Regioselective aliphatic C-H functionalization using frustrated radical pairs.

Autor: Lu Z; Department of Chemistry and Chemical Biology, Cornell University, Ithaca, NY, USA., Ju M; Department of Chemistry and Chemical Biology, Cornell University, Ithaca, NY, USA., Wang Y; Department of Chemistry and Chemical Biology, Cornell University, Ithaca, NY, USA., Meinhardt JM; Department of Chemistry and Chemical Biology, Cornell University, Ithaca, NY, USA., Martinez Alvarado JI; Department of Chemistry and Chemical Biology, Cornell University, Ithaca, NY, USA., Villemure E; Department of Discovery Chemistry, Genentech, Inc., South San Francisco, CA, USA., Terrett JA; Department of Discovery Chemistry, Genentech, Inc., South San Francisco, CA, USA., Lin S; Department of Chemistry and Chemical Biology, Cornell University, Ithaca, NY, USA. songlin@cornell.edu.
Jazyk: angličtina
Zdroj: Nature [Nature] 2023 Jul; Vol. 619 (7970), pp. 514-520. Date of Electronic Publication: 2023 Jul 05.
DOI: 10.1038/s41586-023-06131-3
Abstrakt: Frustrated Lewis pairs (FLPs) are well documented for the activation of small molecules such as dihydrogen and carbon dioxide 1-4 . Although canonical FLP chemistry is heterolytic in nature, recent work has shown that certain FLPs can undergo single-electron transfer to afford radical pairs 5 . Owing to steric encumbrance and/or weak bonding association, these radicals do not annihilate one another, and they have thus been named frustrated radical pairs (FRPs). Notable preliminary results suggest that FRPs may be useful reagents in chemical synthesis 6-8 , although their applications remain limited. Here we demonstrate that the functionalization of C(sp 3 )-H bonds can be accomplished using a class of FRPs generated from disilazide donors and an N-oxoammonium acceptor. Together, these species undergo single-electron transfer to generate a transient and persistent radical pair capable of cleaving unactivated C-H bonds to furnish aminoxylated products. By tuning the structure of the donor, it is possible to control regioselectivity and tailor reactivity towards tertiary, secondary or primary C-H bonds. Mechanistic studies lend strong support for the formation and involvement of radical pairs in the target reaction.
(© 2023. The Author(s), under exclusive licence to Springer Nature Limited.)
Databáze: MEDLINE
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