We report here a new method for the synthesis of organohydrosilanes from phenols and ketones. This method is established through reductive C−Si coupling of chlorohydrosilanes via unconventional Si−Cl cleavage. The reaction offers access to aryl‐ and alkenylhydrosilanes with a scope that is complementary to those of the established methods. Electron‐rich, electron‐poor, and ortho‐/meta‐/para‐substituted (hetero)aryl electrophiles, as well as cyclic and acyclic alkenyl electrophiles, were coupled successfully. Functionalities, including Grignard‐sensitive groups (e.g., primary amine, amide, phenol, ketone, ester, and free indole), acid‐sensitive groups (e.g., ketal and THP protection), alkyl‐Cl, pyridine, furan, thiophene, Ar‐Bpin, and Ar‐SiMe3, were tolerated. Gram‐scale reaction, incorporation of ‐Si(H)R2 into complex biologically active molecules, and derivatization of formed organohydrosilanes are demonstrated.

The regiocontrolled functionalization of 1,3-dienes has become a powerful tool for divergent synthesis, yet it remains a long-standing challenge for aliphatic substrates. Herein, we report a reductive approach for a branch-selective 1,2-hydrovinylation of aliphatic 1,3-dienes with R–X electrophiles, which represents a new selectivity pattern for diene functionalization. Simple butadiene, aromatic 1,3-dienes, and highly conjugated polyene were also tolerated. The combination of Ni(0) and the phosphine–nitrile ligand generally resulted in >20:1 regioselectivity with the retention of the geometry of the C3–C4 double bonds. This reaction proceeds with a broad substrate scope, and it allows for the conjugation of two biologically active units to form more complex polyene molecules, such as tetraene and pentaene as well as heptaene.

We report here a new method for the synthesis of organohydrosilanes from phenols and ketones. This method is established through reductive CÀ Si coupling of chlorohydrosilanes via unconventional SiÀ Cl cleavage. The reaction offers access to aryl-and alkenylhydrosilanes with a scope that is complementary to those of the established methods. Electron-rich, electron-poor, and ortho-/meta-/para-substituted (hetero)aryl electrophiles, as well as cyclic and acyclic alkenyl electrophiles, were coupled successfully. Functionalities, including Grignard-sensitive groups (e.g., primary amine, amide, phenol, ketone, ester, and free indole), acid-sensitive groups (e.g., ketal and THP protection), alkyl-Cl, pyridine, furan, thiophene, Ar-Bpin, and Ar-SiMe 3 , were tolerated. Gram-scale reaction, incorporation of -Si(H)R 2 into complex biologically active molecules, and derivatization of formed organohydrosilanes are demonstrated.

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Transition-metal-catalyzed sila-cycloaddition has been a promising tool for accessing silacarbocycle derivatives, but the approach has been limited to a selection of well-defined sila-synthons. Herein, we demonstrate the potential of chlorosilanes, which are industrial feedstock chemicals, for this type of reaction under reductive nickel catalysis. This work extends the scope of reductive coupling from carbocycle to silacarbocycle synthesis and from single C–Si bond formation to sila-cycloaddition reactions. The reaction proceeds under mild conditions and shows good substrate scope and functionality tolerance, and it offers new access to silacyclopent-3-enes and spiro silacarbocycles. The optical properties of several spiro dithienosiloles as well as structural variations of the products are demonstrated.

In this article, we summarize the four mechanisms according to the experimental and theoretical basis in chronological order. These include the oxidative addition process, base‐assisted nickelation of CH bonds, the ligand‐to‐ligand hydrogen transfer (LLHT) process, and σ‐bond metathesis. Meanwhile, the representative efforts in nickel‐catalyzed CH functionalization in the past two decades are also summarized. These reactions typically involve (i) the hydrocarbonation of unsaturated CC bonds; (ii) the coupling reactions of CH with carbon electrophiles and nucleophiles; (iii) the oxidative CH and CH coupling reactions; and (iv) the construction of carbon–hetero bonds.

We study the symmetric monoidal 2-category of finite semisimple module categories over a symmetric fusion category. In particular, we study E n -algebras in this 2-category and compute their E n -centers for n = 0, 1, 2. We also compute the factorization homology of stratified surfaces with coefficients given by E n -algebras in this 2-category for n = 0, 1, 2 satisfying certain anomaly-free conditions.