Two broad areas of investigation are proposed. The first concentrates on the chemistry of samarium(ll) iodide and in particular its unique ability to mediate sequential processes that selectively transform simple starting materials to interesting products with considerable increase in molecular complexity. Unlike previous efforts in our group, we will devote substantial effort to the assembly of nitrogen heterocycles via synthetic pathways unique to this valuable reagent. Sequenced reactions to be explored include a conjugate addition/nucleophilic acyl substitution sequence, ketyl allene coupling/radical sequences, and sequences initiated by N-centered radicals. ? ? The second area of consideration is the application of organotrifluoroborates to organic synthesis. We have spent some time outlining the ways in which these useful reagents complement more commonly utilized classes of organoboron compounds in Suzuki-Miyaura cross-coupling reactions and certainly considerable advantages exist. In this proposal, however, we focus on the types of transformations that, for structural reasons, simply cannot be carried out with any other organoboron reagents. These include the synthesis of bimetallic reagents in which one of the metal centers is boron, and the development of unique reagents in which organic functionality has been oxidized in the presence of the trifluoroborate moiety. ? ? These types of transformations are anticipated to have broad generality and will thus prove valuable for the rapid, efficient, and unique assembly of complex organic molecules throughout the pharmaceutical industry and beyond. ? ?

National Institute of Health (NIH)
National Institute of General Medical Sciences (NIGMS)
Research Project (R01)
Project #
Application #
Study Section
Medicinal Chemistry Study Section (MCHA)
Program Officer
Schwab, John M
Project Start
Project End
Budget Start
Budget End
Support Year
Fiscal Year
Total Cost
Indirect Cost
University of Pennsylvania
Schools of Arts and Sciences
United States
Zip Code
Presset, Marc; Fleury-Brégeot, Nicolas; Oehlrich, Daniel et al. (2013) Synthesis and minisci reactions of organotrifluoroborato building blocks. J Org Chem 78:4615-9
Molander, Gary A; Traister, Kaitlin M; Barcellos, Thiago (2013) Palladium-catalyzed ?-arylation of 2-chloroacetates and 2-chloroacetamides. J Org Chem 78:4123-31
Tschaen, Brittany A; Schmink, Jason R; Molander, Gary A (2013) Pd-catalyzed aldehyde to ester conversion: a hydrogen transfer approach. Org Lett 15:500-3
Molander, Gary A; Cavalcanti, Livia N (2013) Synthesis of trifluoromethylated isoxazolidines: 1,3-dipolar cycloaddition of nitrosoarenes, (trifluoromethyl)diazomethane, and alkenes. Org Lett 15:3166-9
Presset, Marc; Oehlrich, Daniel; Rombouts, Frederik et al. (2013) Complementary regioselectivity in Rh(III)-catalyzed insertions of potassium vinyltrifluoroborate via C-H activation: preparation and use of 4-trifluoroboratotetrahydroisoquinolones. Org Lett 15:1528-31
Molander, Gary A; Barcellos, Thiago; Traister, Kaitlin M (2013) Pd-catalyzed cross-coupling of potassium alkenyltrifluoroborates with 2-chloroacetates and 2-chloroacetamides. Org Lett 15:3342-5
Argintaru, O Andreea; Ryu, DaWeon; Aron, Ioana et al. (2013) Synthesis and applications of ?-trifluoromethylated alkylboron compounds. Angew Chem Int Ed Engl 52:13656-60
Molander, Gary A; Traister, Kaitlin M (2013) Pd-catalyzed alkynylation of 2-chloroacetates and 2-chloroacetamides with potassium alkynyltrifluoroborates. Org Lett 15:5052-5
Colombel, Virginie; Presset, Marc; Oehlrich, Daniel et al. (2012) Synthesis and reactivity of solid-supported organotrifluoroborates in Suzuki cross-coupling. Org Lett 14:1680-3
Devulapally, Rammohan; Fleury-Bregeot, Nicolas; Molander, Gary A et al. (2012) Synthesis and cross-coupling reactions of imidomethyltrifluoroborates with aryl chlorides. Tetrahedron Lett 53:1051-1055

Showing the most recent 10 out of 72 publications