TY - JOUR
T1 - Bis-Cycloruthenated Complexes in Visible Light-Induced C-H Alkylation with Epoxides
AU - Bentley, Kurt
AU - Hareram, Mishra Deepak
AU - Wang, Gang-Wei
AU - Millman, Alexander A V
AU - Perez-Ortega, Ignacio
AU - Nichols, Luke M
AU - Bories, Cassandre C
AU - Walker, Lauren E
AU - Woodward, Adam W
AU - Golovanov, Alexander P
AU - Natrajan, Louise S
AU - Larrosa, Igor
PY - 2025/2/12
Y1 - 2025/2/12
N2 - Bis-cycloruthenated complexes (BCRCs) of the type [Ru(N^C)
2L
2] are proposed to be key reactive intermediates in the Ru(II)-catalyzed directed C-H functionalization of arenes. While the exceptional ground state reactivity of BCRCs toward a number of electrophiles has been explored, their reactivity upon photoexcitation is still unknown. Herein, we report studies on the photoexcitation of BCRCs that establish their capability to access chemically useful excited states. Remarkably, photoexcited BCRCs demonstrate greatly increased reactivity toward the electron transfer processes required for alkyl halide activation, overcoming current limitations of their ground-state reactivity. We have demonstrated this reactivity by expanding upon the current chemical space occupied by Ru-catalyzed C-H functionalization to include
ortho-alkylation with epoxides.
AB - Bis-cycloruthenated complexes (BCRCs) of the type [Ru(N^C)
2L
2] are proposed to be key reactive intermediates in the Ru(II)-catalyzed directed C-H functionalization of arenes. While the exceptional ground state reactivity of BCRCs toward a number of electrophiles has been explored, their reactivity upon photoexcitation is still unknown. Herein, we report studies on the photoexcitation of BCRCs that establish their capability to access chemically useful excited states. Remarkably, photoexcited BCRCs demonstrate greatly increased reactivity toward the electron transfer processes required for alkyl halide activation, overcoming current limitations of their ground-state reactivity. We have demonstrated this reactivity by expanding upon the current chemical space occupied by Ru-catalyzed C-H functionalization to include
ortho-alkylation with epoxides.
U2 - 10.1021/jacs.4c14835
DO - 10.1021/jacs.4c14835
M3 - Article
C2 - 39901642
SN - 0002-7863
VL - 147
SP - 5035
EP - 5042
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 6
ER -