Nickel-catalyzed divergent Mizoroki–Heck reaction of 1,3-dienes

Abstract

Developing efficient strategies to realize divergent arylation of dienes has been a long-standing synthetic challenge. Herein, a nickel catalyzed divergent Mizoroki–Heck reaction of 1,3-dienes has been demonstrated through the regulation of ligands and additives. In the presence of Mn/NEt3, the Mizoroki–Heck reaction of dienes delivers linear products under Ni(dppe)Cl2 catalysis in high regio- and stereoselectivities. With the help of catalytic amount of organoboron and NaF, the use of bulky ligand IPr diverts the selectivity from linear products to branched products. Highly aryl-substituted compounds can be transformed from dispersive Mizoroki–Heck products programmatically. Preliminary experimental studies are carried out to elucidate the role of additives.

Catalyst‐Controlled Divergent C3/C5 Site‐Selective C−H Arylation of 2‐Pyridylthiophenes

“…With this satisfying result, we screened the reaction conditions by varying the reaction medium. It was tested that CH 3 CN was optimal to give 4 aa in 80% yield (entries [12][13][14][15][16][17]. When the reaction was performed at 120 °C, it proved to be less reactive, which revealed that a relative high temperature was necessary for this transformation (entry 14).…”

“…[14] In 2023, Chen and co-workers achieved a nickel catalyzed divergent arylation of 1,3-dienes through the regulation of ligands and additives. [15] Efficient control over reaction selectivity has been a longstanding goal of organic synthesis, and switchable CÀ H arylation of thiophenes which would allow a simple access to diverse products from identical starting materials is highly desirable. In this work, we demonstrate a regiodivergent CÀ H arylation of 2-pyridylthiophenes via the choice of Ru II and Pd II catalysts to afford the corresponding C3-and C5-arylated thiophenes (Scheme 1d).…”

“…Later on, You's team disclosed an iridium‐mediated regiodivergent heteroarylation of indoles by tuning C−H metalation modes [14] . In 2023, Chen and co‐workers achieved a nickel catalyzed divergent arylation of 1,3‐dienes through the regulation of ligands and additives [15] …”

Dienes as Versatile Substrates for Transition Metal‐Catalyzed Reactions

“…In 2023, the Chen group presented a nickel-catalyzed, regioselective Mizoroki-Heck reaction involving 1,3dienes. [59] By fine-tuning the ligand and additives, they selectively obtained both linear and branched products (Figure 28). Under their linear-selective conditions, electron-rich dienes displayed excellent performance ( and anionic organoborate results in the Ni II complex V'.…”

Controlling Reactivity and Selectivity in the Mizoroki–Heck Reaction: High Throughput Evaluation of 1,5-Diaza-3,7-diphosphacyclooctane Ligands

“…Filling these holes and identifying more general catalysts are two important goals in the development of site-selective methodologies. Methods which enable the synthesis of multiple regioisomers with general reaction conditions remain sparsely reported, though a recent report by Chen and co-workers on the coupling of dienes demonstrated regiocontrol (Scheme B) . In this case, achieving a switch in regiochemistry involves modifying the ligand, base, solvent, and (pseudo)­halide.…”