Selective C–H Activation of Molecular Nanodiamonds via Photoredox Catalysis

Hoang T. Dang; Henry T. O’Callaghan; Mikayla M. Wymore; Jennifer Suarez; David B. C. Martin

doi:10.1021/acscatal.4c00296

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Selective C–H Activation of Molecular Nanodiamonds via Photoredox Catalysis

Journal article

Open access

Peer reviewed

Selective C–H Activation of Molecular Nanodiamonds via Photoredox Catalysis

Hoang T. Dang, Henry T. O’Callaghan, Mikayla M. Wymore, Jennifer Suarez and David B. C. Martin

ACS catalysis, Vol.14(6), pp.4093-4098

03/15/2024

DOI: 10.1021/acscatal.4c00296

PMCID: PMC10949193

PMID: 38510665

Appears in UI Libraries Support Open Access

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Abstract

While substituted adamantanes have widespread use in medicinal chemistry, materials science, and ligand design, the use of diamantanes and higher diamondoids is limited to a much smaller number. Selective functionalization beyond adamantane is challenging, as the number of very similar types of C–H bonds (secondary, 2°, and tertiary, 3°) increases rapidly, and H atom transfer does not provide a general solution for site selectivity. We report a method using pyrylium photocatalysts that is effective for nanodiamond functionalization in up to 84% yield with exclusive 3° selectivity and moderate levels of regioselectivity between 3° sites. The proposed mechanism involving photooxidation, deprotonation, and radical C–C bond formation is corroborated through Stern–Volmer luminescence quenching, cyclic voltammetry, and EPR studies. Our photoredox strategy offers a versatile approach for the streamlined synthesis of diamondoid building blocks.

Letter

Diamondoids

photoredox catalysis

radical functionalization

C−C bond formation

pyrylium photocatalysis

UIOWA OA Agreement

Details

Title: Subtitle: Selective C–H Activation of Molecular Nanodiamonds via Photoredox Catalysis
Creators: Hoang T. Dang - University of Iowa
Henry T. O’Callaghan - University of Iowa
Mikayla M. Wymore - University of Iowa
Jennifer Suarez - University of Iowa
David B. C. Martin - University of Iowa
Resource Type: Journal article
Publication Details: ACS catalysis, Vol.14(6), pp.4093-4098
Publisher: American Chemical Society
DOI: 10.1021/acscatal.4c00296
PMID: 38510665
PMCID: PMC10949193
ISSN: 2155-5435
eISSN: 2155-5435
Grant note: DOI: 10.13039/100008893, name: University of Iowa; DOI: 10.13039/100000057, name: National Institute of General Medical Sciences, award: R35 GM138050
Language: English
Date published: 03/15/2024
Academic Unit: Iowa Neuroscience Institute; Chemistry
Record Identifier: 9984573826602771

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