The
merger of photoredox catalysis with transition metal catalysis,
termed metallaphotoredox catalysis, has become a mainstay in synthetic
methodology over the past decade. Metallaphotoredox catalysis has
combined the unparalleled capacity of transition metal catalysis for
bond formation with the broad utility of photoinduced electron- and
energy-transfer processes. Photocatalytic substrate activation has
allowed the engagement of simple starting materials in metal-mediated
bond-forming processes. Moreover, electron or energy transfer directly
with key organometallic intermediates has provided novel activation
modes entirely complementary to traditional catalytic platforms. This
Review details and contextualizes the advancements in molecule construction
brought forth by metallaphotocatalysis.
Bioconjugation technologies have revolutionized the practice of biology and medicine by allowing access to novel biomolecular scaffolds. New methods for residue-selective bioconjugation are highly sought to expand the toolbox for a variety of bioconjugation applications. Herein we report a site-selective methionine bioconjugation protocol that uses photoexcited lumiflavin to generate open-shell intermediates. This reduction-potential-gated strategy enables access to residues unavailable with traditional nucleophilicity-based conjugation methods. To demonstrate the versatility and robustness of this new protocol, we have modified various proteins and further utilized this functional handle to append diverse biological payloads.
The secondary metabolites that comprise the diterpenoid alkaloids are categorized into C, C, and C families depending on the number of contiguous carbon atoms that constitute their central framework. Herein, we detail our efforts to prepare these molecules by chemical synthesis, including a photochemical approach, and ultimately a bioinspired strategy that has resulted in the development of a unifying synthesis of one C (weisaconitine D), one C (liljestrandinine), and three C (cochlearenine, paniculamine, and N-ethyl-1α-hydroxy-17-veratroyldictyzine) natural products from a common intermediate.
Photocatalysts convert light into potent reactivity. Here, we report a biohybrid catalyst in which a photosynthetic protein performs broad-spectrum light absorption and subsequent energy transfer to a conjugated photocatalyst, leading to improved yields in test reactions. This strategy has the potential to be generalized for applications in industrial and biological catalysis.
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