Bismuth(III) Chloride and Triflate: Novel Catalysts for Acylation and Sulfonylation Reactions. Survey and Mechanistic Aspects

Christophe Le Roux; Jacques Dubac

doi:10.1055/s-2002-19743

ACCOUNT

Bismuth(III) Chloride and Triflate: Novel Catalysts for Acylation and Sulfonylation Reactions. Survey and Mechanistic Aspects

Christophe Le Roux, Jacques Dubac
Hétérochimie Fondamentale et Appliquée (UMR CNRS 5069), Université Paul-Sabatier, 118 route de Narbonne, 31062 Toulouse Cedex, France
Fax: +33(5)61558204; e-Mail: dubac@chimie.ups-tlse.fr; e-Mail: leroux@chimie.ups-tlse.fr;

Abstract

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Abstract

Acylation and sulfonylation reactions catalyzed by bismuth(III) chloride or triflate are reviewed. For Friedel-Crafts reactions the mechanistic study reveals the different behavior of Bi(OTf)₃, depending on the electrophilic agent used; either that of Lewis acid (with acid anhydrides) or that of procatalyst, carrier of triflate groups (with acid chlorides), leading to in situ generation of mixed anhydrides (RCOOTf or RSO₂OTf) responsible for the aromatic electrophilic substitution. Among the metal triflates tested in these reactions, only Ga(III) and In(III) exhibit high activity. Bi(OTf)₃ appears to be superior to other metal triflates known to catalyze the acylation of alcohols using acid anhydrides as reagents. BiCl₃, especially in the presence of a metal iodide, is the only known efficient catalyst for acyldesilylation reactions of allyl- and enoxysilanes. The low cost of bismuth compounds and their low (or absence of) toxicity are emphasized.

1 Introduction
2 Acylation of Aromatics
2.1 Bi(III) Chloride as Catalyst
2.1.1 Mechanistic Aspects
2.2 Bismuth(III) Triflate as Catalyst
2.2.1 Literature Survey of Triflates Used as Catalysts of Friedel-Crafts Acylation
2.2.2 Bismuth(III) Triflate as Catalyst. Results
2.2.3 Mechanistic Aspects
2.2.4 Comparison of the Catalytic Activities of Bi(OTf)₃ and Other Metal Triflates
3 Sulfonylation of Aromatics
3.1 Bismuth(III) Chloride as Catalyst
3.2 Bismuth(III) Triflate as Catalyst
3.3 Mechanistic Aspects
4 Acyldesilylation of Organosilanes
4.1 Acyldesilylation of Allylsilanes
4.2 Acyldesilylation of Enoxysilanes
5 Acylation of Alcohols
6 Conclusion

Key words

acylation - alcohols - allylsilanes - bismuth(III) chloride - bismuth(III) trifluoromethanesulfonate - enoxysilanes - Friedel-Crafts - Lewis acids - sulfonylation

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Preparation of Bismuth(III) Trifluoromethanesulfonate: [52] [56] In a 250 mL flask connected to an argon line were introduced 4.40 g (0.01 mol) of triphenylbismuth and 100 mL of freshly distilled dichloromethane. Then the flask was immersed in an acetone/dry ice bath and 4.50 g (0.03 mol) of triflic acid were added via a syringe under magnetic stirring. After 10 min the bath was removed and the reaction was stirred at r.t. for 10 h. The solid formed was filtered over a glass-frit funnel and washed once with 20 mL of dichloromethane. The very hygroscopic white powder obtained was heated at 50 °C under reduced pressure. Bismuth(III) triflate was isolated in its weakly hydrated forms, [57] [58] mainly the tetrahydrated one (by TGA and XRD) [58] (6.48 g; 89% yield). NMR (acetone-d ₆): ¹³C NMR: δ = 120 ppm (q, ^¹ J (¹³ C/¹⁹ F) = 321 Hz); ¹⁹F NMR: δ (from TfOH) = 0.84 ppm. IR(nujol) : 3450-3550 (m), 1230-1290(vs), 1180 (s), 1034 (s), 1028(sh), 650(sh), 643 (s)cm^-1. A variant of our process using toluene instead of dichloromethane as solvent was recently reported, and Bi(OTf)₃ was described to be stable and active even after two year storage at r.t. [14]

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Mercury (II) triflate [prepared from diphenyl mercury and triflic acid, as Bi(OTf)₃] [56] reveals a good catalytic activity in FC acylation reactions, especially using acid chlorides as reagents. [55]

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