Award Abstract # 2102116
Lewis Base Directed Intermolecular Hydrogen Atom Transfer

NSF Org: CHE
Division Of Chemistry
Recipient: THE JOHNS HOPKINS UNIVERSITY
Initial Amendment Date: April 29, 2021
Latest Amendment Date: April 29, 2021
Award Number: 2102116
Award Instrument: Standard Grant
Program Manager: John C. Jewett
jjewett@nsf.gov
 (703)292-5373
CHE
 Division Of Chemistry
MPS
 Directorate for Mathematical and Physical Sciences
Start Date: September 1, 2021
End Date: August 31, 2025 (Estimated)
Total Intended Award Amount: $500,000.00
Total Awarded Amount to Date: $500,000.00
Funds Obligated to Date: FY 2021 = $500,000.00
History of Investigator:
  • Thomas Lectka (Principal Investigator)
    lectka@jhu.edu
Recipient Sponsored Research Office: Johns Hopkins University
3400 N CHARLES ST
BALTIMORE
MD  US  21218-2608
(443)997-1898
Sponsor Congressional District: 07
Primary Place of Performance: Johns Hopkins University
3400 N. Charles Street
Baltimore
MD  US  21218-2685
Primary Place of Performance
Congressional District:
07
Unique Entity Identifier (UEI): FTMTDMBR29C7
Parent UEI: GS4PNKTRNKL3
NSF Program(s): Chemical Synthesis
Primary Program Source: 01002122DB NSF RESEARCH & RELATED ACTIVIT
Program Reference Code(s): 8037
Program Element Code(s): 687800
Award Agency Code: 4900
Fund Agency Code: 4900
Assistance Listing Number(s): 47.049

ABSTRACT

With support from the Chemical Synthesis Program in the Division of Chemistry, Professor Thomas Lectka of Johns Hopkins University is studying new ways to selectively modify one carbon-hydrogen bond in a complex molecule that features many carbon-hydrogen bonds. These types of reactions are important for systematically altering biologically active molecules to study their reactivity without having to build each individual molecule from scratch. Professor Lectka and his research team are determining how loci in a complex molecule interact with a carbon-hydrogen bond-activating agent and using this information to predict and improve the ability to choose a single carbon-hydrogen bond for activation. The carbon-hydrogen bonds in these studies are being converted to carbon-fluorine, carbon-bromine, carbon-oxygen, and carbon-nitrogen bonds, valuable C-H activation transformations in organic synthesis. Professor Lectka is also partnering with the JHU Women in Science and Engineering (WISE) program and the JHU-NSF STEM Achievement in Baltimore Elementary Schools (SABES) program to provide research experiences for local high school students.

Site-selective C-H functionalization in complex molecular settings is a current grand challenge motivated by the desire to be able to study and modify natural products and pharmaceutical targets without having to individually prepare each analogue from basic building blocks. Professor Lectka and his research group are investigating a new approach to this problem through the development of hydrogen-atom transfer reagents that can specifically coordinate to a substrate and selectively activate a single carbon-hydrogen bond for C-X bond formation. Simultaneously, this team is also exploring the types of functional groups beyond ketones and enones that can influence the selectivity of the hydrogen-atom transfer reagents and determining the effect of substrate coordination to metal additives. These activities are providing a strong training platform for the professional development of graduate students and research experiences for undergraduate students.

