Abstract

The aim of the following proposal is the development of the asymmetric rhodium-catalyzed allylic alkylation reaction, and the application of this unique chemistry to the synthesis of biologically important natural products. The rhodium-catalyzed allylic alkylation reaction represents a powerful method for the construction of common stereochemical motifs present in a variety of complex biologically important natural products and is particularly useful for the asymmetric synthesis of acyclic ternary and quaternary carbon stereogenic centers. Further development and application of this chemistry is necessary in order to define the scope and limitations of this important synthetic transformation. Preliminary studies will focus on the examination of stabilized carbon and nitrogen nucleophiles.

  Funding Agency

Agency
National Institute of Health (NIH)
Institute
National Institute of General Medical Sciences (NIGMS)
Type
Research Project (R01)
Project #
1R01GM058877-01A1
Application #
2909009
Study Section
Medicinal Chemistry Study Section (MCHA)
Project Start
1999-09-30
Project End
2002-09-29
Budget Start
1999-09-30
Budget End
2000-09-29
Support Year
1
Fiscal Year
1999
Total Cost
Indirect Cost

  Institution

Name
University of Delaware
Department
Chemistry
Type
Schools of Arts and Sciences
DUNS #
059007500
City
Newark
State
DE
Country
United States
Zip Code
19716

  Publications

Evans, P Andrew; Oliver, Samuel; Chae, Jungha (2012) Rhodium-catalyzed allylic substitution with an acyl anion equivalent: stereospecific construction of acyclic quaternary carbon stereogenic centers. J Am Chem Soc 134:19314-7
Baik, Mu-Hyun; Mazumder, Shivnath; Ricci, Paolo et al. (2011) Computationally designed and experimentally confirmed diastereoselective rhodium-catalyzed Pauson-Khand reaction at room temperature. J Am Chem Soc 133:7621-3
Evans, P Andrew; Clizbe, Elizabeth A (2009) Unlocking ylide reactivity in the metal-catalyzed allylic substitution reaction: stereospecific construction of primary allylic amines with aza-ylides. J Am Chem Soc 131:8722-3
Wang, Huijun; Sawyer, James R; Evans, P Andrew et al. (2008) Mechanistic insight into the diastereoselective rhodium-catalyzed Pauson-Khand reaction: role of coordination number in stereocontrol. Angew Chem Int Ed Engl 47:342-5
Evans, P Andrew; Qin, Jun; Robinson, John E et al. (2007) Enantioselective total synthesis of the polycyclic guanidine-containing marine alkaloid (-)-batzelladine D. Angew Chem Int Ed Engl 46:7417-9
Evans, P Andrew; Lai, Kwong Wah; Zhang, Hai-Ren et al. (2006) Regioselective and enantiospecific rhodium-catalyzed allylic amination with thymine: synthesis of a new conformationally rigid nucleoside. Chem Commun (Camb) :844-6
Evans, P Andrew; Sawyer, James R; Lai, Kwong Wah et al. (2005) Intermolecular rhodium-catalyzed [2+2+2] carbocyclization reactions of 1,6-enynes with symmetrical and unsymmetrical alkynes. Chem Commun (Camb) :3971-3
Evans, P Andrew; Lai, Kwong Wah; Sawyer, James R (2005) Regio- and enantioselective intermolecular rhodium-catalyzed [2+2+2] carbocyclization reactions of 1,6-enynes with methyl arylpropiolates. J Am Chem Soc 127:12466-7
Evans, P Andrew; Leahy, David K; Andrews, William J et al. (2004) Stereodivergent construction of cyclic ethers by a regioselective and enantiospecific rhodium-catalyzed allylic etherification: total synthesis of gaur acid. Angew Chem Int Ed Engl 43:4788-91
Evans, P Andrew; Leahy, David K; Slieker, Laura M (2003) Halide ion effects in the rhodium-catalyzed allylic substitution reaction using copper(I) alkoxides and enolates. Tetrahedron Asymmetry 14:3613-3618

Showing the most recent 10 out of 24 publications