Search results for "Rearrangement"
showing 10 items of 298 documents
Use of a bulky phosphine of weak σ-donicity with palladium as a versatile and highly-active catalytic system: allylation and arylation coupling react…
2005
Abstract Carbon–carbon(sp2–sp2 and sp1–sp2) and carbon–nitrogen (nucleophilic allylation) coupling processes are promoted by a catalytic system containing [PdCl(η3–C3H5)]2 with the new ferrocenyl bis(difurylphosphine) 1,1′-bis[di(5-methyl-2-furyl)phosphino]ferrocene, Fc[P(FuMe)2]2. Starting from aryl bromides or allylic acetates this versatile catalyst system may be used at low palladium loadings (10−1–10−4 mol%) in some Heck, Suzuki, Sonogashira and allylic amination reactions to give cross-coupled products in excellent yield. Remarkably high activity is obtained in allylic substitution reactions, providing a significant impetus for the development of bulky phosphines possessing weak σ-don…
N1-Functionalized Indole-Phosphane Oxazoline (IndPHOX) Ligands in Asymmetric Allylic Substitution Reactions
2012
N-Functionalized IndPHOX ligands bearing various groups have been synthesized and the effects of the N1-substituent on the reaction rate, yield, and asymmetric induction in a palladium-catalyzed allylic substitution reaction are reported. The presence of an oxygen atom in the ligands, namely an N-MOM or N-THP group, led to enhancement of the enantioselectivity in the allylic amination reaction. In addition, a ligand with a chiral oxazoline ring at C-1 and a phosphane substituent at C-2 provided high enantioselectivity in good yield in an asymmetric allylic alkylation reaction.
ChemInform Abstract: N1-Functionalized Indole-Phosphane Oxazoline (IndPHOX) Ligands in Asymmetric Allylic Substitution Reactions.
2012
N-Functionalized IndPHOX ligands bearing various groups have been synthesized and the effects of the N1-substituent on the reaction rate, yield, and asymmetric induction in a palladium-catalyzed allylic substitution reaction are reported. The presence of an oxygen atom in the ligands, namely an N-MOM or N-THP group, led to enhancement of the enantioselectivity in the allylic amination reaction. In addition, a ligand with a chiral oxazoline ring at C-1 and a phosphane substituent at C-2 provided high enantioselectivity in good yield in an asymmetric allylic alkylation reaction.
On the Reaction of 3-Bromo-2-nitrobenzo[b]thiophene 13C-Labeled at C-2 with 3-(Trifluoromethyl)aniline: A Preliminary Insight into a Nucleophilic Su…
1997
The results of the title reaction have furnished proofs against a rearrangement of the carbon-atom skeleton and for a nitro group shift in the relevant nucleophilic substitution.
Asymmetric Conjugate Addition of Malonate Esters to α,β-UnsaturatedN-Sulfonyl Imines: An Expeditious Route to Chiral δ-Aminoesters and Piperidones
2013
The asymmetric conjugate addition of malonate esters to α,β-unsaturated N-sulfonyl imines is catalyzed by PyBOX/La(OTf)3 complexes in the presence of 4 Å MS. The reaction gives the corresponding E enamines bearing a stereogenic center at the allylic position with good yields and enantiomeric ratios up to 97:3. This reaction provides a synthetic entry to chiral δ-aminoesters and piperidones.
ChemInform Abstract: Asymmetric Conjugate Addition of Malonate Esters to α,β-Unsaturated N-Sulfonyl Imines: An Expeditious Route to Chiral δ-Aminoest…
2014
The asymmetric conjugate addition of malonate esters to α,β-unsaturated N-sulfonyl imines is catalyzed by PyBOX/La(OTf)3 complexes in the presence of 4 A MS. The reaction gives the corresponding E enamines bearing a stereogenic center at the allylic position with good yields and enantiomeric ratios up to 97:3. This reaction provides a synthetic entry to chiral δ-aminoesters and piperidones.
A contribution to the preparation of phenolic polynuclear compounds with sulfonyl bridges
1964
For the preparation of phenolic di- and tricyclic compounds with sulfonyl bridges the Fries rearrangement is suitable, and for the corresponding products with three and four benzene rings the Friedel-Crafts reaction may be used. The exchange of sulfonyl bridges for methylene bridges produces a marked increase in the melting point.
Synthesis of Isoxazoline Derivatives through Boulton–Katritzky Rearrangement of 1,2,4-Oxadiazoles
2013
The base-induced rearrangement of 1,2,4-oxadiazoles into isoxazoline derivatives is reported. This represents the first example of a three-atom side-chain rearrangement that involves a saturated CCO side chain at C-3 of the oxadiazole. Nonaromatic 3-amino-isoxazoline derivatives are obtained in good yields. Interestingly, this reaction occurs through the rearrangement of aromatic oxadiazoles to form less stable bonds than those that are broken.
ChemInform Abstract: Synthesis of (+)-Pechueloic Acid and (+)-Aciphyllene. Revision of the Structure of (+)-Aciphyllene.
2008
Abstract 1α H ,7α H ,10α H -Guaia-4,11-dien-3-one and its 1β H ,10β H diastereomer, easily obtained from (+)-dihydrocarvone, are good starting materials for the synthesis of natural guaiane derivatives. Allylic oxidation of the 1α H ,10α H isomer gave as main product its 13-hydroxy derivative and a small amount of (+)-7β-hydroxy-1α H ,10α H -guaia-4,11-dien-3-one, whereas the 1β H ,10β H diastereomer afforded selectively the (−)-7α-hydroxy-1β H ,10β H enantiomer in excellent yield. From the 13-hydroxy derivative (+)-pechueloic acid and (+)-methyl pechueloate were synthesized. Deoxygenation at C 3 of the 1β H ,10β H guaiadienone afforded a guaiadiene with the reported structure for aciphylle…
Volume change characteristics of fine-grained soils due to sequential thermo-mechanical stresses
2019
Know-how of volume change characteristics, VCC, of the fine-grained soils, exposed to thermal stresses, is essential for design of various thermo-active structures. These stresses are known to induce excess pore-water pressure, Δu θ , in the saturated state of such soils, which in turn affects their compression and shear strength characteristics. In this context, through several experimental studies, the effect of thermo-mechanical stress-path, the over-consolidation ratio (OCR) and degree of saturation on VCC (viz., thermally induced volumetric strain, ε vθ , compression and re-compression indices, c c and c r ) of the fine-grained soils has been demonstrated by earlier researchers. Howeve…