighri Michel A. Huneault Uttandaraman Sundararaj 《Macromolecular rapid communications》2003,24(13):783-788
The deformation and breakup of a single polycarbonate drop in a polyethylene matrix is studied at high temperatures under simple shear flow using a transparent Couette device. We observed “parallel breakup” where the drop breaks after being stretched into a thin sheet parallel to the flow. The breakup occurs at a viscosity ratio greater than 3.5. Deborah number and a stress ratio incorporating elastic moduli can characterize the “parallel breakup”.
137.
Michel Mons Evan G. Robertson Lavina C. Snoek John P. Simons 《Chemical physics letters》1999,310(5-6)
The structures of 2-phenylethanol and its 1:1 water complexes have been investigated by UV–UV holeburning and IR–UV ion-dip spectroscopy, coupled with ab initio computation. The most populated molecular conformer is stabilized by an intramolecular π-type H-bond and its rotational band contours suggest the incidence of vibronic coupling involving motion of the side chain. Its 1:1 water complexes are associated with two distinct structures – water binds either as a proton donor or an acceptor. In the latter, the intramolecular H-bond is disrupted and the water molecule inserts between the OH and the aromatic ring. A second, extended anti conformer can also be detected. 相似文献
138.
Christian Deshayes Michel Chabannet Suzanne Gelin 《Journal of heterocyclic chemistry》1986,23(5):1595-1598
The title compounds were prepared by acid-catalyzed cyclization of aryloxymethyl- or (2-arylethyl)-4-carboxymethylisoxazoles which in turn were synthesized from aryloxymethyl- or (2-arylethyl)isoxazole-4-carboxylic acids by Arndt-Eistert homologation. 相似文献
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140.