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.
Modern proximity labeling techniques
have enabled significant advances
in understanding biomolecular interactions. However, current tools
primarily utilize activation modes that are incompatible with complex
biological environments, limiting our ability to interrogate cell-
and tissue-level microenvironments in animal models. Here, we report
μMap-Red, a proximity labeling platform that uses a red-light-excited
SnIV chlorin e6 catalyst to activate a phenyl azide biotin
probe. We validate μMap-Red by demonstrating photonically controlled
protein labeling in vitro through several layers
of tissue, and we then apply our platform in cellulo to label EGFR microenvironments and validate performance
with STED microscopy and quantitative proteomics. Finally, to demonstrate
labeling in a complex biological sample, we deploy μMap-Red
in whole mouse blood to profile erythrocyte cell-surface proteins.
This work represents a significant methodological advance toward light-based
proximity labeling in complex tissue environments and animal models.
Here we report the direct conversion of strong, aliphatic C(sp 3 )−H bonds into the corresponding alkyl sulfinic acids via decatungstate photocatalysis. This transformation has been applied to a diverse range of C(sp 3 )-rich scaffolds, including natural products and approved pharmaceuticals, providing efficient access to complex sulfur-containing products. To demonstrate the broad potential of this methodology for the divergent synthesis of pharmaceutically relevant molecules, procedures for the diversification of the sulfinic acid products into a range of medicinally relevant functional groups have been developed.
C-H functionalization of electron-deficient heteroarenes using commercial unactivated alkyl halides through reductive quenching photoredox catalysis was developed. Mainstream approaches rely on the use of an excess of strong acids that result in regioselectivities dictated by the innate effect of the protonated heteroarene, leaving the functionalization of other carbons unexplored. We report a mild method under basic conditions that allows access to previously underexplored regioselectivities by relying on a combination of conjugate and halogen ortho-directing effects. Overall, this methodology gives quick access to a variety of alkylated heteroarenes that will be of interest to medicinal chemistry programs.
This work describes an expedient access to sp3-rich nitrogen heterocycles via mild photoredox cleavage of 4-alkyl-1,4-dihydropyridines followed by cyclization of the resultant carbon-centered radicals with tethered imines.
Despite the growing use of visible-light photochemistry in both chemistry and biology, no general low-heat photoreactor for use across these different disciplines exists. Herein, we describe the design and use of a standardized photoreactor for visiblelight-driven activation and photocatalytic chemical transformations. Using this single benchtop photoreactor, we performed photoredox reactions across multiple visible light wavelengths, a high-throughput photocatalytic cross-coupling reaction, and in vitro labeling of proteins and live cells. Given the success of this reactor in all tested applications, we envision that this multi-use photoreactor will be widely used in biology, chemical biology, and medicinal chemistry settings.
Kinetic measurements of the reaction between CpRu(PPh3)2Cl (1a) and 1-bromobutane reveal a nearly first order dependance on the concentration of haloalkane and a negative entropy of activation, ∆S†<0. The rate...
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