An Efficient and Selective Hydroarylation of Styrenes with Electron‐Rich Arenes, Catalyzed by Bismuth(III) Chloride and Affording Markovnikov Adducts

Abstract

In the presence of BiCl3, the hydroarylation of styrenes with electron‐rich arenes afforded Markovnikov adducts selectively in good to high yields. Under arene‐free conditions, the intermolecular hydroarylation of α‐substituted styrenes and subsequent intramolecular hydroarylation produced the cyclic dimers of α‐substituted styrenes in good yields. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)

Highly efficient gold(III)-catalyzed intermolecular hydroarylation of unactivated alkenes with arenes under mild conditions

“…Transition metal catalysts for such transformation reactions are of particular importance due to their high selectivity, synthetic efficiency and environmental friendliness [8][9][10]. In the literatures, hydroarylations of styrene derivatives with electron-rich aryl and heterocyclic compounds have also been carried out with FeCl 3 [11] , Bi(OTf) 3 [12], or BiCl 3 [13] as the catalyst for the synthesis of a variety of 1,1-diarylalkanes. However, these reported intermolecular hydroarylation reactions usually require high reaction temperature (80-110°C) and/or prolonged reaction time ($24 h).…”

Access to Polycyclic Derivatives by Triflate‐Catalyzed Intramolecular Hydroarylation

“…Intramolecular catalytic reactions [11] have been achieved with Rh I complexes, [12] In-(OTf) 3 (OTf = triflate), [13] InBr 3 , [14] BiCl 3 , [15] RuCl 3 /AgOTf [16] or performed with catalytic systems such as [PPh 3 AuCl]/AgSbF 6 [17] or AuCl 3 /AgOTf; [18] these reactions essentially involve the aryl coupling with terminal double bonds. Very few references deal with the intramolecular hydroarylation of internal alkenes (with AlCl 3 or TfOH).…”

Addition Reactions: Polar Addition

“…Under arene-free conditions, the intermolecular hydroarylation of α-substituted styrenes and subsequent intramolecular hydroarylation produced the cyclic dimers of α-substituted styrenes in good yields. 122,123 Ytterbium and lutetium ionic complexes, derived from enantiopure substituted (R)-binaphthylamine ligands of the general formula [Li(THF) n ][Ln[(R)C 20 H 12 (NR) 2 ] 2 ], have been investigated as catalysts for hydroamination/cyclization of several unsatu-ee rated amines CH 2 =CH(CH 2 ) n C(R 2 )CH 2 NH 2 (n = 1 or 2). Complexes with isopropyl or cyclohexyl substituents on nitrogen atoms were found to be efficient catalysts for the formation of N-containing heterocycles under mild conditions with enantiomeric excesses up to 78%.…”