Decarboxylative cross-nucleophile coupling via ligand-to-metal charge transfer photoexcitation of Cu(ii) carboxylates

Li, Qi Yukki; Gockel, Samuel N.; Lutovsky, Grace A.; DeGlopper, Kimberly S.; Baldwin, Neil J.; Bundesmann, Mark W.; Tucker, Joseph W.; Bagley, Scott W.; Yoon, Tehshik P.

doi:10.1038/s41557-021-00834-8

Cited by 126 publications

(102 citation statements)

References 43 publications

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“… 36 , 37 Higher abundance and lower cost are often quoted as key motivators for research in this direction, 38 but aside from such practical aspects, there is still much room for fundamental and groundbreaking discovery in the photophysics and the photochemistry of first-row transition-metal complexes. 39 − 44 …”

Section: Introductionmentioning

confidence: 99%

Cobalt(III) Carbene Complex with an Electronic Excited-State Structure Similar to Cyclometalated Iridium(III) Compounds

et al. 2022

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Many organometallic iridium(III) complexes have photoactive excited states with mixed metal-to-ligand and intraligand charge transfer (MLCT/ILCT) character, which form the basis for numerous applications in photophysics and photochemistry. Cobalt(III) complexes with analogous MLCT excited-state properties seem to be unknown yet, despite the fact that iridium(III) and cobalt(III) can adopt identical low-spin d 6 valence electron configurations due to their close chemical relationship. Using a rigid tridentate chelate ligand (L CNC ), in which a central amido π-donor is flanked by two σ-donating N-heterocyclic carbene subunits, we obtained a robust homoleptic complex [Co(L CNC ) 2 ](PF 6 ), featuring a photoactive excited state with substantial MLCT character. Compared to the vast majority of isoelectronic iron(II) complexes, the MLCT state of [Co(L CNC ) 2 ](PF 6 ) is long-lived because it does not deactivate as efficiently into lower-lying metal-centered excited states; furthermore, it engages directly in photoinduced electron transfer reactions. The comparison with [Fe(L CNC ) 2 ](PF 6 ), as well as structural, electrochemical, and UV–vis transient absorption studies, provides insight into new ligand design principles for first-row transition-metal complexes with photophysical and photochemical properties reminiscent of those known from the platinum group metals.

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Section: Introductionmentioning

confidence: 99%

Cobalt(III) Carbene Complex with an Electronic Excited-State Structure Similar to Cyclometalated Iridium(III) Compounds

et al. 2022

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“…10 Coordination of reactive functional groups with metal complexes enables chemoselective oxidation via direct excitation of metal–ligand complexes, generating reactive radical species to trigger a series of useful transformations, such as C–H functionalization, 11 β-scission, 12 and decarboxylative coupling reactions. 13 Among the transition metals utilized, iron is the most abundant one in the Earth's crust, and the photoactive nature of iron-substrate complexes provides ample opportunity to activate organic molecules and initiate the desired transformations via iron photoredox catalysis. 14…”

Section: Introductionmentioning

confidence: 99%

Iron-catalyzed ring-opening of cyclic carboxylic acids enabled by photoinduced ligand-to-metal charge transfer

Gao

Luo

et al. 2022

Green Chem.

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“…A recent study of Yoon showed that copper(II) carboxylate would form the relevant chromophore to trigger decarboxylative crossnulceophile coupling via ligand-to-metal charge transfer under visible light irradiation. 24,25 In sharp contrast, no similar decarboxylative cross-coupling side products were observed in the current Photo-ATRA-type reactions. Furthermore, the reaction could also be successfully extended to a range of cyclic secondary aliphatic carboxylic acids 4f-i of various ring sizes, and carboxylic acids 4j-k with a heterocyclic scaffold, affording the corresponding cross-coupled products 7f-k in 69-80% yields with 89-95% ee.…”

Section: Resultsmentioning

confidence: 63%

Copper-Catalyzed Three-Component Photo-ATRA-Type Reaction for Asymmetric Intermolecular C-O Coupling

Wang

Liang

et al. 2022

Preprint

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Atom transfer radical addition (ATRA) reaction of alkenes has had a tremendous impact on the field of radical difunctionalizations of alkenes. Particularly in the three-component photo-ATRA-type processes, a rich chemical space and structural diversity could be achieved by smart combination of redox-active radical precursors and the third coupling components (e.g., halides, C-, N-, and O-nucleophiles) under mild con-ditions. However, the inherent complicated mechanisms involving radical chain or outer-sphere SET of the incipient radical intermediates render dearth of general catalytic methods for highly enantioselective variants, especially these regarding asymmetric intermolecular C-O bond formation. Here, we report a visible-light-induced copper-catalyzed asymmetric three-component photo-ATRA-type reaction of alkenes with oxime esters and carboxylic acids. In this process, a highly enantioselective intermolecular C-O cross-coupling between incipient sp3-hybridized carbon radicals and carboxylic acids was enabled by aryl π-bond-engaged [σ + π]-copper complex. This three-component photo-ATRA-type reaction exhibits broad substrate scope and high functional group tolerance with respect to each component, giving the desired cross-coupled products with generally good yields and excellent enantioselectivity (>70 examples; up to 97% ee). Combined experimental and computational studies are also performed to gain insight into the mechanism. This finding provides a new platform for the development of other enantioselective benzylic-type radical-based cross-coupling reactions.

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Decarboxylative cross-nucleophile coupling via ligand-to-metal charge transfer photoexcitation of Cu(ii) carboxylates

Cited by 126 publications

References 43 publications

Cobalt(III) Carbene Complex with an Electronic Excited-State Structure Similar to Cyclometalated Iridium(III) Compounds

Cobalt(III) Carbene Complex with an Electronic Excited-State Structure Similar to Cyclometalated Iridium(III) Compounds

Iron-catalyzed ring-opening of cyclic carboxylic acids enabled by photoinduced ligand-to-metal charge transfer

Copper-Catalyzed Three-Component Photo-ATRA-Type Reaction for Asymmetric Intermolecular C-O Coupling

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