Cu-catalyzed Pd-free Sonogashira coupling has been proposed as a straightforward and convenient route to valuable steroidal enynes. A biligand catalyst system based on Ph3P and TMEDA has been designed. The protocol was utilized for the efficient coupling of iodosteroids with diverse terminal alkynes and 1-trimethylsilylalkynes. A possible role of an auxiliary ligand as a phase-transfer catalyst...

trans-[Pt(C[triple bond]C(Ar)C[triple bond]CH)2(PMe3)2](Ar = C(6)Me(4)-3,4,5,6) (1) reacts with PPN[Au(acac)(2)](Hacac = acetylacetone; 1 : 1.16 molar ratio; PPN = (Ph3P)2N) to give PPN[(Au[Pt(PMe3)2]2)(mu-Ar(C[triple bond]C)2)3] (2) the crystal structure of which showed the anions as quasi equilateral triangles stacked parallel to each other through C-HAu interactions, resulting in channels of...

Z. Naturforsch. 52 b, 209-213 (1997); received December 4, 1996 Gold(I) Coordination, Amine Complexes, Secondary Amines, Ammonium Complexes Treatment of N,N'-diisopropyl-ethylenediamine or 1,4-piperazine with two equivalents of [(Ph^P)Au]+ BF4leads to binuclear complexes of the diamines: {[(Ph3P)Au]HN('Pro)NCH2-}22+ 2 BF4~ (1) and {[(Ph3P)Au]HNCH2CH2}22+ 2 BF4~ (2), respectively. In the product...

The chemistry of complexes with diatomic chalcogen ligands has attracted much attention due to their unique structure, biological interest, potential for hydrogen-transfer catalysis, and synthetic utility as a precursor of new metal cluster complexes. However, since sulfur and selenium ligands have a strong propensity for bridging metal atoms, it is often difficult to prepare their mononuclear ...

Both monoand bisylide zwitterionic complexes of gold(I), [(C6F5){PhCH(PPh3)}Au] (4), [(C6F5)2(C6H4-p){CH(PPh3)}2Au2] (5) and [(C6F5)2(C6H4-m){CH(PPh3)}2Au2] (6) were prepared by THT substitution in [C6F5(THT)Au] (THT = tetrahydrothiophene) using deprotonated monoand bis-phosphonium salts. Lithiation of 4,4′-dibromo-2,3,5,6,2′ ,3′,5′,6′-octafluoro-1,1′biphenyl and transmetallation with [Cl(Ph3P)...

A carbodiphosphorane ((Ph3P)2C) mediated synthesis of the first triflyloxyphosphonium dication (12+) bearing two electrophilic sites is presented. Depending on the nucleophile, 12+ reacts selectively either at the sulfur atom of the triflyloxy moiety or at the directly attached phosphorus atom. In substitution reactions at the phosphorus atom the triflyloxy moiety serves as a leaving group and ...

A striking dependence on the method of workup has been found for annulation benzonitriles ArC≡N to N-methyl 2-toluamide (1), facilitated by n-BuLi (2 equiv): quenching reaction a slow addition water produced expected 1-isoquinolones 2; contrast, pouring mixture into afforded cyclic aminals 5 (retaining NMe group original toluamide). The mechanism two processes is discussed in terms actual H+ co...