Bismuth(III) tris(trifluoro-methanesulfonate)

Biographical Sketches

Sylvain Antoniotti was born in Nice, France in 1975. He studied Life Sciences and Chemistry at the University of Nice-Sophia Antipolis, France, and is currently pursuing a PhD on the catalytic oxidation of epoxides by bismuth compounds under the advisory of E. Duñach in the same university.

Introduction

Among several bismuth compounds described for their use in organic synthesis, [1] bismuth(III) tris(trifluoromethanesulfonate), commonly called bismuth triflate, has received increasing interest over the last few years, and many publications have reported its powerful Lewis acidity, offering a new reagent for various catalytic reactions. Bismuth(III) triflate can be prepared from cheap triphenylbismuth [2] or bismuth(III) oxide Bi₂O₃, [3] and triflic acid. The displacement of trifluoroacetate groups of bismuth(III) trifluoroacetate by an excess of triflic acid has also been reported. [4]

Abstracts

(A) Bismuth(III) triflate is an efficient catalyst for the Mukaiyama aldol-type reaction and shows higher catalytic activity than other metallic triflates such as scandium, ytterbium, or cerium. [5] Ketones, aldehydes, and acetals may be used as electrophiles with aromatic and aliphatic silyl enol ethers to lead to the corresponding b-hydroxycarbonyl compounds in the presence of 1-5 mol% of catalyst.
(B) Friedel-Crafts acylation of monosubstituted benzene derivatives by acetyl and benzoyl chlorides catalyzed by bismuth(III) triflate has been reported to occur in 75-96% yields. Good selectivities for the para product were observed. [6]
(C) Bismuth triflate catalyses both classical and non-classical Diels-Alder reactions involving conjugated olefins, [7] carbonyl compounds, [8] and imines, [9] e.g. the reaction of various unfunctionalized dienes and glyoxilic acid in water. [8a]
(D) The rearrangement of aryl epoxides has been reported to lead to aldehydes and ketones in 73-92% yields by using 0.1 mol% of bismuth triflate as catalyst. [10] The reaction was found to be regio­selective, particularly for stilbene oxide, for which only the phenyl group migration was observed.
(E) Bismuth triflate catalyses the conversion of epoxides to 1,3-dioxolanes in the presence of acetone in 94-99% yields. [11] The activity of bismuth triflate, compared to those of bismuth trifluoro­acetate and bismuth trichloride, was shown to be superior.
(F) The use of bismuth(III) triflate in acetylation of alcohols and diols by acetic anhydride has been reported simultaneously by several research groups. [12] From Otera’s group [12a] acetylation of various functionalized primary and secondary alcohols is easily carried out in the presence of small amounts of bismuth triflate (0.01-1 mol%) in yields of 80-99%.
(G) Bismuth(III) triflate catalyses the three-component reaction through the Biginelli reaction, where urea, a b-ketoester and an aldehyde are assembled into a dihydropyrimidinone in 58-95% yields. [13]
(H) Bi(OTf)3 catalyses the allylation of aldehydes and aldimines using allyltributylstannane. [14] The catalyst is re-usable without loss of activity during four cycles. Acetals, in the presence of allyltrimethylsilane as the allyl donnor, undergo also an allylation reaction to homoallylic ethers. [15]
(I) Bismuth(III) triflate promotes the intramolecular Sakurai cyclisation (IMSC) of homoallylic alcohols and aldehydes leading to the corresponding 4-methylidenetetrahydropyrane derivatives in 84-98% yields. [16]
(J) The first example of bismuth(III) triflate-catalysed oxidation of organic compounds has been reported in the one-pot selective oxidation of internal epoxides to a-diketones. [17] The reaction proceeds in DMSO under an oxygen atmosphere (1 atm).

References

Reviews:

1a Suzuki H. Ikegami T. Matano Y. Synthesis  1997,  249 

1b Le Roux C. Dubac J. Synlett  2002,  181 

1c Leonard NM. Wieland LC. Mohan RS. Tetrahedron  2002,  58:  8373 

2 Labrouillère M. Le Roux C. Gaspard H. Laporterie A. Dubac J. Desmurs J.-R. Tetrahedron Lett.  1999,  40:  285 

3 Répichet S. Zwick A. Vendier L. Le Roux C. Dubac J. Tetrahedron Lett.  2002,  43:  993 

4 Singh S. Verma RD. Indian J. Chem., Sect. A  1983,  22:  814 

5 Le Roux C. Ciliberti L. Laurent-Robert H. Laporterie A. Dubac J. Synlett  1998,  1249 

6a Desmurs J.-R. Labrouillère M. Le Roux C. Gaspard H. Laporterie A. Dubac J. Tetrahedron Lett.  1997,  38:  8871 

6b Répichet S. Le Roux C. Dubac J. Desmurs J.-R. Eur. J. Org. Chem.  1998,  2743 

7a Garrigues B. Oussaid A. J. Organomet. Chem.  1999,  585:  253 

7b Dhimane H. Meunier S. Vanucci-Bacqué C. Lhommet G. Tetrahedron Lett.  2002,  43:  1645 

8a Laurent-Robert H. Le Roux C. Dubac J. Synlett  1998,  1138 

8b Oussaid A. Garrigues B. Phosphorus, Sulfur Silicon  2002,  177:  825 

9 Laurent-Robert H. Garrigues B. Dubac J. Synlett  2000,  1160 

10 Bhatia KA. Eash KJ. Leonard NM. Oswald MC. Mohan RS. Tetrahedron Lett.  2001,  42:  8129 

11 Mohammadpoor-Baltork I. Khosropour AR. Aliyan H. Synth. Commun.  2001,  31:  3411 

12a Orita A. Tanahashi C. Kakuda A. Otera J. J. Org. Chem.  2001,  66:  8926 

12b Carrigan MD. Freiberg DA. Smith RC. Zerth HM. Mohan RS. Synthesis  2001,  2091 

12c Mohammadpoor-Baltork I. Aliyan H. Khosropour AR. Tetrahedron  2001,  57:  5851 

13 Varala R. Mujahid Alam M. Adapa SR. Synlett  2003,  67 

14 Choludary BM. Chidara S. Raja Sekhar ChV. Synlett  2002,  1694 

15 Wieland LC. Zerth HM. Mohan RS. Tetrahedron Lett.  2002,  43:  4597 

16 Leroy B. Markó IE. Tetrahedron Lett.  2001,  42:  8685 

17 Duñach E, and Antoniotti S. inventors; (Rhodia Chimie), Fr Pat. Appl.  Fr 2829490.