Cascade radical cyclisations of imines

Heck arylations of pent-4-enoates or allylmalonate using a palladium/tetraphosphine catalyst

“…13 2-Methyl-5-(4-nitrophenyl)-pent-4-enoic acid ethyl ester (21) ( Table 3, 13 Table 3, The reaction with electron-deficient aryl bromides such as 4-bromoacetophenone, 4-bromobenzaldehyde or 4-bromobenzonitrile can be performed with as little as 0.01 mol% catalyst. In all cases, the (E)-5-arylpent-4-enoates 1a-7a were obtained in 85-89% selectivity ( Table 1, entries [1][2][3][4][5][6][7][8][9][10][11][12][13][14]. As expected, lower turnover numbers (TONs) of 46-540 were obtained with electron-excessive aryl bromides such as 4-bromoanisole or 4-N,N-dimethylaminobromobenzene.…”

“…Finally, the reaction also proceeds with Pd(OAc) 2 without added ligand. Iodobenzene reacted with allylmalonate using N(n-Bu) 3 as base and 2 mol% Pd(OAc) 2 gave 90% of 3-phenylprop-2-en-1-yl propanedioate [11]. If monophosphine ligands have been successfully used for the reaction with pent-4-enoate or allylmalonate derivatives, to the best of our knowledge, the efficiency of polydentate ligands has not been demonstrated.…”

(2E)-3-(2-Chlorophenyl)-1-[1′-(2-chlorophenyl)indoline-3-spiro-3′-perhydropyrrolo[1,2-a]indol-2′-yl]prop-2-en-1-one

“…For related literature, see: Beddoes et al (1986); Bowman et al (1996); Cremer & Pople (1975); Esker & Newcomb (1993); Fallis & Brinza (1997); Guindon et al (2001); Jeyabharathi et al (2001); Nardelli (1983); Rajeswaran et al (1999); Seshadri et al (2003).…”

Methyl 2-benzyl-1-benzyloxy-6a-methyl-1,2,3,3a,4,6a-hexahydrocyclopenta[b]pyrrole-3a-carboxylate: hydrogen-bondedR44(24) sheets

“…aminyl, iminyl, amidyl radicals etc. (Esker & Newcomb, 1993;Fallis & Brinza, 1997;Bowman et al 1996;Guindon et al, 2001) However, no reports about the capture of neutral alkyloxyaminyl radicals by a multiple function have been published up to date for the preparation of fused pyrrolidine derivatives. We describe here a fused pyrrolidine derivative, (I), prepared for the first time via an alkyl-oxyaminyl radical, which has been generated through the reductive intermolecular or intramolecular addition of carbon radicals to the carbon atom of oxime ethers (Friestad, 2001;Naito et al, 2000;Tauh & Fallis, 1999;Marco-Contelles et al, 1996;Enholm et al, 1990).…”