Catalytic enantioselective O-H insertion reactions.

J Am Chem Soc

Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, USA.

Published: April 2006

AI Article Synopsis

  • A new method has been created that allows for effective catalytic enantioselective insertions into O-H bonds.
  • This method uses a copper/bisazaferrocene catalyst to combine alcohols (like 2-trimethylsilylethanol) with alpha-aryl-alpha-diazo esters.
  • The result is a high yield and good enantiomeric excess (ee) in the reaction.

Article Abstract

The first effective method for catalytic enantioselective insertions into O-H bonds has been developed. Specifically, a copper/bisazaferrocene catalyst couples alcohols such as 2-trimethylsilylethanol with alpha-aryl-alpha-diazo esters in high yield and good ee.

Download full-text PDF

Source
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC2517123PMC
http://dx.doi.org/10.1021/ja0607739DOI Listing

Publication Analysis

Top Keywords

catalytic enantioselective
8
enantioselective o-h
4
o-h insertion
4
insertion reactions
4
reactions effective
4
effective method
4
method catalytic
4
enantioselective insertions
4
insertions o-h
4
o-h bonds
4

Similar Publications

Copper-Catalyzed Asymmetric Nucleophilic Opening of 1,1,2,2-Tetrasubstituted Donor-Acceptor Cyclopropanes for the Synthesis of α-Tertiary Amines.

J Am Chem Soc

December 2024

State Key Laboratory of Structural Chemistry, Center for Excellence in Molecular Synthesis, Fujian Institute of Research on the Structure of Matter, University of Chinese Academy of Sciences, Fuzhou 350100, China.

Catalytic asymmetric transformation of donor-acceptor cyclopropanes (DACs) has been proven to be a highly valuable and robust strategy to construct diverse types of enantioenriched molecules. However, the use of 1,1,2,2-tetrasubstituted DACs to form products bearing quaternary stereocenters remains a long-term unsolved challenge. Here, we report the copper-catalyzed asymmetric aminative ring opening of tetrasubstituted alkynyl DACs that delivers a myriad of α-tertiary amines with high levels of enantioselectivities.

View Article and Find Full Text PDF

Chiral metal clusters, due to their intriguing optical properties and unique resemblance in size to biomolecules, have attracted a lot of attention in recent times as potential candidates for application in bio-detection and therapy. While several strategies are reported for the synthesis of optically active clusters, a facile approach that enhances a multitude of properties has remained a challenge. Herein, we report a simple strategy wherein the use of a chiral cationic surfactant, during the synthesis of achiral clusters, leads to the fabrication of chiral assemblies possessing enhanced luminescence and optical activity.

View Article and Find Full Text PDF

Enantioselective Vinylogous Addition of Enones to Allenes Enabled by Synergistic Borane/Palladium Catalysis.

J Am Chem Soc

December 2024

State Key Laboratory and Institute of Elemento-Organic Chemistry, Haihe Laboratory of Sustainable Chemical Transformations, Frontiers Science Center for New Organic Matter, College of Chemistry, Nankai University, Tianjin 300071, China.

Herein, we report a method for enantioselective vinylogous addition of enones to alkoxyallenes enabled by synergistic borane/palladium catalysis. The inductive effect provided by borane coordination to the ketone was essential for closing the gap between the conditions needed for the generation of a dienolate and those needed for initiation of the palladium catalytic cycle by protonation of the metal catalyst. Furthermore, we accomplished the first example of stereodivergent synthesis with chiral borane/transition-metal catalysts.

View Article and Find Full Text PDF

A dual photoredox/cobalt-catalyzed protocol for chemo-, regio-, diastereo- and enantioselective reductive coupling of 1,1-disubstituted allenes and cyclobutenes through chemo-, regio-, diastereo- and enantioselective oxidative cyclization followed by stereoselective protonation promoted by a chiral phosphine-cobalt complex is presented. Such process represents an unprecedented reaction pathway for cobalt catalysis that enables selective transformation of the less sterically congested alkenes of 1,1-disubstituted allenes with cyclobutenes, incorporating a broad scope of tetrasubstituted alkenes into the cyclobutane scaffolds in up to 86% yield, >98:2 chemo- and regioselectivity, >98:2 dr and >99.5:0.

View Article and Find Full Text PDF

The [1,2]-rearrangement of allylic ammonium ylides is traditionally observed as a competitive minor pathway alongside the thermally allowed [2,3]-sigmatropic rearrangement. Concerted [1,2]-rearrangements are formally forbidden, with these processes believed to proceed through homolytic C-N bond fission of the ylide, followed by radical-radical recombination. The challenges associated with developing a catalytic enantioselective [1,2]-rearrangement of allylic ammonium ylides therefore lie in biasing the reaction pathway to favor the [1,2]-reaction product, alongside controlling a stereoselective radical-radical recombination event.

View Article and Find Full Text PDF

Want AI Summaries of new PubMed Abstracts delivered to your In-box?

Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!