Recollections of organopalladium chemistry

Abstract

Organopalladium chemistry has 40 years' history. It was born in late 1950s by the invention of the Wacker process. Inspired by the Wacker reaction, we discovered the ®rst example of the carbon±carbon bond formation by means of a Pd complex, and opened the ®eld of p-allylpalladium chemistry. Historical account of organopalladium chemistry, and major accomplishments in our laboratory in 1960s are presented.

Oxidative addition of allyl and propargyl halides on palladium(0) complexes bearing bidentate ligands with quinolinic structure

“…The solid residual was treated with CH 2 Cl 2 and activated charcoal for 5/10 min and filtered on a celite filter. 3.34;N,3.32. Found: C,36.81;H,3.25;N,3.13. The following compounds were obtained according to the above described procedure using the appropriate ligand.…”

“…Calcd for C 10 H 9 NS: C,68.53;H,5.18;N,7.99. Found: C,68.71;H,5.23;N,8.12. Synthesis of the ligand T-tBQ 9.90 g (47.82 mmol) of 8-bromoquinoline were dissolved in 50 ml of DMSO in a 250 ml flask bearing a bubble condenser.…”

“…Calcd for C 10 H 9 NS: C,68.53;H,5.18;N,7.99. Found: C,68.71;H,5.23;N,8.12. Synthesis of the ligand T-tBQ 9.90 g (47.82 mmol) of 8-bromoquinoline were dissolved in 50 ml of DMSO in a 250 ml flask bearing a bubble condenser. 32.3 ml (286.9 mmol) of 2-methyl-2-propanthiol and 21.46 g (382.5 mmol) of KOH were inserted in the flask and the resulting mixture was heated under vigorous stirring at 80 c for 72 h (the reaction progress was monitored by TLC).…”

“…1 H-NMR (300 MHz, CDCl 3 , T ¼ 298 K, ppm) d: 1.40 (s,9H,t Bu),7.44 (dd,1H,J ¼ 8.3,4.2 Hz,H 3 ),7.53 (dd,1H,J ¼ 8.2,7.2 Hz,H 6 ),7.84 (dd,1H,J ¼ 8.2,1.4 Hz,H 5 ),8.06 (dd,1H,J ¼ 7.2,1.4 Hz,H 7 ),8.18 (dd,1H,J ¼ 8.3,1,8 Hz,H 4 ),9.08 (dd,1H,J ¼ 4.2,1.8 Hz,H 2 Anal. Calcd for C 16 H 17 NO 4 PdS: C,45.13;H,4.02;N,3.29. Found: C,45.31;H,4.22;N,3.14.…”

“…IR (KBr pellets): n C¼N 1592 cm À1 ; n ClO 1099 cm À1 ; d ClO 621 cm À1 .Anal. Calcd for C16 H 20 ClNO 4 PdS: C, 41.39; H, 4.34;N, 3.02. Found: C, 41.47; H, 4.51;N, 2.89.…”