Tertiary phosphine–palladium(0)–ethylene complexes

Abstract

The synthesis of L2Pd-ethylene complexes (L = triphenylphosphine, tricyclohexylphosphine, or tri-otolyl phosphite) and of L2Pd (L == tricyclohexylphosphine) is reported ; these easily accessible compounds may serve as starting materials in oxidative addition reactions.

Acrylate formation from CO2 and ethylene: catalysis with palladium and mechanistic insight

“…Alternative routes towards a palladalactone were explored with various palladium precursors and ligands: (Dialkyl)Pd(II)-complexes are prone to undergo reductive elimination, either thermally or acid-induced. 14 Indeed, (dcpe)Pd(CH 2 CH 3 ) 2 (3), 15 which was synthesized starting from Pd(OAc) 2 and Et 3 Al in 50% yield, formed (dcpe)Pd(H 2 CQCH 2 ) 15,16 upon heating (70 1C, THF-d 8 , 2 h).…”

Allylic alkylation: nucleophilic attack on .pi.-allylpalladium complexes

“…H); IR (CHC13) 1730, 1655 cm-1; mass spectrum m/e (rel %)222 (3), 147(16), 133(17), 121(22), 105 (100), 93(23), 91(32), 79 (26), 77(22) (caled forC14H2202, 222.1620; found, 222.1620).…”

Allylic alkylation: nature of the nucleophile and application to prenylation

“…7 (x = 2; Y = PhS): NMR (CC14) 7.40 (m, 5 H), 4.88, 4.74 and 4.71 (3s, 2 H), 3.98 (m, 1 H), 3.59 (s, 3 H), 2.65 (m, 1 ), 1.2-2.6 (m, 8 H); IR (CC14) 3070, 2938, 2860, 1740, 1550cm-'; mass spectrum m/e (rel %) 276 (26), 182 (100), 167 (45), 166 (18), 149 (25), 135 (21) , 123 (88), 121 (65), 110 (54), 109 (37), 108 (30), 95 (93), 93 (32) , 91 (48), 79 (70), 78 (37), 77 (54), 67 (45), 66 (42), 55 (35), 53 (33) , 51 (31), 41 (66), 40 (72), 39 (60) (caled for C16H20O2S, 276.1 1835; found, 276.11856).…”

“…The combined ether extracts were washed with water, 10% aqueous hydrochloric acid solution, and saturated aqueous sodium chloride solution. After drying and evaporation in vacuo, the crude oil was purified by PLC eluting with chloroform to give 66 mg (100%) of l-(2'-carbomethoxyethyl)-4-tert-butylcyclohexene: NMR (CDC13) 5.38 (m, 1 H), 3.64 (s, 3 ), 1.0-2.6 (m, 11 ), 0.85 (s, 9 H); IR (CC14) 1740 cm-1; mass spectrum m/e (rel %) 224 (1), 168 (47), 146 (33), 145 (20), 108 (41), 107 (38), 95 (21), 94 (64), 93 (88), 92 (28), 91 (22), 79 (32), 58 (100) (caled for C]4H2402, 224.1776; found, 224.1778).…”