Latest News:

05/30/2014 - Best of luck to Dr. Tyler Davis as he leaves to start his new position as a research scientist for GSK.


03/31/2014 - Best of luck to Dr. Benjamin Kohn as he leaves his post-doc position to begin working for Takeda.


02/13/2014 - Congratulations to Dr. Kevin Oberg for successfully defending his Ph.D. thesis. Kevin is off to The Scripps Research Institute for a Postdoc with Professor Phil Baran.

RECENT PUBLICATIONS:


Cobaltate Anion Couples Terminal Dienes with Trifuloroacetic Anhydride: A Direct Fluoroacylation of 1,3-Diene

Benjamin L. Kohn, Tomislav Rovis

CHEMICAL SCIENCE (2014) (ASAP)

                                                             

Perfluoroketones are useful products and intermediates in medicinal chemistry. Herein, cobalt-mediated fluoroacylation of 1,3-dienes is described using perfluorinated anhydrides such as TFAA. The reaction is thought to proceed through a fluoroacylcobalt reagent formed in situ. Perfluoroacylation of 1,3-dienes can also be performed to attain longer chain perfluorinated ketones.

Rapid Construction of (-)-Paroxetine and (-)-Femoxetine via an N-Heterocylic Carbene Catalyzed Homoenolate Addition to Nitroalkanes

Nicholas A. White, Kerem E. Ozboya, Darrin M. Flanigan, Tomislav Rovis

ASIAN JOURNAL OF ORGANIC CHEMISTRY, 3, 442-444 (2014)


A concise enantionselective synthesis of (-)-paroxetine (Paxil) and (-)-femoxetine has been achieved. Key to these syntheses is an N-heterocyclic carbene catalyzed homoenolate addition to a nitroalkene followed by in situ reduction of the nitro group to rapidly access δ-lactams.


Stereoselective Synthesis of Dioxolanes and Oxazolidines via a Desymmetrization Acetalization/Michael Cascade

David M. Rubush, Tomislav Rovis

SYNLETT, 25, 713-717 (2014)

                                                            

The desymmetrization of p-quinols using a Brønsted acid catalyzed acetalization/Michael cascade was achieved in high yields and diastereoselectivities for aldehydes and imines. Use of a chiral Brønsted acid allowed for the synthesis of 1,3-dioxolane and 1,3-oxazolidine products in modest enantioselectivity.


Rh(III)-Catalyzed Decarboxylative Coupling of Acrylic Acids with Unsaturated Oxime Esters: Carboxylic Acids Serve as Traceless Activators

Jamie M. Neely, Tomislav Rovis

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 136, 2735-2738 (2014)



α,β-Unsaturated carboxylic acids undergo Rh(III)-catalyzed decarboxylative coupling with α,β-unsaturated O-pivaloyl oximes to provide substituted pyridines in good yield. The carboxylic acid, which is removed by decarboxylation, serves as a traceless activating group, giving 5-substituted pyridines with very high levels of regioselectivity. Mechanistic studies rule out a picolinic acid intermediate, and an isolable rhodium complex sheds further light on the reaction mechanism.


Rhodium(III)-Catalyzed Intramolecular Hydroarylation, Amidoarylation, and Heck-type Reaction: Three Distinct Pathways Determined by an Amide Directing Group

Tyler A. Davis, Todd K. Hyster, Tomislav Rovis

ANGEWANDTE CHEMIE INTERNATIONAL EDITION, 52, 14181-14185 (2013)



The amide decides: Three different rhodium(III)-catalyzed reaction pathways of a wide variety of tethered alkenes can be accessed through changing the amide directing group. This provides an efficient route to a myriad of complex polycyclic products, many containing newly formed all-carbon quaternary centers. Amidoarylations can diastereoselectively deliver products with up to three contiguous stereocenters.