A facile large-scale synthesis of the “push–pull”-substituted ligand bis(diethylamino)(pentafluorophenyl)phosphane is reported. A selenophosphorane as well as complexes with CuI and PdCl2, can be formed almost quantitatively from suitable starting materials. The PdII complex shows a square-planar coordination with significant distortions of the Cl–Pd–Cl moiety in the solid state. In contrast, t...

2-Ynamides can be synthesised through PdII catalysed oxidative carbonylation, utilising low catalyst loadings. A variety of alkynes and amines can be used to afford 2-ynamides in high yields, whilst overcoming the drawbacks associated with previous oxidative methods, which rely on dangerous solvents and gas mixtures. The use of [NBu4 ]I allows the utilisation of the industrially recommended sol...

An enantioselective PdII /Brønsted acid-catalyzed carbonylative carbocyclization of enallenes ending with a cross-dehydrogenative coupling (CDC) with a terminal alkyne was developed. VAPOL phosphoric acid was found as the best co-catalyst among the examined 28 chiral acids, for inducing the enantioselectivity of α-chiral ketones. As a result, a number of chiral cyclopentenones were easily synth...

Asymmetric coupling proceeds efficiently between propargylic acetates, cycloalkenes and electron-rich heteroarenes including indoles, pyrroles, activated furans thiophenes. 2,3-Disubstituted tetrahydrofurans pyrrolidines are produced in trans configuration excellent enantiomeric ratios. The reaction via Wacker-type attack of nucleophilic on alkenes by allenyl PdII species.

A PdII catalyst system has been used to successfully catalyse two mechanistically distinct reactions in a one-pot procedure: dehydrogenation of 2,2-disubstituted cyclopentane-1,3-diones and the subsequent oxidative Heck coupling. This auto-tandem catalytic reaction is applicable to both batch and continuous flow processes, with the latter being the first example of a tandem aerobic dehydrogenat...

Abstract: The anionic polymerization of 1-phosphaisoprene [Mes*P=C(Me)−CH=CH2 (E-1)] affords poly(1-phosphaisoprene) 2 in high yield (75%). Concentrated solutions polymer (Mn = 21,800 g mol–1; Đ 1.02) a P-analogue natural rubber, undergo gelation upon treatment with [Pd(cod)Cl2] (0.15 P equiv). Evidence for P-coordination to PdII was obtained by 31P and 1H NMR spectroscopy. is reversed the addi...

Heck reactions were performed with 4-bromoacetophenone and n-butyl acrylate, yielding the trans-arylated acrylate ester with high selectivity. Pd–zeolite catalysts were compared with supported Pd metal catalysts. In order to obtain an active and heterogeneous catalyst, the preformed or in situ-formed catalytically active Pd0 species and the PdII intermediates must be sufficiently stabilized on ...