Abstract

Based on the discovery of the radical mediated [3+2] methylenecyclopentane annulation of unactivated and electron-rich olefins with 2-phenylsulfonylmethylene-cyclopropanes, this proposal aims to develop new free-radical mediated annulation and addition reactions. Toward that end, the initial objective will be to develop a series of [3+2] annulation reagents allowing the methylenecyclopentane annulation of unactivated and electron-rich olefins, and a new class of methylenecyclopentane annulations of electron-poor olefins. Another objective is to develop new addition reactions of unactivated olefins using alpha-sulfonyl radicals. A final objective is to develop, for the first time, methods for the catalytic control of the absolute and relative stereochemistry of some radical cyclizations. The health relatedness of the project derives from its impact on methods for the synthesis of a wide variety of medicinally important natural and artificial substances.

  Funding Agency

Agency
National Institute of Health (NIH)
Institute
National Institute of General Medical Sciences (NIGMS)
Type
Research Project (R01)
Project #
5R01GM045617-03
Application #
3305066
Study Section
Medicinal Chemistry Study Section (MCHA)
Project Start
1991-01-01
Project End
1993-12-31
Budget Start
1993-01-01
Budget End
1993-12-31
Support Year
3
Fiscal Year
1993
Total Cost
Indirect Cost

  Institution

Name
Texas A&M University
Department
Type
Schools of Arts and Sciences
DUNS #
City
College Station
State
TX
Country
United States
Zip Code
77845

  Publications

Kurouchi, Hiroaki; Singleton, Daniel A (2018) Labelling and determination of the energy in reactive intermediates in solution enabled by energy-dependent reaction selectivity. Nat Chem 10:237-241
Bailey, Johnathan O; Singleton, Daniel A (2017) Failure and Redemption of Statistical and Nonstatistical Rate Theories in the Hydroboration of Alkenes. J Am Chem Soc 139:15710-15723
Issaian, Adena; Faizi, Darius J; Bailey, Johnathan O et al. (2017) Mechanistic Studies of Formal Thioboration Reactions of Alkynes. J Org Chem 82:8165-8178
Aziz, Hannah R; Singleton, Daniel A (2017) Concert along the Edge: Dynamics and the Nature of the Border between General and Specific Acid-Base Catalysis. J Am Chem Soc 139:5965-5972
Kurouchi, Hiroaki; Andujar-De Sanctis, Ivonne L; Singleton, Daniel A (2016) Controlling Selectivity by Controlling Energy Partitioning in a Thermal Reaction in Solution. J Am Chem Soc 138:14534-14537
Patel, Ashay; Chen, Zhuo; Yang, Zhongyue et al. (2016) Dynamically Complex [6+4] and [4+2] Cycloadditions in the Biosynthesis of Spinosyn A. J Am Chem Soc 138:3631-4
Nieves-Quinones, Yexenia; Singleton, Daniel A (2016) Dynamics and the Regiochemistry of Nitration of Toluene. J Am Chem Soc 138:15167-15176
Biswas, Bibaswan; Singleton, Daniel A (2015) Controlling Selectivity by Controlling the Path of Trajectories. J Am Chem Soc 137:14244-7
Plata, R Erik; Singleton, Daniel A (2015) A case study of the mechanism of alcohol-mediated Morita Baylis-Hillman reactions. The importance of experimental observations. J Am Chem Soc 137:3811-26
Andujar-De Sanctis, Ivonne L; Singleton, Daniel A (2012) Racing carbon atoms. Atomic motion reaction coordinates and structural effects on Newtonian kinetic isotope effects. Org Lett 14:5238-41

Showing the most recent 10 out of 25 publications