Abstract:Visible
light-mediated photocatalysis, which relies on the ability
of photocatalysts to absorb low-energy visible light and engage in
single-electron transfer (SET) or energy transfer (ET) processes with
organic substrates, has emerged as one of the fastest growing fields
in organic synthesis. This catalytic platform enables a highly selective
approach to promote radical-based organic transformations which unlocks
unique reaction pathways. Due to the extremely mild conditions of
these transformations and compa… Show more
“…Although photocatalytic synthesis with visible light is a relatively young branch of organic chemistry, it quickly became an integral part of the synthetic chemists’ toolbox. The advantages associated with visible light photocatalysis resulted in various applications in medicinal chemistry, including drug discovery, bioconjugation, late-stage C–H functionalization, and isotopic labeling ( Figure 2 ) ( Douglas et al., 2016 ; Li et al., 2020 ). Figure 2 Representative examples of photocatalytic reactions of interest in medicinal chemistry (A–D) Bioconjugations (A), late-stage C-H functionalization (B), C sp3 -C sp2 cross-coupling reactions (C), isotopic labeling (D).…”
Section: Photocatalysis In Medicinal Chemistry and The Pharmaceuticalmentioning
Summary
Visible light photocatalysis has become a powerful tool in organic synthesis that uses photons as traceless, sustainable reagents. Most of the activities in the field focus on the development of new reactions via common photoredox cycles, but recently a number of exciting new concepts and strategies entered less charted territories. We survey approaches that enable the use of longer wavelengths and show that the wavelength and intensity of photons are import parameters that enable tuning of the reactivity of a photocatalyst to control or change the selectivity of chemical reactions. In addition, we discuss recent efforts to substitute strong reductants, such as elemental lithium and sodium, by light and technological advances in the field.
“…Although photocatalytic synthesis with visible light is a relatively young branch of organic chemistry, it quickly became an integral part of the synthetic chemists’ toolbox. The advantages associated with visible light photocatalysis resulted in various applications in medicinal chemistry, including drug discovery, bioconjugation, late-stage C–H functionalization, and isotopic labeling ( Figure 2 ) ( Douglas et al., 2016 ; Li et al., 2020 ). Figure 2 Representative examples of photocatalytic reactions of interest in medicinal chemistry (A–D) Bioconjugations (A), late-stage C-H functionalization (B), C sp3 -C sp2 cross-coupling reactions (C), isotopic labeling (D).…”
Section: Photocatalysis In Medicinal Chemistry and The Pharmaceuticalmentioning
Summary
Visible light photocatalysis has become a powerful tool in organic synthesis that uses photons as traceless, sustainable reagents. Most of the activities in the field focus on the development of new reactions via common photoredox cycles, but recently a number of exciting new concepts and strategies entered less charted territories. We survey approaches that enable the use of longer wavelengths and show that the wavelength and intensity of photons are import parameters that enable tuning of the reactivity of a photocatalyst to control or change the selectivity of chemical reactions. In addition, we discuss recent efforts to substitute strong reductants, such as elemental lithium and sodium, by light and technological advances in the field.
“…Visible light photocatalysis hase mergedo ver the last decade as ap owerful tool for the synthesis of various substratesi ne co-friendlyc onditions. [14] More specifically,p hotoredox-catalyzed decarboxylation is an approachw hich was widely described and, in particular, the use of R-ECH 2 CO 2 Hs ubstratesa ss tartingm aterials was considered. [15] Indeed, such substrates are easy to obtain by carboxymethylation of corresponding chalcogenolsw ithh aloacetate reagents.…”
The synthesis of molecules bearing (trifluoromethylselenyl)methylchalcogenyl groups is described via an efficient two‐step strategy based on a metal‐free photoredox catalyzed decarboxylative trifluoromethylselenolation with good yields up to 88 %, which raised to 98 % in flow chemistry conditions. The flow methods allowed also to scale up the reaction. The mechanism of this key reaction was studied. The physicochemical characterization of these emerging groups was performed by determining their Hansch–Leo lipophilicity parameters with high values up to 2.24. This reaction was also extended to perfluoroalkylselenolation with yields up to 95 %. Finally, this method was successfully applied to the functionalization of relevant bioactive molecules such as tocopherol or estrone derivatives.
“…Current or future technologies and processes developed can be further adopted and transferred to other photochemical or even thermal applications [ 39 , 40 , 41 , 42 , 43 , 44 , 45 , 46 , 47 , 134 ]. Visible-light photoredox catalysis, for example, has seen remarkable growth over the last decade [ 135 , 136 , 137 ], but no large-scale solar processes have been reported yet [ 138 ]. Likewise, new solar chemical reactor concepts have been recently developed, including continuous-flow trough and luminescent solar concentrators [ 139 , 140 , 141 ].…”
Photooxygenation reactions involving singlet oxygen (1O2) are utilized industrially as a mild and sustainable access to oxygenated products. Due to the usage of organic dyes as photosensitizers, these transformations can be successfully conducted using natural sunlight. Modern solar chemical reactors enable outdoor operations on the demonstration (multigram) to technical (multikilogram) scales and have subsequently been employed for the manufacturing of fine chemicals such as fragrances or biologically active compounds. This review will highlight examples of solar photooxygenations for the manufacturing of industrially relevant target compounds and will discuss current challenges and opportunities of this sustainable methodology.
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