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The nickel-catalyzed reductive coupling of alkynes and imines with Et(2)Zn as a reductant by using electron-rich phosphine ligands has been developed, affording various allylic amines with high yields and excellent chemoselectivities. Chiral induction was also achieved in this reductive coupling reaction when a nickel catalyst containing a chiral spiro phosphine ligand was used.

A highly efficient nickel-catalyzed asymmetric alkylative coupling of alkynes, aldehydes, and dimethylzinc has been realized by using bulky spirobiindane phosphoramidite ligands, affording allylic alcohols with a tetrasubstituted olefin functionality in high yields, high regioselectivities, and excellent enantioselectivities.

We have developed a method for constructing tricyclic [1,2‐a]indoles via nickel‐catalyzed intramolecular imine‐alkene coupling reactions. This method enables syntheses of 6‐5‐5 and 6‐5‐6 tricyclic [1,2‐a]indoles. The use of NIXantphos or DPPPent as a ligand and 4‐(trifluoromethyl)benzoic acid as a co‐catalyst is crucial for the reaction. The synthetic utility of the method was demonstrated by converting the product into useful indole amines. [ABSTRACT FROM AUTHOR]

We have developed a nickel‐catalyzed desymmetric reductive cyclization/coupling of 1,6‐dienes. The reaction provides an efficient method for constructing a chiral tertiary alcohol and a quaternary stereocenter by a single operation. The method has excellent diastereoselectivity and high enantioselectivity, a broad substrate scope, as well as good tolerance of functional groups. Preliminary mechanism studies show that alkyl nickel(I) species are involved in the reaction. [ABSTRACT FROM AUTHOR]

This account describes our latest advances in the field of nickel(0)-catalyzed hydrofunctionalization of π components. All reactions proceed either through internal hydride transfer or by using an external proton as the hydride source, thereby eliminating the use of stoichiometric amounts of reductants or oxidants. These nickel-catalyzed atom-economical coupling reactions demonstrate that nickel not only is an inexpensive metal catalyst, but also possesses unique and versatile catalytic abilities. Current limitations and the outlook of these reactions are also discussed. 1 Introduction 2 Nickel(0)-Catalyzed Hydroacylation of Styrenes with Simple Aldehydes 3 Nickel(0)-Catalyzed Hydroalkenylation of Imines and Aldehydes with Alkenes 4 Nickel(0)-Catalyzed Hydroarylation of Styrenes and 1,3-Dienes with Organoboronic Derivatives 5 Nickel(0)-Catalyzed Hydroalkylation of 1,3-Dienes with Simple Ketones 6 Summary and Outlook [ABSTRACT FROM AUTHOR]

A Brønsted acid enabled nickel-catalyzed hydroalkenylation of aldehydes and styrene derivatives has been developed. The Brønsted acid acts as a proton shuttle to transfer a proton from the alkene to the aldehyde, thereby leading to an economical and byproduct-free coupling. A series of synthetically useful allylic alcohols were obtained through one-step reactions from readily available styrene derivatives and aliphatic aldehydes in up to 88% yield and with high linear selectivity. [ABSTRACT FROM AUTHOR]

Abstract: A nickel(0)‐catalyzed hydroalkenylation of imines with styrene and its derivatives is described. A wide range of aromatic and aliphatic imines directly coupled with styrene and its derivatives, thus providing various synthetically useful allylic amines with up to 95 % yield. The reaction offers a new atom‐ and step‐economical approach to allylic amines by using alkenes instead of alkenyl‐metallic reagents. Experiments and DFT calculations showed that TsNH2 promotes the proton transfer from the coordinated olefin to the imine, accompanied by a new C−C bond formation. [ABSTRACT FROM AUTHOR]

A Ni-catalyzed hydroarylation of styrenes and 1,3-dienes with organoboron compounds has been developed. The reaction offers a highly selective approach to diarylalkanes and allylarenes under redox-neutral conditions. In this hydroarylation reaction, a new strategy that uses the proton of methanol to generate the active catalyst species Ni−H was developed. The Ni-catalyzed hydroarylation, combined with a Ir-catalyzed C−H borylation, affords a very efficient and straightforward access to a retinoic acid receptor agonist. [ABSTRACT FROM AUTHOR]

A protocol for nickel-catalyzed hydrocarboxylation of alkynes with formic acid was developed. The protocol allowed for highly efficient synthesis of acrylic acid with a TON of up to 7700. [ABSTRACT FROM AUTHOR]