Palladium‐Catalyzed Defluorinative Coupling of 1‐Aryl‐2,2‐Difluoroalkenes and Boronic Acids: Stereoselective Synthesis of Monofluorostilbenes
Authors:
- 11 August 2016
- journal article
- research article
- Published by Wiley in Angewandte Chemie International Edition
- Vol. 55 (38) , 11629-11632
Abstract
The palladium‐catalyzed defluorinative coupling of 1‐aryl‐2,2‐difluoroalkenes with boronic acids is described. Broad functional‐group tolerance arises from a redox‐neutral process by a palladium(II) active species which is proposed to undergo a β‐fluoride elimination to afford the products. The monofluorostilbene products were formed with excellent diastereoselectivity (≥50:1) in all cases, and it is critical, as traditional chromatographic techniques often fail to separate monofluoroalkene isomers. As a demonstration of this method's unique combination of reactivity and functional‐group tolerance, a Gleevec® analogue, using a monofluorostilbene as an amide isostere, was synthesized.Keywords
Funding Information
- NIGMS (R35 GM118190)
This publication has 46 references indexed in Scilit:
- Synthetic approaches to monofluoroalkenesChemical Society Reviews, 2011
- n→ π* Interaction andn)(π Pauli Repulsion Are Antagonistic for Protein StabilityJournal of the American Chemical Society, 2010
- Fluoroalkene modification of mercaptoacetamide-based histone deacetylase inhibitorsBioorganic & Medicinal Chemistry, 2010
- Fluoroolefins as Peptide Mimetics. 2. A Computational Study of the Conformational Ramifications of Peptide Bond ReplacementThe Journal of Physical Chemistry A, 2009
- Peptide bond mimicry by (E)-alkene and (Z)-fluoroalkene peptide isosteres: synthesis and bioevaluation of α-helical anti-HIV peptide analoguesOrganic & Biomolecular Chemistry, 2009
- Fluorinated Moieties for Replacement of Amide and Peptide Bonds2009
- Fluoroolefins as amide bond mimics in dipeptidyl peptidase IV inhibitorsBioorganic & Medicinal Chemistry Letters, 2008
- Chiral dipeptide mimics possessing a fluoroolefin moiety: a relevant tool for conformational and medicinal studiesOrganic & Biomolecular Chemistry, 2007
- Synthesis and Antibacterial Activity of 1-(2-Fluorovinyl)-7-substituted-4-quinolone-3-carboxylic Acid Derivatives, Conformationally Restricted Analogues of FleroxacinJournal of Medicinal Chemistry, 2005
- The synthesis and biological evaluation of a novel series of antimicrobials of the oxazolidinone classBioorganic & Medicinal Chemistry Letters, 2002