Nickel-catalysed bis-allylation of internal alkynes with triallylindium

Abstract

The Ni-catalysed reaction of triallylindium with internal alkynes underwent bis-allylation to afford octa-1,4,7-trienes in high yield.

Organoindium Reagents: The Preparation and Application in Organic Synthesis

“…However, the addition of triallylindium reagent to internal alkynes proved to be difficult, and the reaction failed under palladium catalysis. Efforts made by Hirashita and co-workers revealed that the reaction progressed well in the presence of Ni(acac) 2 (1 equiv) and COD (2 equiv) to produce the bis-allylated product A predominantly (Scheme ) . However, under optimized conditions, the use of other allylmetallic reagents such as allylindium diiodide, allylindium sesquihalide, allylstannane, allylgallium, and allylmagnesium reagents led to poor efficiency.…”

“…Organic chemists have noticed in many cases that organoindium reagents exhibited better performance than their organomagnesium and organozinc counterparts. Thus, the unique property of organoindium reagent also confers specific reactivity for carbon–carbon bond formations, allowing organic transformations to proceed with better selectivities (e.g., product yield and chemoselectivity). ,− …”

Chiral NHC Ligands Bearing a Pyridine Moiety in Copper-Catalyzed 1,2-Addition of Dialkylzinc Reagents to β-Aryl-α,β-unsaturated N-Tosylaldimines

“… a 2.0 equiv of 2 and 10 equiv of HMPA were used unless otherwise noted. b The ratio was determined by 1 H NMR. c The absolute configurations of 3 , except for 3aE , were determined on the basis of the analogous reactions in Table (also see ref ). d The reaction was carried out at 0 °C. e The reaction was carried out at −20 °C. f The ee was determined by HPLC using the corresponding amino alcohol, which was prepared from 3kE by treatment of ozonolysis followed by reduction. g Using 3.0 equiv of 2E . h Using 5.0 equiv of 2M at 0 °C for 120 h. i The peaks of the 1,2- and 1,4-adducts overlapped in 1 H NMR. j Diphenylzinc was prepared by following literature k Diallylzinc was prepared by following literature …”

“…21 k Diallylzinc was prepared by following literature. 22 The Journal of Organic Chemistry corresponding 2-aminoalcohols. We demonstrated ozonolysis of 3aE with 98% ee, which was obtained by recrystallization, followed by reduction to afford the 2-aminoalcohol 14 in 89% yield without any loss of enantioselectivity (eq 2).…”

Making and Breaking of Sn−C and In−C Bonds in Situ: The Cases of Allyltins and Allylindiums

“…Facile transmetalation involving allylmagnesium halide and indium trihalide generates reactive allylindium(III) intermediates in situ, with the latter being utilized in a followup allylation reaction. 172,191,211 For example, allylindiumdichloride 90A mediates the allylation of unprotected carbohydrates such as ribose 90a in aqueous ethanol, providing the corresponding allylated derivate 90b with high diastereoselectivity (Scheme 221). 172 Triallylindium(III), generated via magnesium-to-indium transmetalation, reacts with R,β-unsaturated nitrile and carbonyl compounds to give the corresponding 1,4-addition products (Scheme 222).…”