Preparation of primary arylamines via arylzinc chlorides in good yields

Cosolvent‐promoted electrophilic amination of organozinc reagents

“…Moreover, it was observed that, by using 2 equiv. of DMPU, the yields could be improved up to 72–78% with 10 mol% catalyst 30. HMPA and TMU enhanced the reaction as much as DMPU (Table 1 entries 5–7 and 23).…”

High Regiocontrol in the Zinc‐Mediated Crotylation of Aldehydes and Ketones: A Straightforward and Facile Approach to Linear Homoallylic Alcohols in DMPU

“…To our delight, high α-regioselectivity was observed in the crotylation with 71 % of α-product 2a (Table 1, Entry 1), which is similar to the previous prenylation reaction. [9] Due to the carcinogenicity of HMPA, we explored alternative solvents for the crotylation reaction based on previous work on organozinc reagents, [11] such as dimethyl sulfoxide (DMSO), N,N-dimethylformamide (DMF), tetramethylurea (TMU), DMPU, and 1,3-dimethyl-2-imidazolidinone (DMI). The results showed that DMPU was the most suitable solvent for the crotylation reaction to afford α-adduct 2a exclusively in 68 % yield (Table 1, Entry 5).…”

Synthesis of amines by the electrophilic amination of organomagnesium, -zinc, -copper, and -lithium reagents

“…Primary arylamines can be obtained in high yields by the use of a dipolar aprotic cosolvent (Scheme 25). [99][100][101] Addition of a P-, N-, or S-donor ligand causes a significant reduction in the quantity of copper catalysts and a remarkable increase in the yield of amine (Scheme 26). 101 There is no need to use a copper catalyst to obtain primary arylamines in good yields, if the amination of arylzinc reagents with acetone oxime O-tosylate 5b, in the presence of a cosolvent, is performed at 40 ºC.…”