Convenient Formation of Triarylphosphines by Nickel‐Catalyzed C–P Cross‐Coupling with Aryl Chlorides

Abstract

A convenient strategy has been developed for the preparation of various phosphine ligands in good to excellent yields through a nickel‐catalyzed C–P bond‐forming step. This reaction proceeded smoothly and tolerated a variety of functional groups to provide a new method for the synthesis of important phosphine ligands through the direct cleavage of a C–Cl bond.

Bridge‐Clamp Bis(tetrazine)s with [N]8 π‐Stacking Interactions and Azido‐s‐Aryl Tetrazines: Two Classes of Doubly Clickable Tetrazines

“…Reoxidation to tetrazine was necessary to yield the phosphine oxides 16 a and 16 b (XRD structure solved for 16 b,F igure 7; see the Supporting Information). [36] Tr ifluoromethylated compounds are also topical in medicinal chemistry, [37] and we successfully achieved nucleophilic Cu-catalyzed alkylation of s-tetrazine using trifluoromethylsilane. [38] Theh alogenated trifluoromethylated 17 a-d were synthesized (XRD structure solved for 17 a;see the Supporting Information) using 1,4-dioxane as as olvent, limiting Tz dehalogenation side-reactions.A ll these o-substituted s-aryl tetrazines are highly colored in solution and in the solid state (red to purple;s ee Figures S7 and S8) but are not fluorescent.…”

Ni-Catalyzed C–P Coupling of Aryl, Benzyl, or Allyl Ammonium Salts with P(O)H Compounds

“…In the 1980s, Hirao and co-workers reported the palladium-catalyzed C–P bond construction via reaction of aryl or alkenyl halides with dialkyl phosphites . Since then, a range of organic or organometallic compounds including organohalides, alcohol or phenol derivatives, diazonium salts, arylhydrazines, boronic acids, silanes, organobismuth compounds, sulfides, aryl nitriles, aryl or alkenyl carboxylic acids, acylphosphines, amides, and aromatic esters were employed as the coupling partners. Considering the importance of organophosphorus compounds and the drawbacks of the reported methods such as harsh reaction conditions and limited substrate scope, developing new synthetic methods and searching for alternative coupling partners are still highly desirable.…”

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

“…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 .…”