Vicinal diamines are very important functional moieties which are present in various biologically active compounds and have also been widely used as chiral control elements in asymmetric synthesis. Diamination of olefins presents an attractive strategy for the synthesis of vicinal diamines. While good progress has been made in this area, there are still important problems that remain unsolved. We propose to develop a catalytic diamination process involving diamido metal species to address some of these challenges. The long-term goal of the proposed research is to develop an efficient regio-, diastereo-, and enantioselective catalytic diamination method for olefins with broad scope and the ability to rationalize and predict the regio- and stereo-chemical outcome for a given olefin system. Development of such a method will eventually provide effective synthetic avenues to medicinally important compounds.
The specific aims of the proposed research are: (1) to further understand and develop the Pd- and Cu(I)-catalyzed diamination through studies of reaction mechanism, expansion of substrate scope, and development of catalytic asymmetric processes;(2) to further explore other metal catalysts and nitrogen sources;(3) to explore the synthetic potential of the developed diamination method for the synthesis of useful building blocks and biologically active compounds.

Public Health Relevance

The proposed research is the development of an efficient catalytic diamination method for olefins. The method to be developed will be very useful for the synthesis of medicinal and pharmaceutical compounds.

Agency
National Institute of Health (NIH)
Institute
National Institute of General Medical Sciences (NIGMS)
Type
Research Project (R01)
Project #
5R01GM083944-06
Application #
8450767
Study Section
Synthetic and Biological Chemistry A Study Section (SBCA)
Program Officer
Lees, Robert G
Project Start
2008-05-01
Project End
2015-12-31
Budget Start
2013-01-01
Budget End
2013-12-31
Support Year
6
Fiscal Year
2013
Total Cost
$268,422
Indirect Cost
$75,422
Name
Colorado State University-Fort Collins
Department
Chemistry
Type
Schools of Arts and Sciences
DUNS #
785979618
City
Fort Collins
State
CO
Country
United States
Zip Code
80523
Zhu, Yingguang; Shi, Yian (2014) Cu(I)-catalyzed sequential diamination and dehydrogenation of terminal olefins: a facile approach to imidazolinones. Chemistry 20:13901-4
Zheng, Huaiji; Zhu, Yingguang; Shi, Yian (2014) Palladium(0)-catalyzed Heck reaction/C-H activation/amination sequence with diaziridinone: a facile approach to indolines. Angew Chem Int Ed Engl 53:11280-4
Zhu, Yingguang; Xiong, Tao; Han, Wenyong et al. (2014) Copper-catalyzed oxidative homo- and cross-coupling of Grignard reagents using diaziridinone. Org Lett 16:6144-7
Zhu, Yingguang; Cornwall, Richard G; Du, Haifeng et al. (2014) Catalytic diamination of olefins via N-N bond activation. Acc Chem Res 47:3665-78
Zhu, Yingguang; Shi, Yian (2013) A facile copper(I)-catalyzed homocoupling of terminal alkynes to 1,3-diynes with diaziridinone under mild conditions. Org Biomol Chem 11:7451-4
Ramirez, Thomas A; Wang, Qian; Zhu, Yingguang et al. (2013) Pd(0)-catalyzed sequential C-N bond formation via allylic and aromatic C-H amination of *-methylstyrenes with diaziridinone. Org Lett 15:4210-3
Zhu, Yingguang; Zhao, Baoguo; Shi, Yian (2013) Highly efficient Cu(I)-catalyzed oxidation of alcohols to ketones and aldehydes with diaziridinone. Org Lett 15:992-5
Zhu, Yingguang; Shi, Yian (2013) Facile Cu(I)-catalyzed oxidative coupling of anilines to azo compounds and hydrazines with diaziridinone under mild conditions. Org Lett 15:1942-5
Cornwall, Richard G; Zhao, Baoguo; Shi, Yian (2013) Catalytic asymmetric synthesis of cyclic sulfamides from conjugated dienes. Org Lett 15:796-9
Cornwall, Richard G; Zhao, Baoguo; Shi, Yian (2011) Complementary regioselectivity in the Cu(I)-catalyzed diamination of conjugated dienes to form cyclic sulfamides. Org Lett 13:434-7

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