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43905-G1
Phosphoranyl Radical-Mediated Deoxygenative Transformation of Carbonyl Groups

Liming Zhang, University of Nevada (Reno)

Progress Report for ACS PRF 43905-G1

Advance in Au catalysis

With the partial financial support of this grant, we have made significant progress in Au catalysis for the last year. A total of five papers including four JACS communications and one OL were published.

Our study has been focused on further developing Au catalysis into synthetically highly useful methods. Cycloaddition reactions are of particular importance in organic synthesis due not only to one-pot formation of multiple bonds but also to their bimolecular nature. However, Au chemistry has been of limited use in this area.

We have developed a novel concept of Au-containing all-carbon 1,n-dipoles and explored the reactivities of these species in three studies (JACS 2008, 1814; JACS 2008, ASAP; J. Organomet. Chem. 2008, accepted). The key feature in this design is that the anion end of the 1,n-dipole is capped by a Au complex, thus attenuating its reactivity and allowing the cation end to initiate the stepwise cycloaddition process (Scheme 1).

In addition, we also developed methods generating Au carbene-containing 1,3-dipoles including all-carbon 1,3-dipoles (Org. Lett. 2007, 9, 4627) and carbonyl ylides (JACS 2008, 130, 6944). These novel approaches not only reveal unprecedented chemistry but also offer highly efficient access to benzyl-protected phenol derivatives via a formal [3+3] approach and various highly functionalized bicyclo[3.2.0]heptanes.

Lately, our study on ‘Au-Catalyzed Synthesis of 5,6-Dihydro-8H-indolizin-7-ones from N-(Pent-2-en-4-ynyl)-b-Lactams' was just accepted for publication at Oganic Letters.

These studies have significant impact on the field of Au catalysis as it continues to be one of the hot topics in organic chemistry. These studies have been reviewed favorably and published in highly reputed journals; moreover, the novel concepts developed help to push the frontier of Au catalysis further.

Impact on PI's career and students' education.

The PI's career has substantially benefited from this grant. With its support the PI has published many studies in the past two years in Au catalysis. These publications have attracted significant attention in the synthetic community. As a result, the PI was awarded NSF CAREER (2008), Mousel-Feltner Award for Excellence in Research and/or Creative Activity (UNR. 2008), Amgen Young Investigator's Award (2008) and Thieme Journal Award (2007). Moreover, the PI has been invited to lecture in various Universities (UCLA, University of Connecticut, University of Delaware, and California State University, Fullerton) and pharmaceutical companies (Merck, Eli Lilly and Bristol-Myers Squibb).

With the help of this grant, graduate students and postdocs have progressed very well in their education in the lab and stayed highly productive. Meng Yu, the first graduate student, just graduated with a M. S. degree and will join a pharmaceutical company in China. Dr. Guotao Li, a postdoc partially supported by this grant, landed a senior position in a pharmaceutical company in China. Guozhu Zhang, a third-year graduate, has been very prolific and is well on his way to graduate in only four years. Dr. Yu Peng, a postdoc fellowed supported by this grant for his first two months here, has already had an Org. Lett. manuscript accepted.

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