Abstract

The aim of the following proposal is the development of the regio- and enantiospecific rhodium-catalyzed allylic substitution as a general cross-coupling reaction, and the combination with free radical cyclization and novel metal-catalyzed carbocyclization reactions. It is anticipated that these processes will facilitate the design and application of novel strategies that permit the expeditious total synthesis of the biological important molecules. The specific areas of interest are summarized as follows: New Allylic Amination Reactions with Cyclic Vinylogous Amides and Ureas: the development of new allylic amination reactions with vinylogous amides and ureas for the total synthesis of the alkaloids, lepadiformine and batzelladine D. New Metal-Catalyzed Carbocyclization Reactions: enantioselective metal-catalyzed [2+2+2] carbocyclization reactions using chiral rhodium complexes, and the combination with allylic substitutions for new tandem processes. The development of a temporary silicon-tethered (TST) rhodium-catalyzed [4+2+2] carbocyclization approach to the diterpene, epoxydictymene.

  Funding Agency

Agency
National Institute of Health (NIH)
Institute
National Institute of General Medical Sciences (NIGMS)
Type
Research Project (R01)
Project #
3R01GM058877-06S1
Application #
7167124
Study Section
Medicinal Chemistry Study Section (MCHA)
Program Officer
Schwab, John M
Project Start
1999-09-30
Project End
2008-06-30
Budget Start
2005-07-01
Budget End
2006-06-30
Support Year
6
Fiscal Year
2006
Total Cost
$68,175
Indirect Cost

  Institution

Name
Indiana University Bloomington
Department
Chemistry
Type
Schools of Arts and Sciences
DUNS #
006046700
City
Bloomington
State
IN
Country
United States
Zip Code
47401

  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