Platinum‐Catalyzed Intermolecular Hydroamination of Alkenes: Halide‐Anion‐Promoted Catalysis

Abstract

Tetraalkylphosphonium halides play the role of “promoters” for the previously unknown PtII‐catalyzed hydroamination of alkenes. The promoting effect of these “cocatalysts” depends only upon their anionic moiety. The PtII/nBu4PBr system exhibits an unprecedented catalytic activity (aerobic conditions) for the hydroamination of ethylene and 1‐hexene (regioselectivity > 95 %, Markovnikov).(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

Reactions of Diethylamine and Ethylene Catalyzed by PtII or Pt0 – Transalkylation vs. Hydroamination

“…In the last six years, a number of papers have appeared on the hydroamination of ethylene and other α-olefins catalyzed by Pt-based systems. These include the addition of substituted anilines to ethylene [4] and 1-hexene [5] catalyzed by PtBr 2 /nBu 4 PBr (I) and our recent extension to aqueous media (PtBr 2 / NaBr (aq) , IЈ), [6] the addition of carboxamides to RHC=CH 2 (R = H, Me) catalyzed by [PtCl 2 (H 2 C=CH 2 )] 2 /PPh 3 (II) [7] and that of sulfonamides or anilines to more strained olefins catalyzed by (COD)Pt(OTf) 2 (III). [8] For each type of catalyst the turnover number (TON) or product yield was shown to increase as the amine basicity decreases and no activity was found when the conjugate acid of the amine has a pK a value above a certain cut-off value.…”

“…[1] Amongst hydroamination reactions, the most difficult is the intermolecular process with nonactivated olefins, and solutions based on transition metal catalysis are actively pursued. [1][2][3] With regard to industrial applications, short-chain aliphatic olefins and ethylene constitute the most attractive starting materials. In the last six years, a number of papers have appeared on the hydroamination of ethylene and other α-olefins catalyzed by Pt-based systems.…”

Synthesis and visible light luminescence of mononuclear nine-coordinate lanthanide complexes with 2,4,6-tris(2-pyridyl)-1,3,5-triazine

“…The design and synthesis of the complexes of Ln(III) ions with chelating ligands offer many potential applications such as in fluoroimmunoassay [1], spectroscopic structural probes in biologically important systems [2], laser systems [3], optical amplifications [4] and emitting materials in multilayer organic light emitting diodes (OLEDs) [5]. Shielding of the f-orbitals by the 5 s and 5p shells result in narrow linelike emissions of optically pure colours and long radiative lifetimes.…”

Selective Catalytic Reductions of Amides and Nitriles to Amines

“…There is a continuing interest in the development of easier and cost-efficient methods for their synthesis (for some reviews see [2][3][4][5][6][7][8][9][10][11]). The reduction of amides is one of the most fundamental methods among the different procedures for preparing functionalized amines both on laboratory scale as well as in industry.…”