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

<P>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] </P>

Abstracts

<TD VALIGN="TOP"> (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. </TD><TD VALIGN="TOP">

</TD><TD VALIGN="TOP"> (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] </TD><TD VALIGN="TOP">

</TD><TD VALIGN="TOP"> (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] </TD><TD VALIGN="TOP">

</TD><TD VALIGN="TOP"> (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. </TD><TD VALIGN="TOP">

</TD><TD VALIGN="TOP"> (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. </TD><TD VALIGN="TOP">

</TD><TD VALIGN="TOP"> (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%. </TD><TD VALIGN="TOP">

</TD><TD VALIGN="TOP"> (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] </TD><TD VALIGN="TOP">

</TD><TD VALIGN="TOP"> (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] </TD><TD VALIGN="TOP">

</TD><TD VALIGN="TOP"> (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] </TD><TD VALIGN="TOP">

</TD><TD VALIGN="TOP"> (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). </TD><TD VALIGN="TOP">

</TD>

References

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<A NAME="RV07203ST-17">17</A> Duñach E, and Antoniotti S. inventors; (Rhodia Chimie), Fr Pat. Appl.  Fr 2829490.