Abstract

) The proposed program focuses on synthesis of complex natural products via C-H bond activation. The possibility of site selectivity of these transformations in the context of complex substrates is of significant synthetic potential. Assuming such goals were realized novel and unique synthetic strategies for the assembly of natural products can be envisioned. This program will focus on development of transition metal reagents and catalysts for directed C-H activation. Selectivity of C-H activation reactions will be achieved through the use of a suitable heteroatom/functionality (imine group in most cases) to activate and direct metal complexes to geminal dialkyl groups. Following this logic, new ways to quaternary stereogenic centers will be explored in the context of three classes of natural products (aspidosperma alkaloids, teleocidin alkaloids and selected terpene-derived natural products).

  Funding Agency

Agency
National Institute of Health (NIH)
Institute
National Institute of General Medical Sciences (NIGMS)
Type
Research Project (R01)
Project #
3R01GM060326-05S1
Application #
7259055
Study Section
Medicinal Chemistry Study Section (MCHA)
Program Officer
Schwab, John M
Project Start
2001-03-01
Project End
2007-08-31
Budget Start
2005-03-01
Budget End
2007-08-31
Support Year
5
Fiscal Year
2006
Total Cost
$79,829
Indirect Cost

  Institution

Name
Columbia University (N.Y.)
Department
Chemistry
Type
Other Domestic Higher Education
DUNS #
049179401
City
New York
State
NY
Country
United States
Zip Code
10027

  Publications

Joo, Jung Min; Guo, Pengfei; Sames, Dalibor (2013) C-H bonds as ubiquitous functionality: preparation of multiple regioisomers of arylated 1,2,4-triazoles via C-H arylation. J Org Chem 78:738-43
Vadola, Paul A; Carrera, Ignacio; Sames, Dalibor (2012) C-H bond functionalization via hydride transfer: formation of ýý-arylated piperidines and 1,2,3,4-tetrahydroisoquinolines via stereoselective intramolecular amination of benzylic C-H bonds. J Org Chem 77:6689-702
Guo, Pengfei; Joo, Jung Min; Rakshit, Souvik et al. (2011) C-H arylation of pyridines: high regioselectivity as a consequence of the electronic character of C-H bonds and heteroarene ring. J Am Chem Soc 133:16338-41
Joo, Jung Min; Toure, B Barry; Sames, Dalibor (2010) C-H bonds as ubiquitous functionality: a general approach to complex arylated imidazoles via regioselective sequential arylation of all three C-H bonds and regioselective N-alkylation enabled by SEM-group transposition. J Org Chem 75:4911-20
McQuaid, Kevin M; Sames, Dalibor (2009) C-H bond functionalization via hydride transfer: Lewis acid catalyzed alkylation reactions by direct intramolecular coupling of sp3 C-H bonds and reactive alkenyl oxocarbenium intermediates. J Am Chem Soc 131:402-3
Goikhman, Roman; Jacques, Teresa L; Sames, Dalibor (2009) C-H bonds as ubiquitous functionality: a general approach to complex arylated pyrazoles via sequential regioselective C-arylation and N-alkylation enabled by SEM-group transposition. J Am Chem Soc 131:3042-8
Vadola, Paul A; Sames, Dalibor (2009) C-H bond functionalization via hydride transfer: direct coupling of unactivated alkynes and sp(3) C-H bonds catalyzed by platinum tetraiodide. J Am Chem Soc 131:16525-8
McQuaid, Kevin M; Long, Jonathan Z; Sames, Dalibor (2009) C-H bond functionalization via hydride transfer: synthesis of dihydrobenzopyrans from ortho-vinylaryl akyl ethers. Org Lett 11:2972-5
Gribkov, Denis V; Pastine, Stefan J; Schnurch, Michael et al. (2007) Ruthenium catalyzed decarbonylative arylation at sp3 carbon centers in pyrrolidine and piperidine heterocycles. J Am Chem Soc 129:11750-5
Wang, Xiang; Gribkov, Denis V; Sames, Dalibor (2007) Phosphine-free palladium-catalyzed C-H bond arylation of free (N-H)-indoles and pyrroles. J Org Chem 72:1476-9

Showing the most recent 10 out of 17 publications