Thermal- and Light-driven Metathesis Reactions Between Different Diselenides

<div>Catalytic carbonyl-olefin metathesis reactions have recently been developed as a powerful tool for carbon-carbon bond</div><div>formation. However, currently available synthetic protocols rely exclusively on aryl ketone substrates while the corresponding aliphatic analogs remain elusive. We herein report the development of Lewis acid-catalyzed carbonyl-olefin ring-closing metathesis reactions for aliphatic ketones. Mechanistic investigations are consistent with a distinct mode of activation relying on the in situ formation of a homobimetallic singly-bridged iron(III)-dimer as the active catalytic species. These “superelectrophiles” function as more powerful Lewis acid catalysts that form upon association of individual iron(III)-monomers. While this mode of Lewis acid activation has previously been postulated to exist, it has not yet been applied in a catalytic setting. The insights presented are expected to enable further advancement in Lewis acid catalysis by building upon the activation principle of “superelectrophiles” and broaden the current scope of catalytic carbonyl-olefin metathesis reactions.</div>

Download Full-text

Nickel-Catalyzed Inter- and Intramolecular Carbon-Sulfur Bond Metathesis by Reversible Arylation

10.26434/chemrxiv.8168180.v1 ◽

2019 ◽

Author(s):

Tristan Delcaillau ◽

Alessandro Bismuto ◽

Zhong Lian ◽

Bill Morandi

Keyword(s):

Good Yield ◽

Functional Group ◽

Product Formation ◽

Single Bond ◽

Ring Closing Metathesis ◽

Catalytic Systems ◽

Metathesis Reactions ◽

New Applications ◽

Further Development ◽

Sulfur Bond

A nickel-catalyzed carbon-sulfur bond metathesis has been developed to access high-value thioethers. 1,2-bis(dicyclohexylphosphino)ethane (dcype) is essential to promote this highly functional group tolerant reaction. Further, synthetically challenging macrocycles could be obtained in good yield in an unusual example of ring-closing metathesis which does not involve alkene bonds. In-depth organometallic studies support a reversible Ni(0)-Ni(II) pathway to product formation. Overall, this work does not only disclose a more sustainable and more functional group tolerant alternative to previous catalytic systems based on Pd, but also presents new applications and mechanistic information which are highly relevant to the further development and application of unusual single bond metathesis reactions.

Download Full-text

Enantioselective Preparation of Planar‐Chiral Transition Metal Complexes by Asymmetric Olefin‐Metathesis Reactions in Metal Coordination Spheres

The Chemical Record ◽

10.1002/tcr.202100102 ◽

2021 ◽

Author(s):

Masamichi Ogasawara

Keyword(s):

Transition Metal ◽

Metal Complexes ◽

Transition Metal Complexes ◽

Olefin Metathesis ◽

Metal Coordination ◽

Chiral Transition ◽

Metathesis Reactions ◽

Coordination Spheres

Download Full-text

Self-Healable Polyurethane Elastomer Based on Dual Dynamic Covalent Chemistry Using Diels–Alder “Click” and Disulfide Metathesis Reactions

ACS Applied Polymer Materials ◽

10.1021/acsapm.0c01179 ◽

2021 ◽

Vol 3 (2) ◽

pp. 847-856

Author(s):

Prasanta Kumar Behera ◽

Sagar Kumar Raut ◽

Prantik Mondal ◽

Shrabana Sarkar ◽

Nikhil K. Singha

Keyword(s):

Diels Alder ◽

Polyurethane Elastomer ◽

Dynamic Covalent Chemistry ◽

Metathesis Reactions

Download Full-text

Modification of proteins using olefin metathesis

Materials Chemistry Frontiers ◽

10.1039/c9qm00494g ◽

2020 ◽

Vol 4 (4) ◽

pp. 1040-1051 ◽

Cited By ~ 3

Author(s):

Marco S. Messina ◽

Heather D. Maynard

Keyword(s):

Small Molecules ◽

Olefin Metathesis ◽

Aqueous Media ◽

Metathesis Reactions ◽

P Proteins

Proteins are modified with small molecules and polymers via olefin metathesis reactions in aqueous media.

Download Full-text

Diastereoselective double ring closing metathesis reactions as an approach to symmetrical bicyclodienes

Canadian Journal of Chemistry ◽

10.1139/v00-075 ◽

2000 ◽

Vol 78 (6) ◽

pp. 868-883 ◽

Cited By ~ 12

Author(s):

Mark Lautens ◽

Gregory Hughes ◽

Valentin Zunic

Keyword(s):

Ring Closing Metathesis ◽

Double Ring ◽

New Class ◽

Wide Range ◽

Metathesis Reactions ◽

Bicyclic Dienes

A new class of bicyclic dienes which contain a σ plane of symmetry are efficiently prepared in a diastereoselective fashion using ring closing metathesis reactions. These molecules have potential as starting materials for a wide range of organic targets.Key words: metathesis, catalysis, stereoselective, decalin, desymmetrization.

Download Full-text