Indium(I) iodide promoted highly selective 1,2-addition of allyl and benzyl groups to α,β-unsaturated nitriles under sonication: a new synthesis of conjugated imines

Catalytic Use of Low‐Valent Cationic Gallium(I) Complexes as π‐Acids

“…In contrast with Ga(III)‐ and In(III)‐based catalysts, Ga(I) complexes have remained little exploited in homogeneous molecular catalysis. Unlike low‐valent In(I) salts used in a wide range of organic transformations as catalysts (e. g. InX‐catalyzed allylations, allenylation, propargylations, Reformatsky reactions, 1,2‐additions or radical cyclizations), the use of Ga(I) has been mainly limited to stoichiometric reactions, with a notable recent exception for the formation of C−C bonds from boron‐based pronucleophiles and various electrophiles . The in situ generated [18]‐crown‐6‐Ga(I)⋅(dioxane) n OTf complex was used for its ambiphilic nature, since Ga(I) is both a Lewis acid (by its three vacant p orbitals) and a Lewis base (by its lone pair).…”

Recent Advances in Indium-Promoted Organic Reactions

“…66 A salient reaction is the indium(I) iodide promoted 1,2addition of allyl and benzyl bromides to a,b-unsaturated nitriles that gives the corresponding conjugated imines; high 1,2-selectivity was observed, and surprisingly only 20 mol% of indium(I) iodide was required in the reaction. 67…”

Hydride-Induced Novel Cyclization of Dienedinitriles Leading to Multifunctionalized Cyclopentadienes

“…The addition reaction of nucleophiles to α,β-unsaturated nitriles (for examples acrylonitrile and derivatives) is a fundamental reaction in organic chemistry and of great synthetic interest . We have recently developed an efficient synthetic method for 1,4-dicyano-1,3-butadienes 1 , which can be considered as analogues of acrylonitrile derivatives, but they should have much richer reaction chemistry because of their unique conjugated structure.…”