Search results for " rearrangement"

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…

Proton Acid-Catalysed Transformations of Estrogen Derivatives: New Results and Some Mechanistic Aspects of theKober Colour Reaction

1994

The 3-O-methylated estrogen derivatives 1a-d and α-estradiol (1e) underwent sulfuric acid-catalysed transformations to furnish the steroids 2–6. The processes involved in the reaction sequence are regioselective sulfonation and, above all, the Wagner-Meerwein rearrangement of the methyl group at C-13. With the objective of obtaining further information on the course of the Kober colour reaction of estrogens, some UV/VIS and ESR spectroscopic investigations were also carried out. Protonenkatalysierte Transformationen von Estrogen-Derivaten: Neue Ergebnisse und einige mechanistische Aspekte der Kober-Farbreaktion Die O-methylierten Estrogenderivate 1a-d und α-Estradiol (1e) reagieren in Schwe…

Some applications of the Chambers isoperimetric inequality

2022

In this paper, using the Chambers isoperimetric inequality, we introduce the notion of weighted rearrangement of a function associated to the measure $f dx$, where $f(x)=e^{g(|x|)}$ for $x \in \mathbb{R}^n}$, with $g$ smooth, convex and even. Then we give some of its applications to variational inequalities and PDEs via weighted symmetrization.

Assessing chromosome modifications in GM plants

2012

Synthesis of Spirovetivane Sesquiterpenes from Santonin. Synthesis of (+)-Anhydro-β-rotunol and All Diastereomers of 6,11-Spirovetivadiene

2004

The synthesis of the spirovetivane sesquiterpenes (+)-anhydro-beta-rotunol and all the diastereomers of 6,11-spirovetivadiene in enantiomerically pure form has been achieved starting from santonin. The key step is the silicon-guided acid-promoted rearrangement of a 1-trimethylsilyl-4,5-epoxyeudesmane prepared from santonin in several steps involving lactone reductive opening, conjugate addition of TMSLi-CuCN, deoxygenation of a carbonyl group, and epoxidation. Rearrangement of the epoxide gave a spiro[4,5]decanediol which was used as a synthetic intermediate. From this compound, (+)-anhydro-beta-rotunol was prepared after elimination of the primary hydroxyl group in the side chain, followed…