γ‑Amino Alcohols via Energy Transfer Enabled Brook Rearrangement

• Published in: Journal of the American Chemical Society 2024-04, Vol.146 (15), p.10899-10907
• Main Authors: Laskar, Ranjini, Dutta, Subhabrata, Spies, Jan C., Mukherjee, Poulami, Rentería-Gómez, Ángel, Thielemann, Rebecca E., Daniliuc, Constantin G., Gutierrez, Osvaldo, Glorius, Frank
• Format: Article
• Language: English
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/jacs.4c01667

In the long-standing quest to synthesize fundamental building blocks with key functional group motifs, photochemistry in the recent past has comprehensively established its attractiveness. Amino alcohols are not only functionally diverse but are ubiquitous in the biologically active realm of compounds. We developed bench-stable bifunctional reagents that could then access the sparsely reported γ-amino alcohols directly from feedstock alkenes through energy transfer (EnT) photocatalysis. A designed 1,3-linkage across alkenes is made possible by the intervention of a radical Brook rearrangement that takes place downstream to the EnT-mediated homolysis of our reagent(s). A combination of experimental mechanistic investigations and detailed computational studies (DFT) indicates a radical chain propagated reaction pathway.