Highly Efficient Palladium‐Catalyzed Allylic Alkylation of Cyanoacetamides with Controllable and Chemoselective Mono‐ and Double Substitutions

Abstract

It was found that catalytic allylation of various cyanoacetamides proceeded smoothly and efficiently in environmentally benign PEG‐400 (PEG=poly(ethylene glycol)) in the presence of Pd(OAc)2 and novel triazine‐derived multifunctional ligand L1, with which this reaction could afford the structurally diverse mono‐ and double allylated adducts in good to excellent yields as well as good chemo‐ and regioselectivity. In addition, this Pd/L1/PEG‐400 catalyst system could be recycled for five runs with good yield and high efficiency, which supported the notion that the triazine‐containing Schiff base based phosphine ligand could be a multifunctional and reusable ligand encapsulated in PEG‐400.

Allylic Amination of Pd(II)-Allyl Complexes via High-Valent Pd Intermediates

“…Pd II (allyl) complexes have been previously established as intermediates toward forming allylic substitution products such as allylamine and allyl acetate. − The reaction conditions usually require higher temperatures or longer reaction times for the Pd 0/II -catalyzed allylic substitution reactions. , Recent reports reveal three chemical oxidants (PhI­(OAc) 2 , PhICl 2 , and NFTPT) that have been used to oxidize the Pd II complexes to the stable Pd IV complexes containing a OAc, Cl, or F ligand. − These Pd IV complexes can undergo fast reductive elimination to make C–Cl, C–F or C–OAc bond formation products. Since our [( Me N4)­Pd II (η 3 -allyl)] + complexes proved to be easily oxidized to high-valent Pd species, we performed preliminary investigations of the reactivity of 2 + , 3 + , and 4 + toward C–Cl and C–OAc bond formations using PhICl 2 and PhI­(OAc) 2 . , However, we did not observe Pd IV complexes bearing OAc or Cl ligands, nor C–Cl or C–OAc bond formation products from the reaction of 2 + – 4 + with PhICl 2 and PhI­(OAc) 2 (Table S2).…”

Diiodido-bis{N-[2-(diphenylphosphino)benzylidene]benzylamine-κ2N,P}dicopper(I)

“…In principle, all types of primary amines-aromatic or aliphatic-react in high yields under mild conditions [9][10][11][12][13][14][15][16][17][18][19][20][21]. In this context, of particular interest might be the use of oligo-amines, which lead to the formation of polydentate P∩N ligands [22,23], or the use of chiral amines [24]. Our interest in P∩N copper(I) complexes comes from the fact that many of them feature interesting luminescence properties.…”