Cobalt-Catalyzed Asymmetric Reductive Alkenylation and Arylation of Heterobiaryl Tosylates: Kinetic Resolution or Dynamic Kinetic Resolution?

Atropisomeric Carboxylic Acids Synthesis via Nickel‐Catalyzed Enantioconvergent Carboxylation of Aza‐Biaryl Triflates with CO2

“…Based on the literature reports [14g,l,n] and our experimental observations, a possible mechanism was proposed (Figure 2D). First, the coordination of isoquinoline to in situ generated Ni(0)L* complex might accelerate oxidative addition of C−O bond in 1 a to Ni(0)L*, affording 5‐membered cationic nickelacycle Ar−Ni(II)L* diastereoisomers III .…”

“…The selection of other nickel pre‐catalysts exhibited similar results (entries 2–4) except for achiral phosphine binding Ni(PPh 3 ) 2 Br 2 (entry 5). When CoI 2 was employed, the reaction became sluggish and low enantioselectivity was observed (entry 6), indicating different catalytic activity and selectivity [14j,m,n] . Moreover, tert ‐butoxide base could suppress the undesired reductive protonation probably because it could increase the CO 2 concentration in solution via its reversible reaction with CO 2 (entries 7–8) [8g,15] .…”

“…When racemic ‐ 1 a was employed, the recovered 1 a was kinetically resolved with 18 % ee due to the inherent material‐catalyst match in the oxidative addition step (entry 5). When the configuration of substrate and catalyst is mismatched, the enantioselectivities are relatively lower (Figure 2A, entries 3∼4) than the matched cases (Figure 2A, entries 1∼2) resulting from the intrinsic kinetics of this process [14n,20] . To further corroborate the chelation‐promoted interconversion of nickelacycle, a substrate with 7,8‐benzo[ h ]isoquinoline 1 ac , whose nickelacycle intermediate might have limited ability for rotation, was subjected to our standard conditions.…”

Metal‐Catalyzed Enantioselective Cleavage of Aromatic C−O Bonds

“…In 2024, Wang and co‐workers reported an enantioselective reductive cross‐coupling of racemic heterobiaryl tosylates with C(sp 2 )−X type electrophiles utilizing cobalt catalysis (Scheme 11). [26] Various aryl and alkenyl halides have been recognized as effective precursors in this reaction. It is noteworthy that the process was observed to follow a kinetic resolution pathway when alkenyl bromides and aryl iodides containing strong electron‐withdrawing groups on the para‐position were utilized as electrophiles, whereas a dynamic kinetic asymmetric transformation of heterobiaryl tosylates took place when relatively electron‐rich aryl iodides were employed.…”