This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

PUBLICATIONS PRODUCED AS A RESULT OF THIS RESEARCH

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(Showing: 1 - 10 of 17)
Capilato, Joseph N. and Harry, Stefan A. and Siegler, Maxime A. and Lectka, Thomas "Spectroscopic and Crystallographic Characterization of the R 3 N + CHX Interaction" Chemistry A European Journal , v.28 , 2022 https://doi.org/10.1002/chem.202103922 Citation Details
Cariello, Guilherme and Zeoly, Lucas A and Piscelli, Bruno A and Lectka, Thomas and Cormanich, Rodrigo A "The pitfalls of using J HF spinspin coupling constants to infer hydrogen bond formation in organofluorine compounds" Chemical Communications , v.59 , 2023 https://doi.org/10.1039/d3cc05389j Citation Details
Dehnen, Stefanie and Schafer, Laurel L. and Lectka, Thomas and Togni, Antonio "Fluorine: A Very Special Element and Its Very Special Impacts on Chemistry" The Journal of Organic Chemistry , v.86 , 2021 https://doi.org/10.1021/acs.joc.1c02745 Citation Details
Garrison, Nathaniel G and Harry, Stefan Andrew and Siegler, Maxime A and Cariello, Guilherme and Cormanich, Rodrigo A and Lectka, Thomas "The C FH CF2 interaction: A combination of hydrogen bonding and n  * stabilization" Journal of Fluorine Chemistry , v.272 , 2023 https://doi.org/10.1016/j.jfluchem.2023.110191 Citation Details
Harry, Stefan Andrew and Garrison, Nathaniel G. and Zhu, Andrea and Xiang, Michael Richard and Siegler, Maxime A. and Lectka, Thomas "CF Bonds as Frozen Nucleophiles: Unconsummated S N 2 Reactions" The Journal of Organic Chemistry , v.87 , 2022 https://doi.org/10.1021/acs.joc.2c01788 Citation Details
Harry, Stefan Andrew and Kazim, Muhammad and Nguyen, Phuong Minh and Zhu, Andrea and Xiang, Michael Richard and Catazaro, Jonathan and Siegler, Maxime and Lectka, Thomas "The Close Interaction of a CF Bond with an Amide Carbonyl: Crystallographic and Spectroscopic Characterization" Angewandte Chemie International Edition , v.61 , 2022 https://doi.org/10.1002/anie.202207966 Citation Details
Harry, Stefan Andrew and Vemulapalli, Srini and Dudding, Travis and Lectka, Thomas "Rational Computational Design of Systems Exhibiting Strong Halogen Bonding Involving Fluorine in Bicyclic Diamine Derivatives" The Journal of Organic Chemistry , v.87 , 2022 https://doi.org/10.1021/acs.joc.2c00497 Citation Details
Harry, Stefan Andrew and Xiang, Michael Richard and Holt, Eric and Zhu, Andrea and Ghorbani, Fereshte and Patel, Dhaval and Lectka, Thomas "Hydroxy-directed fluorination of remote unactivated C(sp 3 )H bonds: a new age of diastereoselective radical fluorination" Chemical Science , v.13 , 2022 https://doi.org/10.1039/D2SC01907H Citation Details
Hoffmann, Kurt F. and Wiesner, Anja and Müller, Carsten and Steinhauer, Simon and Beckers, Helmut and Kazim, Muhammad and Pitts, Cody Ross and Lectka, Thomas and Riedel, Sebastian "Structural proof of a [CFC]+ fluoronium cation" Nature Communications , v.12 , 2021 https://doi.org/10.1038/s41467-021-25592-6 Citation Details
Holt, Eric and Garrison, Nathaniel G. and Rowshanpour, Rozhin and Kim, Justin Jeeyoung and Henriquez, Nicolas and Lam, Winson and Kiame, Neil and Williams, Jack and Zhao, Sherrie and Dudding, Travis and Lectka, Thomas "CC Bond Activation and Demethylenation of Epoxides by Amine Radical Dications" The Journal of Organic Chemistry , v.88 , 2023 https://doi.org/10.1021/acs.joc.3c00605 Citation Details
Holt, Eric and Ruskin, Jonah and Garrison, Nathaniel G and Vemulapalli, Srini and Lam, Winson and Kiame, Neil and Henriquez, Nicolas and Borukhova, Fanny and Williams, Jack and Dudding, Travis and Lectka, Thomas "Photoactivated Pyridine Directed Fluorination through Hydrogen Atom Transfer" The Journal of Organic Chemistry , v.88 , 2023 https://doi.org/10.1021/acs.joc.3c02146 Citation Details
(Showing: 1 - 10 of 17)

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