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

Recent Advances in Ni‐Catalyzed 1,1‐Difunctionalization of Unactivated Olefins

“…In 2022, the same group expanded the interest in this method to the utilization of aryl chlorides as coupling partners. [25] In 2021, Martin described the development of a Nicatalyzed 1,1-difunctionalization of alkenes with ambiphilic α-haloboranes and α-halosilanes en route to sp 3 bis-organometallic reagents (Scheme 5). [26] In line with Yin's disclosure, [21] the utilization of a pyridinyl carboxamide ligand was crucial for the reaction to occur.…”

“…The targeted product is produced by reductive elimination, thus recovering back the propagating catalytic Ni(I) species. In 2022, the same group expanded the interest in this method to the utilization of aryl chlorides as coupling partners [25] …”

Nickel-catalyzed reductive 1,1-diarylation of unactivated alkenes with aryl iodides

“…7 Generally, a reliable strategy to control the 1,1-selectivity is to first couple an aryl or boron group to a terminal olefinic carbon, which could promote 1,2-nickel migration by stabilizing the terminal carbon-nickel species. In this regard, redox-neutral 1,1-diarylation, 8 1,1-diborlyation, 9 1,1-arylboration, 10 1,1-alkylboration 11 and 1,1-aminoborylation 12 have been realized under nickel catalysis (path III, Scheme 1). However, there is little literature on the reductive 1,1-difuncationalization of alkenes.…”

Mechanism and Origins of Regio- and Stereoselective Alkylboration of Endocyclic Olefins Enabled by Nickel Catalysis

“…Boron-containing compounds are of great importance in chemical synthesis due to their significant role in medicine and biology. , Transition-metal-catalyzed difunctionalization of alkenes represents one of the most useful alkylboration transformations for the construction of boron-containing compounds. , The stereo- and regioselectivity of addition to electronically unbiased olefins is a major challenge in this area. Through a judicious catalyst design, remarkable success has been achieved in the transition-metal-catalyzed alkylboration of alkenes. , For instance, Song reported the regioselective 1,2-arylboration of vinyl arenes and strained alkenes (Scheme a) .…”