F. Dean Toste

The solutions with the problems regarding the ligand effects in homogeneous catalysis through December 2007 has been given. Specifically, the problems with the obvious differences in reactivity and selectivity that comes from changing neutral or anionic ligands will be addressed with a focus on ligands and complexes that enables enantioselective catalysis. There are at times when catalyst choice gives off better improvement within the reaction yields or efficiencies. Meanwhile, an emphasis will be given on the privileged ligands and catalysts for a given class of reactions. Finally, the Hayashi/Ito asymmetric aldol reaction will be dealt with.

Fluorine is the most electronegative element in the periodic table, and the introduction of one or more fluorine atoms into a molecule can result in greatly perturbed properties. Methods to introduce fluorine into small organic molecules have been actively investigated for many years by specialists in the field of fluorine chemistry. The earliest advances in catalytic asymmetric fluorination were made by exploiting transition metal enolates, capable of a bidentate mode of coordination to a metal. In 2002, Sodeoka and coworkers reported the enantioselective fluorination of β-ketoesters catalyzed by a chiral palladium complex. In 2005, Shibata and co-workers reported enantioselective chlorination and fluorination of carbonyl compounds capable of two-point binding. In 2011, Gade and co-workers described the synthesis of a new class of chiral tridentate N-donor pincer ligands, bis(oxazolinyl-methyldiene)isoindolines.

ADVERTISEMENT RETURN TO ISSUEPREVReviewNEXTSupramolecular Catalysis in Metal–Ligand Cluster HostsCasey J. Brown†, F. Dean Toste*†, Robert G. Bergman*†‡, and Kenneth N. Raymond*†‡View Author Information† Department of Chemistry, University of California, Berkeley, California 94720-1460, United States‡ Division of Chemical Sciences, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States*(F.D.T.) E-mail [email protected]*(R.G.B.) E-mail [email protected]*(K.N.R.) E-mail [email protected]Cite this: Chem. Rev. 2015, 115, 9, 3012–3035Publication Date (Web):April 21, 2015Publication History Received22 February 2013Published online21 April 2015Published inissue 13 May 2015https://pubs.acs.org/doi/10.1021/cr4001226https://doi.org/10.1021/cr4001226review-articleACS PublicationsCopyright © 2015 American Chemical SocietyRequest reuse permissionsArticle Views16624Altmetric-Citations1012LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose SUBJECTS:Catalysis,Catalysts,Cavities,Encapsulation,Supramolecular structures and assemblies Get e-Alerts

Traditionally, transition metal-catalyzed enantioselective transformations rely on chiral ligands tightly bound to the metal to induce asymmetric product distributions. Here we report high enantioselectivities conferred by a chiral counterion in a metal-catalyzed reaction. Two different transformations catalyzed by cationic gold(I) complexes generated products in 90 to 99% enantiomeric excess with the use of chiral binaphthol-derived phosphate anions. Furthermore, we show that the chiral counterion can be combined additively with chiral ligands to enable an asymmetric transformation that cannot be achieved by either method alone. This concept of relaying chiral information via an ion pair should be applicable to a vast number of metal-mediated processes.