A Ni-Al bimetallic catalyzed enantioselective C-H exo-selective cyclization of imidazoles with alkenes has been developed. A series of bi- or polycyclic imidazoles with β-stereocenter were obtained in up to 98% yield and >99% ee. The bifunctional SPO ligand-promoted bimetallic catalysis proved to be critical to this challenging stereocontrol.

An ortho-selective rhodium-catalyzed direct C-H arylation of 1,1'-bi-2-naphthol (BINOL), to deliver the widely used but not easily available 3,3'-diaryl BINOL, has been developed. This highly efficient one-step synthetic approach is the shortest route to date and is greatly facilitated by the newly developed ligand system comprising tBu PCl, Ph -cod, and Cy P⋅HBF . In addition, the same procedure can facilitate the challenging syntheses of 3-bulkyaryl BINOLs in good to excellent yields.

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Enantioselective Ni-catalyzed C(sp 3 )À H bond activation remains an elusive challenge. Herein, we used phosphine oxide-ligated NiÀ Al bimetallic catalyst to realize enantioselective Ni-catalyzed aliphatic C(sp 3 )À H activation of formamides, providing a series of chiral Ncontaining heterocycles in 40-95 % yield and 70-95 % ee.

Twofold CÀH annulation of readily available formamides and alkynes without built-in chelating groups was achieved. NiÀAl bimetallic catalysis enabled by a bulky BINOL-derived chiral secondary phosphine oxide (SPO) ligand proved to be critical for high reactivity and high selectivity. This reaction uses readily available formamides as starting materials and provides a concise synthetic pathway to a broad range of chiral ferrocenes in 40-98 % yield and 93-99 % ee.Supporting information and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.Scheme 4. Scope with respect to the formamides. Reaction conditions: 1 (0.2 mmol), 2 a (0.5 mmol), toluene (1.0 mL) under N 2 for 10 min to 2 h. Yields of isolated product are given. [a] 120 8C. MOM = methoxymethyl, SEM = trimethylsilylethoxymethyl. Angewandte Chemie Communications Angewandte Chemie Communications 9431

An FeBr3 -catalyzed reductive coupling of various aldehydes with alkenes that proceeds through a direct hydride transfer pathway has been developed. With (i) PrOH as the hydrogen donor under mild conditions, previously challenging coupling reactions of unactivated alkyl and aryl aldehydes with simple alkenes, such as styrene derivatives and α-olefins, proceeded smoothly to furnish a diverse range of functionalized alcohols with complete linear regioselectivity.

A bifunctional secondary phosphine oxide (SPO) ligand-controlled method was developed for Ni−Al-catalyzed nonchelated dual C−H annulation of arylformamides with alkynes, providing a series of substituted amide-containing heterocycles in ≤97% yield. The SPO-bound bimetallic catalysis proved to be critical to the reaction efficiency.

A redox-neutral Ni-catalyzed intramolecular hydroarylation of alkene with simple arene has been developed, in which DMF played a proton shuttle role in facilitating the intramolecular coupling, avoiding the use of additional reductants and oxidants. A series of oxindoles with a quaternary center were obtained in up to 99% yield.