The Work Of Pr Karl A. Scheidt Group

2010.09.11

Department of Chemistry, Northwestern UniVersity, Evanston.

Karl Scheidt was exposed to chemistry at a young age thanks to the influence of hisfather. He obtained his PhD with WilliamRoush from Indiana University in 1999.After an NIH postdoctoral fellowship underthe direction of David A. Evans (HarvardUniversity), he joined the faculty of northwestern University (Evanston, IL, USA) in 2002. His research focuses on the development of new organic methodology and the synthesis of bioactive molecules. He is a recent Sloan Foundation Fellow and Novartis Lecturer as well as the recipient of awards from Abbott Laboratories, Amgen, AstraZeneca, Boehringer-Ingelheim, and 3M.

Synthesis of Tertiary â-Hydroxy Amides by Enolate Additions to Acylsilanes

J. AM. CHEM. SOC. 2006, 128, 15566-15567

An unusual dianion equivalent from acylsilanes:

Chem. Commun., 2008, 1926–1928

Highly Stereoselective Synthesis of Substituted g-Lactams fromAcylsilanes

Angew. Chem. Int. Ed. 2008, 47, 2294 –2297J. AM. CHEM. SOC. 2009, 131, 8805–8814

Catalytic Enantioselective a-Acylvinyl Anion Reactions of Silyloxyallenes

Angew. Chem. Int. Ed. 2007, 46, 7806 –7809J. AM. CHEM. SOC. 2006, 128, 15382-15383

The use of N-diphenylphosphinyland N-tert-butanesulfinyl functional groupsattenuates potentially competing aza-Brook rearrangementsand therefore facilitates high yields of R-silylamines.

Org. Lett.,2005,1403

Org. Lett.,2008,5227

General types of N-heterocyclic carbenes.

Dieter Enders .Chem. Rev., 2007, 107 , 5606–5655

Breslow intermediate

The Thiazolium-Catalyzed Sila-Stetter Reaction: Conjugate Addition ofAcylsilanes to Unsaturated Esters and Ketones

J. AM. CHEM. SOC. 2004, 126, 2314-2315

Conversion of r,â-Unsaturated Aldehydes into Saturated Esters

Org. Lett.,2005,7,905

Tandem Oxidation of Allylic and Benzylic Alcohols to Esters Catalyzed by N-Heterocyclic Carbenes

Org. Lett., 2007,9,371Org. Lett.,2008,10,4331

Catalytic Conjugate Additions of Carbonyl Anions underNeutral Aqueous Conditions

J. AM. CHEM. SOC.2005,127,14675

A Highly Enantioselective Intramolecular Michael Reaction Catalyzedby N-Heterocyclic Carbenes

~99%ee

Angew. Chem. Int. Ed. 2007, 46, 3107 –3110

Direct Nucleophilic Acylation of Nitroalkenes Promoted by a Fluoride Anion/Thiourea Combination

J. AM. CHEM. SOC. 2006, 128, 4932-4933

Our incorporation of a thiourea was based on the additions to nitroalkenes recently reported by Takemoto.

Hydroacylation of Activated Ketones Catalyzed by N-Heterocyclic Carbenes

J. AM. CHEM. SOC. 2006, 128, 4558-4559

Nucleophilic Acylation of o-Quinone Methides: An Umpolung Strategy for theSynthesis of r-Aryl Ketones and Benzofurans

J. AM. CHEM. SOC. 2007, 129, 4508-4509

Enantioselective Synthesis of r,r-Disubstituted Cyclopentenes by anN-Heterocyclic Carbene-Catalyzed Desymmetrization of 1,3-Diketones

Up to 96%ee

Proposed Reaction Pathway

J. AM. CHEM. SOC. 2007, 129, 10098-10099

Highly Stereoselective Formal [3 + 3] Cycloaddition of Enals and AzomethineImines Catalyzed by N-Heterocyclic Carbenes

J. AM. CHEM. SOC. 2007, 129, 5334-5335

Direct Amination of Homoenolates Catalyzed by N-Heterocyclic Carbenes

J. AM. CHEM. SOC. 2008, 130, 2740-2741

Highly Diastereo- and Enantioselective Additions of Homoenolates toNitrones Catalyzed by N-Heterocyclic Carbenes

J. AM. CHEM. SOC. 2008, 130, 2416

N-Heterocyclic Carbene-Catalyzed Enantioselective Mannich Reactions withr-Aryloxyacetaldehydes

J. AM. CHEM. SOC. 2009, 131, 18028–18029

Catalytic Enantioselective Synthesis of Flavanones and Chromanones

Up to 94% ee

J. AM. CHEM. SOC. 2007, 129, 3830-3831

Cooperative N-Heterocyclic Carbene/Lewis Acid Catalysis for HighlyStereoselective Annulation Reactions with Homoenolates

98-99% ee

Proposed Catalytic Pathway

We postulate that 2-propanol might accelerate the acylation step from III to regenerate the carbene catalyst and Ti(Oi-Pr)4 by facilitating the disassociation of the tertiary alkoxide.

J. AM. CHEM. SOC. 2010, 132, 5345–5347

Breslow intermediate

Cooperative catalysis by carbenes and Lewis acids in a highly stereoselective route to g-lactams

NATURE CHEMISTRY.2010,766