Search results for "metathesis"

Alkyl Complexes of Rare-Earth Metals That Contain a Furyl-Functionalized Cyclopentadienyl Ligand:  Alkyl Cation Formation and Unexpected Ring-Opening…

2003

Rare-earth metal complexes of the type [Ln{η5:η1-C5Me4SiMe2(C4H3O-2)}(CH2SiMe3)2(THF)] (Ln = Y, Lu) were prepared by σ-bond metathesis of [Ln(CH2SiMe3)3(THF)2] with the 2-furyl-functionalized tetramethylcyclopentadiene (C5Me4H)SiMe2(C4H3O-2) and isolated as colorless crystals. Single-crystal X-ray structure analysis of the lutetium complex confirmed the coordination of the furyl group and THF to give a molecule of trigonal bipyramidal geometry with the oxygen donor atoms in the apical positions. The lability of the oxygen donor atoms results in fluxional behavior. Reaction with triphenylborane in THF gave thermally robust mono(alkyl) cations [Ln{η5:η1-C5Me4SiMe2(C4H3O-2)}(CH2SiMe3)(THF)n]+.…

Controlled Synthesis of Reactive Polymeric Architectures Using 5-Norbornene-2-carboxylic Acid Pentafluorophenyl Ester

2007

Exo-5-norbornene-2-carboxylic acid pentafluorophenyl ester was synthesized from 5-norbornene-2-carboxylic acid and polymerized by ring-opening metathesis polymerization. The obtained polymers were soluble polymeric active esters that could be used for the preparation of multifunctional polymers. The molecular weight of the polymers was controlled by variation of the monomer to initiator ratio. The precursor polymers reacted quantitatively with primary and secondary amines. Time resolved FT-IR studies at different temperatures of the polymer analogous reactions were performed and rate constants were determined.

A “click” approach to ROMP block copolymers

2008

Amphiphilic block copolymers can be conveniently prepared via convergent syntheses, allowing each individual polymer block to be prepared via the polymerization technique that gives the best architectural control. The convergent “click-chemistry” route presented here, gives access to amphiphilic diblock copolymers prepared from a ring opening metathesis polymer and polyethylene glycol. Because of the high functional group tolerance of ruthenium carbene initiators, highly functional ring opening metathesis polymerization (ROMP) polymer blocks can be prepared. The described synthetic route allows the conjugation of these polymer blocks with other end-functional polymers to give well-defined a…

Stereoselective synthesis of the cytotoxic 14-membered macrolide aspergillide A.

2010

A stereoselective synthesis of the cytotoxic 14-membered macrolide aspergillide A has been performed. The preparation of a cis-2,6-disubstituted tetrahydropyran ring via stereoselective reduction of an intermediate cyclic hemiacetal was one key feature of the synthesis. The macrocyclic lactone ring was created by means of a ring-closing metathesis (RCM), whereby the new C=C bond displayed exclusively the undesired Z configuration. Conversion to the required E configuration was achieved via photochemical isomerization.

Asymmetric synthesis of fluorinated amino macrolactones through ring-closing metathesis

2007

The synthesis of new chiral fluorinated amino and azamacrolactones of types 1 and 2 is described. A ring-closing metathesis (RCM) reaction constitutes the key step in this methodology, which uses fluorinated amino alcohols 7 as starting materials. The influence of the CF2 group, which is located in the alpha-position relative to the carbon bearing the amino group, on the efficiency of the RCM reaction is noteworthy. This method allows for the preparation of the desired fluorinated macrolactones in excellent yields.

Functional end groups for polymers prepared using ring-opening metathesis polymerization.

2011

The precise placement of functional groups on the chain-ends of macromolecules is a major focus of polymer research. Most common living polymerization techniques offer specific methods of end-functionalization governed by the active propagating species and the kinetics of the polymerization reaction. Ring-opening metathesis polymerization has established itself as one of the most functional-group-tolerant living polymerization techniques known, but this tolerance has limited the number of available functionalization reactions. Metathesis chemists have therefore been required to develop a variety of end-functionalizations, adapting each of them to the reactivity scheme of the particular cata…

On the structure of passifloricin A: asymmetric synthesis of the delta-lactones of (2Z,5S,7R,9S,11S)- and (2Z,5R,7R,9S,11S)tetrahydroxyhexacos-2-enoi…

2003

Stereoselective syntheses of the delta-lactone of (2Z,5S,7R,9S,11S)-tetrahydroxyhexacos-2-enoic acid, the structure reported for passifloricin A, and of its (5R)-epimer are described. The creation of all stereogenic centers relied upon Brown's asymmetric allylation methodology. The lactone ring was created via ring-closing metathesis. The NMR data of both synthetic products, however, were different from those of the natural product. The published structure of passifloricin A is thus erroneous and will require further synthetic work to be unambiguously assigned. [structure: see text]

Olefin-Bond Chemodifferentiation through Cross-Metathesis Reactions: A Stereocontrolled Approach to Functionalized β2,3 -Amino Acid Derivatives

2017

Chemodiscrimination of Olefin Bonds Through Cross‐Metathesis Reactions – Synthesis of Functionalized β‐Lactam and β‐Amino Acid Derivatives

2019

Diastereoselective synthesis of fluorinated, seven-membered beta-amino acid derivatives via ring-closing metathesis.

2003

[reaction: see text] Cis and trans seven-membered gamma,gamma-difluorinated beta-amino acid derivatives (III) have been prepared with a sequence that starts with imidoyl halides (I), which are condensed with suitable ester enolates to give intermediates (II). These, in turn, can be cyclized by means of a ring-closing olefin metathesis reaction and the product stereoselectively reduced to yield compounds (III) in good overall yields.