Transcript 40. The Work Of Pr Karl A. Scheidt Group

The Work Of Pr Karl A. Scheidt Group
Department of Chemistry, Northwestern
UniVersity, Evanston.
2010.09.11
Karl Scheidt was exposed to chemistry at
a young age thanks to the influence of his
father. He obtained his PhD with William
Roush from Indiana University in 1999.
After an NIH postdoctoral fellowship under
the direction of David A. Evans (Harvard
University), 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 from
Acylsilanes
Angew. Chem. Int. Ed. 2008, 47, 2294 –2297
J. AM. CHEM. SOC. 2009, 131, 8805–8814
Catalytic Enantioselective a-Acylvinyl Anion Reactions of
Silyloxyallenes
Angew. Chem. Int. Ed. 2007, 46, 7806 –7809
J. AM. CHEM. SOC. 2006, 128, 15382-15383
Org. Lett.,2008,5227
The use of N-diphenylphosphinyland N-tert-butanesulfinyl functional groups
attenuates potentially competing aza-Brook rearrangements
and therefore facilitates high yields of R-silylamines.
Org. Lett.,2005,1403
General types of Nheterocyclic carbenes.
Dieter Enders .Chem. Rev., 2007, 107 , 5606–5655
Breslow intermediate
The Thiazolium-Catalyzed Sila-Stetter Reaction: Conjugate Addition of
Acylsilanes 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., 2007,9,371
Org. Lett.,2008,10,4331
Catalytic Conjugate Additions of Carbonyl Anions under
Neutral Aqueous Conditions
J. AM. CHEM. SOC.2005,
127,14675
A Highly Enantioselective Intramolecular Michael Reaction Catalyzed
by 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
Our incorporation of a thiourea was based on the additions to
nitroalkenes recently reported by Takemoto.
J. AM. CHEM. SOC. 2006, 128, 4932-4933
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 the
Synthesis of r-Aryl Ketones and Benzofurans
J. AM. CHEM. SOC. 2007, 129, 4508-4509
Enantioselective Synthesis of r,r-Disubstituted Cyclopentenes by an
N-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 Azomethine
Imines 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 to
Nitrones Catalyzed by N-Heterocyclic Carbenes
J. AM. CHEM. SOC. 2008, 130, 2416
N-Heterocyclic Carbene-Catalyzed Enantioselective Mannich Reactions with
r-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 Highly
Stereoselective Annulation Reactions with Homoenolates
98-99% ee
Proposed Catalytic Pathway
Breslow intermediate
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
Cooperative catalysis by carbenes and Lewis acids in a highly
stereoselective route to g-lactams
NATURE CHEMISTRY.2010,766