Ab is(cycloocta-1,5-diene)nickel-catalyzed highly regio-and (E)-stereoselectivehydrocarboxylation of 2-alkynylanilines under very mild conditions has been developed to afford( E)-[2-(o-aminophenyl)]acrylic acids,w hich coulde asily be converted to (E)-3-alkylidene-2-indolinones with important potential bioactivity. Thes tereoselective syntheses of two biologically active molecules,( E)-3-benzylidene-2-indolinone( chemo-preventive potential in inducing NQO1 activity) and (E)-3-(3-methylbutylidene)-2-indolinone( an atural product isolated from Cimicifuga foetida with cytotoxic activity against HL-60 cells) are presented as examples.

of main observation and conclusion β-H elimination is an intrinsic problem in transition metal-catalyzed reactions. We describe herein an interesting ligand effect for Et 2 Zn acting as either ethyl provider or H provider, respectively: by applying SPhos or Gorlos-Phos as the ligand, β-H elimination has been successfully controlled in the corresponding Negishi coupling reaction affording different poly-substituted allenes in good yields and excellent selectivities. SAESI-MS (Solvent Assisted Electrospray Ionization Mass Spectrometry) has been applied to successfully capture the highly reactive organometallic intermediates, which show the different coordination behaviors of Pd with SPhos or Gorlos-Phos as the ligand in the catalytic cycle. In addition, the different reactivities of Int 1 and Int 2 towards the formation of the final allene products have been demonstrated via SAESI-MS/MS experiments. These MS studies visualized the whole catalytic cycle for the Negishi coupling reaction while nicely explain the observed reactivity and selectivity.www.cjc.wiley-vch.de

A highly efficient Pd/H+-cocatalyzed kinetic resolution reaction of tertiary propargylic alcohols has been reported. The method provides an efficient approach to prepare a series of propargylic alcohols bearing a chiral...

A completely different approach for the asymmetric construction of oxazoline derivatives with an excellent enantioselectivity via the palladium-catalyzed coupling-cyclization of N-(buta-2,3-dienyl)amides with aryl iodides has been reported.

A palladium-catalyzed C-O bond formation reaction between phenols and allenylic carbonates to give 2,3-allenic aromatic ethers with decent to excellent yields under mild reaction conditions has been described. A variety...