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This article discusses the development of a catalytic method for the magnesiation of alkyl fluorides using magnesium powder. Alkylmagnesium reagents, such as Grignard reagents, are important tools in organic synthesis, but the preparation of alkylmagnesium reagents from alkyl fluorides has been challenging due to the high bond-dissociation energy of C-F bonds. The researchers used a bimetallic rhodium-aluminum complex as a catalyst to activate the C-F bond and successfully magnesiate alkyl fluorides, including secondary and tertiary ones. The method offers a new approach for the synthesis of alkylmagnesium reagents and expands the range of available starting materials. [Extracted from the article]

Functionalized 3‐azabicyclo[3.1.0]hexanes are highly interesting for their physiochemical and pharmacological properties. We report an unprecedented direct bridge‐head C(sp3)−H borylation by cooperative iridium/aluminum catalysis. This reaction proceeds under mild conditions in good yields with moderate to complete site selectivities. Moreover, the use of a BINOL‐based chiral aluminum catalyst renders the synthesis of enantioenriched alkylboronate products. We also disclose its synthetic utility through rapid diversifications without any loss of the stereochemical information. [ABSTRACT FROM AUTHOR]

[11] The use of tin hydride is, however, associated with some drawbacks such as its bio- and ecotoxicity, [15] formation of inseparable tin-containing byproducts, necessity of fresh tin hydride to ensure high experimental reproducibility. Nitroalkane, 9-fluorenol, single-electron transfer, radical, organocatalysis, denitration [7] The emergence of alkyl radicals along with denitration is conventionally mediated by tin hydride in the presence of a radical initiator to result in reductive denitration (Scheme 1). Keywords: nitroalkane; 9-fluorenol; single-electron transfer; denitration; radical; organocatalysis EN nitroalkane 9-fluorenol single-electron transfer denitration radical organocatalysis 1482 1486 5 07/11/23 20230725 NES 230725 Graph Radical reactions are powerful methodology to construct complex carbon frameworks such as quaternary centers and fused rings serving important structural motifs for bioactive substances and advanced materials. [Extracted from the article]

Despite the widespread success in the functionalization of C(sp2)−H bonds, the deliberate functionalization of C(sp3)−H bonds in a highly site‐ and stereoselective manner remains a longstanding challenge. Herein, we report an iridium/aluminum cooperative catalytic system that enables the β‐selective C−H borylation of saturated cyclic amines and lactams. Furthermore, we have accomplished an enantioselective variant using binaphthol‐derived chiral aluminum catalysts to forge C−B bonds with high levels of stereocontrol. Computational studies suggest that the formation of a Lewis pair with the substrates is crucial to lower the energy of the transition state for the rate‐determining reductive elimination step. [ABSTRACT FROM AUTHOR]

A series of cysteine bearing hydrophobic polypeptides analogous to a light-harvesting one beta-polypeptide (LH1beta) from the LH1 complex from the purple photosynthetic bacterium, Rhodobacter sphaeroides, is synthesized using an Escherichia coli expression system. It is found that the polypeptide orientation strongly influences the LH1-type complex formation.

Results elucidate the nickel-catalyzed hydroamination via a nickel allyl complex with an endothermic attack of amine on the coordinated diene and displacement of the allylic amine by diene to form nickel(0).