Anti-Markovnikov Addition of Both Primary and Secondary Amines to Terminal Alkynes Catalyzed by the TpRh(C₂H₄)₂/PPh₃ System

Microwave-Assisted Synthesis and Characterization of [Rh2(OAc)4(L)2] Paddlewheel Complexes: A Joint Experimental and Computational Study

“…Instead, multiple signals are observed from 7.5 to 6.7 ppm, which are assigned to aromatic protons, attributed to the formation of oligoand polyphenylacetylene (PPA) species, with a concomitant complete consumption of PA. Similar results have been reported using other rhodium mononuclear complexes as catalytic species [59][60][61][62][63]. At the same time, free amine is observed and quantitatively recovered.…”

“…Based on the properties of the catalyst, this reaction can afford either the Markovnikov or anti-Markovnikov products ( Figure 2) [52][53][54][55][56][57][58]. Furthermore, a few Rh species have been reported as excellent catalysts for this process [59][60][61][62][63]. However, to the best of our knowledge, complex I has not yet been reported as a catalytic precursor for this reaction.…”

Hydro(trispyrazolyl)borato‐Ruthenium(II) Diphosphinoamino Complex‐Catalyzed Addition of β‐Diketones to 1‐Alkynes and Anti‐Markovnikov Addition of Secondary Amines to Aromatic 1‐Alkynes

“…[9] The CsOH-catalyzed hydroamination of phenylacetylene with substituted anilines and N-heterocycles was the only known example of anti-Markovnikov addition of secondary amines to terminal alkynes until recently when it was reported that TpRhA C H T U N G T R E N N U N G (C 2 H 4 ) 2 /PPh 3 catalyzes the anti-Markovnikov hydroamination of terminal alkynes with secondary amines as well as primary ones. [10][11] We report here that a hydrotris(pyrazolyl)-borate ruthenium complex supported by a diphosphinoamine ligand is an excellent catalyst for the addition of b-diketones to 1-alkynes and is also effective for the unusual anti-Markovnikov addition of secondary amines to aromatic terminal alkynes.…”

Well‐Defined Regioselective Iminopyridine Rhodium Catalysts for Anti‐Markovnikov Addition of Aromatic Primary Amines to 1‐Octyne

“…Rhodium or iridium complexes have previously been reported to catalyze intermolecular hydroaminations. [9,20] Iminopyridines constitute a broad family of chelating dinitrogen ligands whose coordination chemistry has been used in palladium and nickel catalysis, particularly in olefin polymerization. [11,21] The results of these studies motivated us to study complexes 1-4 as suitable active catalysts in intermolecular hydroamination reactions.…”

“…[8] Recently, Fukumoto et al described the first catalytic system that allows both primary and secondary amines to react with terminal alkynes to give anti-Markovnikov products. [9] The work described here concerns our initial approach to develop effective methods for C À N bond formation. The importance of steric protection in late metal-catalyzed chemistry stimulated our interest in the synthesis of bulky iminopyridine-rhodium complexes.…”