Photochemical phosphorus-enabled scaffold remodeling of carboxylic acids
The excitation of carbonyl compounds by light to generate radical intermediates has historically been restricted to ketones and aldehydes; carboxylic acids have been overlooked because of high energy requirements and low quantum efficiency. A successful activation strategy would necessitate a bathochromic shift in the absorbance profile, an increase in triplet diradical lifetime, and ease of further functionalization. We present a single-flask transformation of carboxylic acids to acyl phosphonates that can access synthetically useful triplet diradicals under visible light or near-ultraviolet irradiation. The use of phosphorus circumvents unproductive Norrish type I processes, promoting selectivity that enables hydrogen-atom transfer reactivity. Use of this strategy promotes the efficient scaffold remodeling of carboxylic acids through various annulation, contraction, and expansion manifolds.
Authors
- Qiupeng Peng (ORCID: https://orcid.org/0000-0002-5501-3947)
- Ryan Michael Young (ORCID: https://orcid.org/0000-0002-5108-0261)
- Yunfan Qiu (ORCID: https://orcid.org/0000-0002-4666-1424)
- Osvaldo Gutiérrez (ORCID: https://orcid.org/0000-0001-8151-7519)
- Karl A. Scheidt (ORCID: https://orcid.org/0000-0003-4856-3569)
- Ángel Rentería‐Gómez (ORCID: https://orcid.org/0000-0002-9411-8805)
- Michael R. Wasielewski (ORCID: https://orcid.org/0000-0003-2920-5440)
- Poulami Mukherjee (ORCID: https://orcid.org/0000-0002-2876-7612)
- Meemie U. Hwang
Institutions
- Northwestern University (US)
- Sustainability Institute (ZA)
- Texas A&M University (US)
Publication Details
- Journal
- Science
- Published
- 2024-09-26
- DOI
- https://doi.org/10.1126/science.adr0771
- Citations
- 25
- Primary Topic
- Radical Photochemical Reactions
- Type
- article
- Field-Weighted Citation Impact
- 6.25
Funders
- U.S. Department of Energy
- Texas AgriLife Research
- Northwestern University
- National Institutes of Health
- Office of Science
- High Performance Research Computing, Texas A and M University
- National Institute of General Medical Sciences
- Basic Energy Sciences