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1. EC-MS dataset of electrocatalytic transformations of butane on Pt

   https://doi.org/10.5281/zenodo.12801616  

   Lucky, Christine; Jiang, Shengli; Shih, Chien-Rung; Zavala, Victor; Schreier, Marcel (January 2024, Zenodo)

   This distribution provides the code and reference data for the manuscript of "Understanding the interplay between electrocatalytic C(sp3)‒C(sp3) fragmentation and oxygenation reactions" 

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2. Biocatalytic enantioselective C(sp3)–H fluorination enabled by directed evolution of non-haem iron enzymes

   https://doi.org/10.1038/s44160-024-00536-2  

   Zhao, Liu-Peng; Mai, Binh Khanh; Cheng, Lida; Gao, Fangqiu; Zhao, Yunlong; Guo, Rui; Wu, Hao; Zhang, Yongda; Liu, Peng; Yang, Yang (April 2024, Nature Synthesis)

   Due to the scarcity of C–F bond-forming enzymatic reactions in nature and the contrasting prevalence of organofluorine moieties in bioactive compounds, developing biocatalytic fluorination reactions represents a pre-eminent challenge in enzymology, biocatalysis and synthetic biology. Additionally, catalytic enantioselective C(sp3)–H fluorination remains a challenging problem facing synthetic chemists. Although many non-haem iron halogenases have been discovered to promote C(sp3)–H halogenation reactions, efforts to convert these iron halogenases to fluorinases have remained unsuccessful. Here we report the development of an enantioselective C(sp3)–H fluorination reaction, catalysed by a plant-derived non-haem enzyme 1-aminocyclopropane-1-carboxylic acid oxidase (ACCO), which is repurposed for radical rebound fluorination. Directed evolution afforded a C(sp3)–H fluorinating enzyme ACCOCHF displaying 200-fold higher activity, substantially improved chemoselectivity and excellent enantioselectivity, converting a range of substrates into enantioenriched organofluorine products. Notably, almost all the beneficial mutations were found to be distal to the iron centre, underscoring the importance of substrate tunnel engineering in non-haem iron biocatalysis. Computational studies reveal that the radical rebound step with the Fe(III)–F intermediate has a low activation barrier of 3.4 kcal mol−1 and is kinetically facile. 

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3. Divergent Concerted Proton–Electron Transfer (CPET) and Hydrogen Atom Transfer (HAT) Pathways of Amidyl Radical Reactivity Enable Chemoselective Functionalization

   https://doi.org/10.1021/acs.orglett.5c03705  

   Handlin, Alexandra D; Leibfarth, Frank A; Alexanian, Erik J (October 2025, Organic Letters)

   Amidyl radicals mediate a diverse array of intermolecular aliphatic C(sp3)–H and decarboxylative functionalizations. Interestingly, we have observed that decarboxylative processes proceed with excellent chemoselectivity even with substrates containing weak C(sp3)–H bonds. Herein, we report a mechanistic basis for understanding this high chemoselectivity of amidyl radicals through divergent reaction pathways. A computational assessment of the transition state SOMOs and intrinsic bonding orbitals for amidyl radical hydrogen atom transfer (HAT) and concerted proton-electron transfer (CPET) processes support a shift in mechanism between aliphatic C(sp3)–H or carboxylic acid O–H abstraction, which is supported by experimental studies. These findings provide a rationale for the chemoselectivity of decarboxylative reactions mediated by amidyl radicals. 

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4. Catalytic asymmetric C–H insertion reactions of vinyl carbocations

   https://doi.org/10.1126/science.ade5320  

   Nistanaki, Sepand K.; Williams, Chloe G.; Wigman, Benjamin; Wong, Jonathan J.; Haas, Brittany C.; Popov, Stasik; Werth, Jacob; Sigman, Matthew S.; Houk, K. N.; Nelson, Hosea M. (December 2022, Science)

   Organocatalysts impart enantiocontrol over dicoordinated vinyl carbocations in C(sp3) –H functionalization reactions. 

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5. Copper Catalyzed sp3 C-H a-Acetylation

   https://doi.org/10.26434/chemrxiv.11407116  

   Okoromoba, O; Jang, E.S.; McMullin, C.; Cundari, T. R.; Warren, T. H. (December 2019, ChemRxiv)

   null (Ed.)

   α-substituted ketones are important chemical targets as synthetic intermediates as well as functionalities in in natural products and pharmaceuticals. We report the sp3 C-H α-acetylation of sp3 C-H substrates R-H with arylmethyl ketones ArC(O)Me to provide α-alkylated ketones ArC(O)CH2R at RT with tBuOOtBu as oxidant via copper(I) β-diketiminato catalysts. Proceeding via alkyl radicals R•, this method enables α-substitution with bulky substituents without competing elimination that occurs in more traditional alkylation reactions between enolates and alkyl electrophiles. DFT studies suggest the intermediacy of copper(II) enolates [CuII](CH2C(O)Ar) that capture alkyl radicals R• to give R-CH2C(O)Ar under competing dimerization of the copper(II) enolate to give the 1,4-diketone ArC(O)CH2CH2C(O)Ar. 

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