Nickel-Catalyzed Stereoselective Migratory Carboboration of 1,4-Cyclohexadiene

Multi-substituted cyclohexanes play a crucial role as scaffolds in bioactive compounds.While significant progress has been made in synthesizing substituted cyclohexanes,methods for the stereoselective assembly of 1,3-disubstituted cyclohexanes remain scarce.This study presents a novel approach involving nickel catalysis to achieve stereoselective carboboration of 1,4-cyclohexadiene.This innovative process allows for the simultaneous introduction of a boron group and an aryl or an alkyl fragment into the 1,4-cyclohexadiene framework under mild conditions,with exclusive regioselectivity and excellent cis configuration.The resulting products feature a double carbon bond and the incorporation of the boron group,offering significant potential for subsequent transformations and downstream applications.

1,1-Regioselective alkenylboration of styrenes enabled by palladium catalysis

Despite the 1,2-difunctionalization reactions of styrenes have been well developed, the 1,1-regioselective addition reaction remains challenging. We disclose herein a palladium-catalyzed, highly 1,1-regioselective alkenylboration of styrenes by using alkenyl triflates and a diboron reagent as the coupling partners. A wide scope of styrenes derivatives and alkenyl triflates participate this reaction to provide the corresponding allyl boronates with high regioisomeric ratios. The success of this reaction is ascribed to the application of 1,10-phenanthroline-derivated ligand and the addition of ammonium chloride salt. Moreover, acrylate esters can also selectively afford the 1,1-alkenylboration products under the same reaction conditions.

Homogeneous Light-Driven Catalytic Direct Carboxylation with CO2

Carbon dioxide is a ubiquitous and inexpensive one-carbon source for chemical synthesis, and the efficient incorporation of CO2 into organic molecules is of widespread research interest both for economic and ecological reasons. The methodologies to employ carbon dioxide as a single-carbon unit to construct molecules relevant for agrochemical and pharmaceutical research include many elegant approaches, including asymmetric transformations. Even though remarkable achievements have been made in the field of light-driven catalysis, especially photoredox catalysis, homogeneous light-driven catalytic carboxylation by employing CO2 as the key reagent has only become a subject of increasing attention in recent years. Therefore, this concise review will discuss the latest advances in this research area.

Recent advances in the synthesis of 1,1-diarylalkanes by transitionmetal catalysis

1,1-Diaryl moieties are core structures in a wide range of bioactive and pharmaceutical compounds.Transition-metal catalysis is a convenient approach to accessing these invaluable compounds affording high yields and enantioselectivities.This review summarizes 1,1-diarylalkanes synthesis through transition metal catalysis.Particular focus is given to recent developments,such as reductive cross-electrophile couplings,benzylic C–H bond arylation,transformations involving metal migration,asymmetric hydrogenation of 1,1-diarylalkenes and three-component coupling reactions.

Modular Synthesis of Diarylalkanes by Nickel-Catalyzed 1,1-Diarylation of Unactivated Terminal Alkenes

A nickel-catalyzed 1,1-diarylation of electronically unbiased alkenes has been developed,providing straightforward access to diarylalkanes from readily available materials.Importantly,both the efficiency and the regioselectivity of this transformation are ensured by reaction conditions,rather than the coordinating group of substrates.We also demonstrate that under balloon pressure,ethylene and propylene can also be utilized as substrates.Preliminary mechanistic experiments suggest that this transformation involves a Ni(0)/Ni(Ⅱ)catalytic cycle rather than a Ni(Ⅰ)/Ni(Ⅲ)cycle.

Catalyst-controlled regiodivergent 1,2-difunctionalization of alkenes with two carbon-based electrophiles

Regiodivergent catalysis provides an efficient strategic approach for the construction of architecturally different molecules from the same starting materials. In this field, the intermolecular regiodivergent 1,2-difunctionalization of alkenes with two electrophiles is still a challenging task. A ligand-controlled, nickel-catalyzed regiodivergent dicarbofunctionalization of alkenes using both aryl/vinyl halides and acetals as electrophiles under mild reductive reaction conditions has been accomplished. This study provides a general approach to accessing both β-methoxyl esters and γ-methoxyl esters from readily available acrylates,aryl halides and acetals. Experimental mechanistic evidence supports that the difference in regioselective outcomes is attributed to the ligand tuning the reactivity of the nickel catalyst, which results in different catalytic cycles operating for these two reaction conditions.

Integrating aryl chlorides into nickel-catalyzed 1,1-difunctionalization of alkenes

Difunctionalization of alkenes have developed into an important type of reactions for rapidly and efficiently assemble complex molecules.While extensive advancements have been achieved by the assistance of transition metal catalysis,the employment of cheap,abundant aryl chlorides as coupling partner is still a challenging task in this field.Herein,we report our first achievement in 1,1-difunctionalization of alkenes with aryl chlorides as coupling partners.The success is predominantly ascribed to the judicious selection of 1,2-diamine ligand.This study provides an efficient protocol for the synthesis of secondary benzyl boronates from easily accessible feedstock chemicals.Furthermore,the distinguished features of this method include excellent 1,1-regio-and chemoselectivity,good functional group tolerance and easily-operational catalytic reaction conditions.