Regiocontrolled Reductive Vinylation of Aliphatic 1,3-Dienes with Vinyl Triflates by Nickel Catalysis

Abstract

The regiocontrolled functionalization of 1,3-dienes has become a powerful tool for divergent synthesis, yet it remains a long-standing challenge for aliphatic substrates. Herein, we report a reductive approach for a branch-selective 1,2-hydrovinylation of aliphatic 1,3-dienes with R–X electrophiles, which represents a new selectivity pattern for diene functionalization. Simple butadiene, aromatic 1,3-dienes, and highly conjugated polyene were also tolerated. The combination of Ni(0) and the phosphine–nitrile ligand generally resulted in >20:1 regioselectivity with the retention of the geometry of the C3–C4 double bonds. This reaction proceeds with a broad substrate scope, and it allows for the conjugation of two biologically active units to form more complex polyene molecules, such as tetraene and pentaene as well as heptaene.

Enantioselective Reductive Divinylation of Unactivated Alkenes by Nickel-Catalyzed Cyclization Coupling Reaction

“…Cross-electrophile coupling has recently emerged as a promising tool for forging the C–C bonds . Our group has an ongoing interest in developing new and unconventional coupling partners for this type of chemistry . Very recently, we reported a nickel-catalyzed enantioselective cross-electrophile aryl-vinylation reaction of unactivated alkenes .…”

Nickel-catalyzed cross-electrophile allylation of vinyl bromides and the modification of anti-tumour natural medicine β-elemene

“…In addition, the present methods still suffer from a limited substrate scope and lack of further exploration for the practicality of these transformations. And no examples of the corresponding Ni-catalyzed reductive cross-coupling of vinyl electrophiles 13 with allylic electrophiles have been reported. Therefore, systematic studies on the transition-metal-catalyzed coupling of substituted vinyl electrophiles with allylic electrophiles are still in need.…”

Phosphination of Phenol Derivatives and Applications to Divergent Synthesis of Phosphine Ligands

“…Specifically, the nucleophilic phosphination typically involves nucleophilic aromatic substitutions (S N Ar) and transition-metal catalyzed cross-couplings of phosphines with aromatic halides . The reaction of halophosphine with organometallic reagents, such as organolithium and Grignard reagents, is usually involved in the electrophilic phosphination . In addition, radical phosphination is an alternative to provide the organophosphines without employing metal reagents or catalysts .…”

“…Consequently, their preparation has attracted immense attention recently, and considerable progress has been achieved . Classical C­(sp 2 )–P bond formation reactions include nucleophilic and electrophilic phosphination − (Figure b). Specifically, the nucleophilic phosphination typically involves nucleophilic aromatic substitutions (S N Ar) and transition-metal catalyzed cross-couplings of phosphines with aromatic halides .…”