Titanocene difluorides can be obtained by halide metathesis of the respective titanocene dichlorides with trimethyltin fluoride (Me(3)SnF), giving access to a new class of cytotoxic active substances. Furthermore, an improved method for the synthesis of diaryl-substituted titanocene dichlorides is presented.

Dimethylsulfonium methylide mediated olefination of 2-phenylethenylidene phosphonoacetate followed by the Horner-Wadsworth-Emmons reaction with aromatic aldehydes provided access to reactive 1,5-diaryl-2-ethoxycarbonyl [3]dendralenes which in situ underwent Diels-Alder cyclodimerisation leading to highly functionalised cyclohexenes with very high regio- and stereoselectivity.

A highly efficient and chemoselective method for the synthesis of diaryl disulfides is developed via a visible light-promoted coupling of readily accessible arenediazonium tetrafluoroborates and CS2. This practical and convenient protocol provides a direct pathway for the assembly of a series of disulfides in an environmentally friendly manner with good to excellent yields.

[reaction: see text] Bu(3)Sn-mediated 5-exo-dig radical cyclization of diaryl enediynes provides a mild and efficient approach to tin-substituted fulvenes. Further synthetic opportunities opened by this process and general factors responsible for the observed regio- and stereoselectivity are outlined.

Iron-catalyzed trifluoromethylation with concomitant 1,2-migration of an aryl group starting from diaryl allyl alcohol was achieved under mild conditions. This reaction system affords α-substituted-β-trifluoromethyl carbonyl compounds in high efficiency. In the case of substrates bearing different aryl groups, selective migration was observed.

The diarylalkenyl propargylic complex framework has been found in many natural products and medicinal regents. Herein, we have disclosed an unprecedented FeCl(3) catalyzed ene-type reaction of propargylic alcohols with 1,1-diaryl alkenes which enabled us to furnish a diarylalkenyl propargylic complex framework in moderate to high chemical yields (up to 98%).

A novel radical phosphinylation of α,α-diaryl allylic alcohols with arylphosphine oxides was described for the direct preparation of α-aryl-β-phosphinylated carbonyl ketones in medium to good yields via 1,2-aryl migration. In this reaction, formation of new C(Ar)-C(sp(3)) and C(sp(3))-P bonds was observed.

A high yielding, batch mode synthesis of diaryl ethers and sulfides by an S(N)Ar fluoride-mediated process in scCO(2) has been developed; the use of a polymer-supported imidazolium fluoride reagent in batch mode led to the development of a fixed-bed continuous flow process, with high conversions.

Methyl 1-aryl-3-cinnamoyl-4,5-dioxo-4,5-dihydro-1H-pyrrole-2-carboxylates interact with 3-(arylamino)-1H-inden-1-ones to give the corresponding 1,1'-diaryl-3'-cinnamoyl-4'-hydroxy-1H-spiro[indeno[1,2-b]pyrrole-3,2'-pyrrole]-2,4,5'(1'H)-triones in good yields.