Diene Complexes oftrans-5-Palladatricyclo[4.1.0.02,4]heptanes

Abstract

The complexes rac‐5 and rac‐6 of the trans‐5‐palladatricyclo[4.1.0.02,4]heptane rac‐2a with norbornadiene and 1,5‐cyclooctadiene were prepared and investigated by X‐ray structure determination. With open‐chained, unsaturated substrates, e.g. 7 and 8, no complexes could be isolated. In all cases no insertion of the olefin into the metal–carbon bond of the palladacycloalkane was observed.

Dimethyl dipropargylmalonate

“…Dimethyl dipropargylmalonate, (I), is a frequently used building block for organic synthesis [for selected examples, see Yamamoto et al (2005), Trost & Rudd (2005), Grigg et al (2003), Hashmi et al (1998) and Hashmi et al (1997)]. The related dimethyl monopropargylmalonate is even more popular, but a selective monopropargylation is difficult; usually in the known procedures significant amounts of the dimethyl dipropargylmalonate as a side product cannot be avoided (Atkinson & Grimshire, 1986;Brillon, 1986;Curran et al, 1991;Dö tz et al, 1987;Llerena et al, 1998).…”

Bis{μ-dimethyl 1-[1-methoxycarbonyl-3-(methoxyoxalyl)-2-methylpropenyl]-3,3-dimethylcyclopropane-1,2-dicarboxylato(2–)}bis[(triphenylphosphine)palladium(II)] acetone solvate

“…Comment 5-Pallada-anti-tricyclo[4.1.0.0 2,4 ]heptanes are an interesting class of chiral organopalladium compounds which are usually stable in water and air (Hashmi, 2002). Several complexes of these compounds have been prepared (Hashmi, Naumann, Probst et al, 1997;Hashmi, Naumann, Bolte & Rivas Nass, 1998;Hashmi, Bats et al, 1998) and their reactivity has been studied (Hashmi et al, 1999). We have now tried to prepare the complex with the simple triphenylphosphine ligand, which immediately led to a precipitate with low solubility.…”