Award Abstract # 1205646
CCI Center in Selective C-H Functionalization

NSF Org: CHE
Division Of Chemistry
Recipient: EMORY UNIVERSITY
Initial Amendment Date: September 11, 2012
Latest Amendment Date: September 2, 2016
Award Number: 1205646
Award Instrument: Cooperative Agreement
Program Manager: Katharine Covert
kcovert@nsf.gov
 (703)292-4950
CHE
 Division Of Chemistry
MPS
 Directorate for Mathematical and Physical Sciences
Start Date: September 15, 2012
End Date: August 31, 2018 (Estimated)
Total Intended Award Amount: $20,000,000.00
Total Awarded Amount to Date: $20,635,696.00
Funds Obligated to Date: FY 2012 = $4,000,000.00
FY 2013 = $8,635,696.00

FY 2014 = $2,479,471.00

FY 2015 = $1,520,529.00

FY 2016 = $4,000,000.00
History of Investigator:
  • Huw Davies (Principal Investigator)
    hmdavie@emory.edu
Recipient Sponsored Research Office: Emory University
201 DOWMAN DR NE
ATLANTA
GA  US  30322-1061
(404)727-2503
Sponsor Congressional District: 05
Primary Place of Performance: Emory University
1515 Dickey Dr. NE, 4th floor
Atlanta
GA  US  30322-1003
Primary Place of Performance
Congressional District:
05
Unique Entity Identifier (UEI): S352L5PJLMP8
Parent UEI:
NSF Program(s): OFFICE OF MULTIDISCIPLINARY AC,
CHE CENTERS,
Science Across Virtual Instits
Primary Program Source: 01001213DB NSF RESEARCH & RELATED ACTIVIT
01001314DB NSF RESEARCH & RELATED ACTIVIT

01001415DB NSF RESEARCH & RELATED ACTIVIT

01001516DB NSF RESEARCH & RELATED ACTIVIT

01001617DB NSF RESEARCH & RELATED ACTIVIT
Program Reference Code(s): 1995, 5921, 5936, 5942, 5946, 8037, 8058, 8248, 8396, 8398, 8650, 9156, 9223
Program Element Code(s): 125300, 199500, 807700
Award Agency Code: 4900
Fund Agency Code: 4900
Assistance Listing Number(s): 47.049

ABSTRACT

The Center for Selective C-H Functionalization (CCHF) will develop new reactions and synthetic methodologies for activating and functionalizing carbon-hydrogen bonds. The carbon-hydrogen bond has traditionally been considered inert, but recent advances have shown that this bond can be productively exploited. A multi-faceted research team will build the mechanistic understanding required for the development of next-generation, selective catalysts and will develop predictive models for determining site selectivity in complex target synthesis. New catalysts systems and new methods for C-H modification will be challenged and refined in the context of natural product synthesis, library preparation and drug discovery, and materials preparation. Selective C-H bond functionalization will also be extensively investigated and further evolved for the single-step tailoring of the structure and physical properties of known molecules.

The field of C-H functionalization is projected to impact the fine chemicals industry, with the potential of revolutionizing synthetic strategies targeting pharmaceuticals and materials. By collaboration and partnership with industry leaders and other major research centers, CCHF will ensure the translation of discoveries in basic research to commercial innovations. A Center-wide commitment to continuing educating of the chemical community on the synthetic potential of this new chemistry will facilitate the development of innovations that lie beyond the scope of the proposed research. The Center also will take an active role in reaching out beyond the chemistry community to engage young students, the public, and underrepresented audiences in developing an understanding of and appreciation for the chemical sciences. Through a novel "Chemistry Communications" program, CCHF will educate and train their scientists on the best practices in communicating science to different audiences. Products generated by this program such as blogs, science animations, and science journalism will serve to educate different audiences (general public, high school teachers, K-12 students) about CCHF's research discoveries, placing the Center in a unique position to make a positive impact on the perception of chemistry in the Nation and the inclusion of more diversity in people pursuing careers in chemistry. Course development, research opportunities, and research partnerships will further enhance the influence that the Center will have on the engagement of students and underrepresented minorities.

The Center for Selective C-H Functionalization is funded as part of the Centers for Chemical Innovation (CCI) program.

