Patrick J. Walsh

Professor of Chemistry
Inorganic Chemistry

Office: 3002 IAST
Phone: (215) 573-2875
Fax: 215) 573-6743
Email: pwalshsasupennedu
Research Group Website: http://titanium.chem.upenn.edu/walsh/index.html

Jump to: Research Statement | Education and Academic History | Selected Publications

Research Statement
Research in the Walsh group merges the fields of catalysis and organic and inorganic synthesis with the goal of achieving new catalytic asymmetric transformations for the synthesis of chiral building blocks. The transformations we have chosen to study are asymmetric C-C and C-O bond forming reactions, because construction of these bonds lies at the very heart of organic synthesis. We are also interested in the development of tandem reactions that combine several steps in a single reaction vessel. By introducing tandem reactions, we can increase synthetic efficiency while reducing the number of purification steps necessary.

Shown below are examples of tandem reactions developed in the Walsh group:

We are also interested in reaction mechanisms, which gives us the opportunity to synthesize some interesting catalysts. Shibasaki's M3(THF)n(BINOLate)3Ln (Ln = lanthanide, M = Li, Na, K) catalyst are among the most efficient known in asymmetric catalysis. We have studied the structure and reactivity of these amazing catalysts, one of which is shown below.4-6

We are also interested in structural organozinc chemistry. The first example of zinc coordinated to C-C double bond was recently reported from our group.7

In 2006 the Walsh group crystallographically characterized about 40 compounds, most of which contained metals.

Education and Academic History

Selected Publications
Jeon, S. J.; Li, H.; Walsh, P. J. A Green Chemistry Approach to a More Efficient Asymmetric Catalyst: Solvent-Free and Highly Concentrated Alkyl Additions to Ketones J. Am. Chem. Soc. 2005, 127, 16416-16425.

Rowley Kelly, A.; Lurain, A. E.; Walsh, P. J. Highly Enantio- and Diastereoselective One-Pot Synthesis of Acyclic Epoxy Alcohols and Allylic Epoxy Alcohols J. Am. Chem. Soc. 2005, 127, 14668-14674.

Kim, H. Y.; Lurain, A. E.; García-García, P.; Carroll, P. J.; Walsh, P. J. Highly Enantio- and Diastereoselective Tandem Generation of Cyclopropyl Alcohols with up to Four Contiguous Stereocenters J. Am. Chem. Soc. 2005, 127, 13138-13139.

Wooten, A. J.; Carroll, P. J.; Walsh, P. J. Evidence for Substrate Binding by the Lanthanide Centers in Li3(THF)n(BINOLate)3Ln: Solution and Solid-State Characterization of 7- and 8-Coordinate Li3(sol)n(BINOLate)3Ln(S)m Adducts Angew. Chem., Int. Ed. 2006, 45, 2549-2552.

Wooten, A. J.; Carroll, P. J.; Walsh, P. J. Impact of Na- and K-C π-Interactions on the Structure and Binding of M3(sol)n(BINOLate)3Ln Complexes Org. Lett. 2007, 9, 3359-3362.

Wooten, A. J.; Salvi, L.; Carroll, P. J.; Walsh, P. J. Characterization of Dimeric and Tetrameric m-Hydroxide Ytterbium(III) Binaphtholate Complexes Adv. Syn. & Cat. 2007, 349, 561-565.

Wooten, A.; Carroll, P. J.; Maestri, A. G.; Walsh, P. J. Unprecedented Alkene Complex of Zinc(II): Structures and Bonding of Divinylzinc Complexes J. Am. Chem. Soc. 2006, 128, 4624-4631.