Further Rearrangement of Meisenheimer Products of Allyl Aryl Amine Oxides

One‐Pot Synthesis of O‐Allylhydroxylamines through the Organocatalytic Oxidation of Tertiary Allylic Amines Followed by a [2,3]‐Meisenheimer Rearrangement

“…Although Majumdar and Jana reported that all kinds of allylic amines provide this additional shift at elevated temperatures for extended reaction times,9 we only observed this shift on conjugated allylic systems (Table 3). Initially, various phenyl‐substituted allylic amines ( 1 m – r ) were tested, leading to allylic alcohols 9 a – e and 10 in high yields.…”

“…To our surprise, an additional rearrangement took place. Literature reports indicate such an additional rearrangement could occur only at extended heating and with a change of solvent 9. However, in our case, this happened only when an aromatic or a conjugated aromatic moiety was utilized at the terminal substituent of the allylic amine (Table 3).…”

Regioselective synthesis of thieno[2,3-b]indoles by tandem cyclisation involving sequential sigmatropic rearrangements

“…2-Hydroxy- 3-methylene-8-methyl-2-phenoxymethyl-2H-thieno [2,3-b] C,70.56;H,5.30;N,4.33. Found C,70.75;H,5.46;N,-2H-thieno [2,3-b]…”

Tsuji–Trost allylations with palladium recovery by phosphines/Pd(0)-triolefinic macrocyclic catalysts

“…THF was stored over potassium hydroxide for one day and then dried by distillation from sodium-benzophenone ketyl just before use. 1 H NMR spectra (250 or 360 MHz) and 13 C NMR (62.5 or 90 MHz) were usually recorded on a Bruker DPX-250 or on a Bruker DPX-360. Chemical shifts (d, ppm) are referenced to Me 4 Si ( 1 H and 13 C).…”

“…N-methylaniline 3a (31 lL, 0.989 g/mL, 0.281 mmol) and anhydrous and degassed THF (3 mL) were added. The mixture was magnetically stirred at room temperature under argon for 22 h. The solvent was evaporated and the residue was purified by flash-chromatography (silica gel) with hexane-ethyl acetate 97:3, to afford 4a [13] as an oil (53 mg, 86% yield); 1 H NMR (CDCl 3 ) d = 2.97 (s, 3H), 4.07 (d, J = 5.5 Hz, 2H), 6.23 (dt, J = 15.7 and 5.4 Hz, 1H), 6.51 (d, J = 15.7 Hz, 1H), 6.75 (m, 3H), 7.22 (m, 7H); 13 C NMR (CDCl 3 ) d = 38.1, 55.0, 112. 8, 116.7, 125.9, 126.5, 127.5, 128.7, 129.3, 131.4, 137.1, 149.7.…”