PUBLICATIONS PRODUCED AS A RESULT OF THIS RESEARCH

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(Showing: 1 - 10 of 172)
Aaron G Green, Peng Liu, Craig A Merlic, and K. N. Houk "Distortion/Interaction Analysis Reveals the Origins of Selectivities in Iridium-Catalyzed C?H Borylation of Substituted Arenes and 5-Membered Heterocycles" Journal of the American Chemical Society , v.136 , 2014 , p.4575 10.1021/ja411699u
Abrams, Dylan J. and West, Julian G. and Sorensen, Erik J. "Toward a mild dehydroformylation using base-metal catalysis" Chem. Sci. , v.8 , 2017 , p.1954--195 10.1039/C6SC04607J
Adrián Varela-Álvarez, Djamaladdin G. Musaev "Can the bis(imino)pyridine Iron, (PDI)FeL1L2, Complex Catalyze the C-H bond functionalization?" Chemical Sciences , v.4 , 2013 , p.3758 10.1039/C3SC51723C
Adrián Varela-Álvarez, Lanny S. Liebeskind, and Djamaladdin G. Musaev "Mechanistic Insights into the Aerobic Copper(I)-Catalyzed Cross-Coupling of S-Acyl Thiosalicylamide Thiol Esters and Boronic Acids" Organometallics , v.31 , 2012 , p.7958-7968 10.1021/om300612u
Adrián Varela-Álvarez, Tzuhsiung Yang, Heather Jennings, Katherine P. Kornecki, Samantha N. Macmillan, Kyle M. Lancaster, James B. C. Mack, J. Du Bois, John F. Berry, and Djamaladdin G. Musaev "Rh2(II,III) Catalysts with Chelating Carboxylate and Carboxamidate Supports: Electronic Structure and Nitrene Transfer Reactivity" Journal of the American Chemical Society , v.138 , 2016 , p.2327 10.1021/jacs.5b12790
Ahmad Masarwa, Manuel Weber, and Richmond Sarpong "Selective C?C and C?H Bond Activation/Cleavage of Pinene Derivatives: Synthesis of Enantiopure Cyclohexenone Scaffolds and Mechanistic Insights" J. Am. Chem. Soc., , 2015 , p.ASAP 10.1021/jacs.5b02254
Alex J. Nett, Wanxiang Zhao, Paul M. Zimmerman and John Montgomery "Highly Active Nickel Catalysts for C-H Functionalization Identified through Analysis of Off-Cycle Intermediates" Journal of the American Chemical Society , v.137 , 2015 , p.7636 10.1021/jacs.5b04548
Alison R. H. Narayan, David H. Sherman "Re-engineering Nature's Catalysts" Science , v.339 , 2013 , p.283-284 10.1126/science.1233324
Alison R. H. Narayan, Gonzalo Jiménez-Osés, Peng Liu, Solymar Negretti, Wanxiang Zhao, Michael M. Gilbert, Raghunath O. Ramabhadran, Yun-Fang Yang, Lawrence R. Furan, Zhe Li, Larissa M. Podust, John Montgomery, K. N. Houk, and David H. Sherman "Enzymatic Hydroxylation of an Unactivated Methylene C?H Bond Guided by Molecular Dynamics Simulations" Nature Chemistry , v.7 , 2015 , p.653 10.1038/nchem.2285
Amanda R. Corcos, Omar Villanueva, Richard C. Walroth, Savita K. Sharma, John Bacsa, Kyle M. Lancaster, Cora E. MacBeth, and John F. Berry "Oxygen Activation by Co(II) and a Redox Non-Innocent Ligand: Spectroscopic Characterization of a Radical?Co(II)?Superoxide Complex with Divergent Catalytic Reactivity" Journal of the American Chemical Society , v.138 , 2016 , p.1796 10.1021/jacs.5b12643
Andorfer, Mary C. and Grob, Jonathan E. and Hajdin, Christine E. and Chael, Julia R. and Siuti, Piro and Lilly, Jeremiah and Tan, Kian L. and Lewis, Jared C. "Understanding Flavin-Dependent Halogenase Reactivity via Substrate Activity Profiling" ACS Catalysis , v.7 , 2017 , p.1897--190 10.1021/acscatal.6b02707
(Showing: 1 - 10 of 172)

PROJECT OUTCOMES REPORT

Disclaimer

This Project Outcomes Report for the General Public is displayed verbatim as submitted by the Principal Investigator (PI) for this award. Any opinions, findings, and conclusions or recommendations expressed in this Report are those of the PI and do not necessarily reflect the views of the National Science Foundation; NSF has not approved or endorsed its content.

