A nanomicelle-forming amphiphile """"""""PTS"""""""" has been identified that allows for several Pd- and Ru-catalyzed cross-couplings to take place in water as the only solvent, and at room temperature, in high isolated yields. The new processes include Heck, Suzuki, Sonogashira, and olefin cross-metathesis reactions, where product isolation is especially facile. Several additional studies are planned based on the """"""""micellar effect."""""""" The notion of """"""""designer"""""""" surfactants applied to organometallic catalysis is advanced in this proposal, and represents a variable essentially overlooked by the synthetic community. This technology also is to be applied to other important cross-couplings, such as aminations and asymmetric additions of hydride to Michael acceptors, all in water at room temperature.

Public Health Relevance

Selected common transition metal-catalyzed reactions normally run in organic solvents can be done in pure water using an inexpensive and readily available, nanoparticle- forming, additive. These reactions also benefit in that they can be conducted at room temperature, thus requiring no external input of energy. In a broader sense, the technology is potentially valuable as a contribution to green chemistry

Agency
National Institute of Health (NIH)
Institute
National Institute of General Medical Sciences (NIGMS)
Type
Research Project (R01)
Project #
5R01GM086485-02
Application #
7914481
Study Section
Synthetic and Biological Chemistry B Study Section (SBCB)
Program Officer
Hagan, Ann A
Project Start
2009-08-15
Project End
2011-08-31
Budget Start
2010-08-01
Budget End
2011-08-31
Support Year
2
Fiscal Year
2010
Total Cost
$295,906
Indirect Cost
Name
University of California Santa Barbara
Department
Chemistry
Type
Schools of Arts and Sciences
DUNS #
094878394
City
Santa Barbara
State
CA
Country
United States
Zip Code
93106
Nishikata, Takashi; Abela, Alexander R; Huang, Shenlin et al. (2016) Cationic Pd(II)-catalyzed C-H activation/cross-coupling reactions at room temperature: synthetic and mechanistic studies. Beilstein J Org Chem 12:1040-64
Bhattacharjya, Anish; Klumphu, Piyatida; Lipshutz, Bruce H (2015) Ligand-free, palladium-catalyzed dihydrogen generation from TMDS: dehalogenation of aryl halides on water. Org Lett 17:1122-5
Handa, Sachin; Slack, Eric D; Lipshutz, Bruce H (2015) Nanonickel-catalyzed Suzuki-Miyaura cross-couplings in water. Angew Chem Int Ed Engl 54:11994-8
Bhattacharjya, Anish; Klumphu, Piyatida; Lipshutz, Bruce H (2015) Kumada-Grignard-type biaryl couplings on water. Nat Commun 6:7401
Isley, Nicholas A; Hageman, Matt S; Lipshutz, Bruce H (2015) Dehalogenation of Functionalized Alkyl Halides in Water at Room Temperature. Green Chem 2015:307
Fennewald, James C; Landstrom, Evan B; Lipshutz, Bruce H (2015) Reductions of aryl bromides in water at room temperature. Tetrahedron Lett 56:3608-3611
Handa, Sachin; Fennewald, James C; Lipshutz, Bruce H (2014) Aerobic oxidation in nanomicelles of aryl alkynes, in water at room temperature. Angew Chem Int Ed Engl 53:3432-5
Krasovskiy, Arkady L; Haley, Stephen; Voigtritter, Karl et al. (2014) Stereoretentive Pd-catalyzed Kumada-Corriu couplings of alkenyl halides at room temperature. Org Lett 16:4066-9
Lipshutz, Bruce H; Ghorai, Subir (2014) Transitioning organic synthesis from organic solvents to water. What's your E Factor? Green Chem 16:3660-3679
Isley, Nicholas A; Dobarco, Sebastian; Lipshutz, Bruce H (2014) Installation of protected ammonia equivalents onto aromatic & heteroaromatic rings in water enabled by micellar catalysis. Green Chem 16:1480-1488

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