Asymmetric Carbon−Carbon Coupling of Phenols or Anilines with Aryllead Triacetates

Abstract

The asymmetric coupling of various phenol or aniline derivatives with bulky aryllead triacetates was thoroughly investigated using optically active amines, including strychnine and brucine. We found that conformationally restricted tertiary amines, as well as lithium aryloxides and molecular sieves, are essential for accelerating the rate of phenol coupling. Consequently, the reaction can be carried out at a low temperature (-40 to -20 degrees C) and gives a high degree of diastereo- and enantioselectivity. In contrast to the effectiveness of lithiation in phenol coupling, magnesation of anilines was a critical technique for aniline coupling with aryllead triacetates. Using these coupling methods, a diverse set of di-, tri, and polyaryl compounds with axial chirality can be easily obtained, and these should be useful for the construction of a variety of aryl-aryl frameworks involved in metal ligands, natural products, and artificial helical polymers.

Reactions of 1-Naphthols with .PI.-Acceptor p-Benzoquinones: Oxidative Aryl Coupling vs. Non-Oxidative Electrophilic Arylation

“…[1][2][3][4] Natural biaryls and triaryls have been isolated from several plants and show various biological activities. 4) The usual methods for construction of bi-and triaryl frameworks can be divided into the following categories: (i) oxidative biaryl coupling (so-called phenolic oxidation) of various arenas including metal phenolates 5) using a chemical method 6) or an electrochemical, 7) (ii) biaryl coupling between aryl halides and arylmetal compounds 8) or arylmetal species, 9) and (iii) electrophilic arylation of quinone derivatives with hydroxyarenes in the presence of acids or bases. [10][11][12][13][14][15] Nature makes extensive use of the oxidative coupling reaction for the selective construction of complex compounds from simple starting materials, such as naphthols and phenols.…”

Ten years of research in Chicago

“…45 Although this perspectives describes the most of my contributions during our research in Chicago, there are still several additional topics for further study in future. 1,2,4,5,7,11,14,16–18,20–22,25,32,35,43,53,62 …”

An expedient one-pot synthesis of novel 10-substituted 9-aminophenanthrenes

“…11 A third route introduced an aryl group on position 10 by coupling with an aryllead triacetate (route 3). 12 More recently the synthesis of 10-aryl-9-aminophenanthrenes has been reported by reaction of the anion of 9-aminophenanthrene with aryl halides (route 4). 13 All these syntheses are introducing the diversity from an already prepared phenanthrene ring system.…”