Aryl C(sp2)-X Coupling (X = C, N, O, Cl) and Facile Control of N-Mono- and N,N-Diarylation of Primary Alkylamines at a Pt(IV) Center

We present the first example of an unprecedented and fast aryl C(sp(2))-X reductive elimination from a series of isolated Pt(IV) aryl complexes (Ar = p-FC6H4) (LPtF)-F-IV(py)(Ar)X (X = CN, Cl, 4-O6H4NO2) and (LPtF2)-F-IV (Ar)(HX) (X = NHAlk; Alk = n-Bu, PhCH2, cyclo-C6H11, t-Bu, cyclopropylmethyl) bearing a bulky bidentate 2-[bis(adamant-1-yl)phosphino]phenoxide ligand (L). The C(sp(2))-X reductive elimination reactions of all isolated Pt(IV) complexes follow first-order kinetics and were modeled using density functional theory (DFT) calculations. When a difluoro complex (LPtF2)-F-IV(Ar)(py) is treated with TMS-X (TMS = trimethylsilyl; X= NMe2, SPh, OPh, CCPh) it also gives the corresponding products of the Ar-X coupling but without observable (LPtF)-F-IV(py)(Ar)X intermediates. Remarkably, the (LPtF2)-F-IV (Ar)(HX) complexes with alkylamine ligands (HX = NH(2)Alk) form selectively either mono- (ArNHAlk) or diarylated (Ar(2)NAlk) products in the presence or absence of an added Et3N, respectively. This method allows for a one-pot preparation of diarylalkylamine bearing different aryl groups. These findings were also applied in unprecedented mono- and di-N-arylation of amino acid derivatives (lysine and tr tophan) under very mild conditions.