Synthetic organic chemistry is a relatively young field of scientific investigation. Up until 150 years ago "organic chemistry" referred to chemicals created in living organisms, such as plants and animals. A theory called "Vitalism", that originated over 2000 years ago stated that a "vital force" possessed only by living organisms, was required to make organic molecules. This all changed when scientists in the mid-nineteenth century made organic molecules in the lab for the first time. This fundamentally shift of thought was the birth of synthetic organic chemistry.

 

The ability to design, construct and modify organic compounds on a molecular level transformed society and manufacturing. The industrial revolution is often credited with changing the world, but at the same time the sciences were undergoing a molecular revolution, but with a less effective PR office. Everything from the pharmaceuticals and drugs that have transformed medicine to the plastics and materials that are the common building blocks of modern manufacturing fundamentally rely on synthetic organic chemistry.

 

While synthetic organic chemistry has had a transformative impact on society, it is not without its drawbacks. In the same way that fossil fuel-based technologies drove innovation in the past and now modern research focuses on the development of cleaner, less polluting and more sustainable energy sources, traditional methods in synthetic organic chemistry that drove these advances generate waste by-products that can be harmful and difficult to dispose of. CH Functionalization is at the forefront of research developing approaches that are more efficient, generate less waste and streamline access to important medicinal and material compounds.

 

The teaching and practice of synthetic organic chemistry has traditionally revolved around the classification and reaction of compounds according to the functional groups they contain. A basic precept of all introductory organic chemistry texts is the contrast between the reactivity of functional groups and the "inert" CH and CC bonds that make up the skeleton of essentially all organic molecules. The teaching and application of this approach has enabled synthetic organic chemistry to develop into a transformative science, foundational to modern medicine and manufacturing. That does not mean that this approach is without its drawbacks. The overarching goal of the Center for Selective CH Functionalization (CCHF) is to offer an alternative to the established mode of thinking and while doing so, train the next generation of scientists. Through the development and application of effective and robust catalysts capable of transformations that selectively convert a CH bond into the functional group or structural motif of choice.

 

This strategy for constructing molecules has the potential to broadly impact not only synthetic organic chemistry, but also the disciplines that rely on this highly enabling field, such as the pharmaceutical, material and agrochemical sciences. The CH functionalization approach embodies many of the drivers that motivate modern science and can be summarized as a truly sustainable strategy by four key statements; 1). As a primarily catalytic transformation only very small amounts of high value reagents (catalysts) are required to convert large amounts of feedstock chemicals into essential commodities. 2). Employing a CH bond as the reaction partner removes the need for introduction or inter-conversion of functional groups, significantly expanding the scope of feedstock chemicals available for reaction and thus 3). considerably reducing the number of operations required to achieve a desired molecular change. 4). A meaningful reduction in the volume of hazardous waste generated by using the CH bond as a reaction partner (typical byproducts include hydrogen and nitrogen gas or water).

 

The Center for Selective CH Functionalization has built a collaborative community that brings together a broad range of scientific expertise to develop this young field into a mainstream technology. These collaborative endeavors have driven significant advances in this field. New small molecule organometallic catalysts have been developed that not only expand the scope of this chemistry to new target space but operate more efficiently. Center scientists have harnessed and re-engineered Nature's reaction machinery to afford enzymes capable of exquisitely selective reactions on synthetically valuable structures. Transformations have been discovered that harness the earth-abundant first row transition metals to mediate reactions. These advances have helped change the way this field operates, starting to override the influence of substrate properties on reaction outcome and instead building sophisticated catalysts that are beginning to offer the end user control over this reaction, a critical factor in this approach becoming a mainstream technology. The Center has developed close ties with industry and many pharmaceutical companies are exploring collaborative projects with the Center.  These efforts have enhanced the incorporation of CH functionalization into industrial workflows, increasing the competitiveness of US companies.

 


Last Modified: 11/20/2018
Modified by: Huw M Davies

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