BiCl₃‐Catalyzed Hydroamination of Norbornene with Aromatic Amines

Abstract

A BiCl 3 -catalyzed hydroamination reaction of norbornene, in which a variety of electron-withdrawing groups were tolerated on amines, was presented. The current transformation possesses the advantages of being highly selective, cheap, and eco-friendly, and this process also represents a rare sys-

Synthesis, structure and reactivity of complexes containing a transition metal–bismuth bond

“…BiCl 3 can similarly act as a low-cost and air-stable Lewis-acid catalyst in hydroamination reactions, a process traditionally catalysed by late transition metal systems [44]. MoO 3 /Bi 2 O 3 phases have been utilised as heterogeneous catalysts for the oxidation of olefins, e.g.…”

Lewis Acid Catalyzed Intermolecular Olefin Hydroamination: Scope, Limitation, and Mechanism

“…As a continuation of our previous study,18 the current report aims at revealing the scope, limitation, and mechanism of the intermolecular hydroamination of olefins catalyzed by various Lewis acids. By conducting the hydroamination reactions of norbornene with aromatic amines, the optimal reaction conditions for different Lewis acid catalysts (FeCl 3 , ZrCl 4 , BiCl 3 , and AlCl 3 ) are presented, and the catalytic performances of these catalysts are compared.…”

“…The work of Komeyama et al found that the FeCl 3 catalyst is quite efficient for the intramolecular hydroamination of unactivated olefins, and both five‐ and six‐membered nitrogen heterocycles are accessible under ambient conditions 17. On expanding the catalyst scope, previous results of our group found that the reusable, air‐ and moisture‐tolerable BiCl 3 catalyst is capable of catalyzing the intermolecular hydroamination of norbornene with aromatic amines 18…”

“…These newly developed Lewis acid catalytic systems have the advantages of being readily available and easy to handle and they are also ecofriendly. However, the reactions have so far only been applied to a limited number of olefin substrates 16–18. Another problem with these reactions is that the mechanism is still unknown.…”

Cationic Bismuth-Catalyzed Hydroamination and Direct Substitution of the Hydroxy Group in Alcohols with Amides

“…In order to find a suitable catalyst for intermolecular hydroaminations of 1,3-dienes, several metal sources were screened for the reaction of diene 1a (4 equiv) with carbamate 2a, and Bi(OTf) 3 gave promising results [21,22]. The optimization studies using Bi(OTf) 3 are summarized in Table 1 and show that 10 mol% of Bi(OTf) 3 gave a 1:1 product 3aa in 17% yield together with polymerized byproducts (Table 1, entry 1).…”