Applications of bismuth(iii) compounds in organic synthesis

Abstract

8388 5.3. Formation of acetals catalyzed by bismuth(III) triflate 8388 5.4. Formation of 1,l-diacetates (acylals) 8389 5.5. Cleavage of epoxides catalyzed by bismuth(III) chloride 8389 5.6. Glycosylation promoted by bismuth(III) chloride 8389 5.7. Selective hydrolysis of aryl esters using bismuth(III) mandelate 5.8. Carbon-sulfur bond formation 5.8.1. Synthesis of thioacetals 8389 5.8.2. Conversion of epoxides to thiiranes 8390 5.9. Sulfonylation of aromatics 8390 5.10. Synthesis of sulfides and selenides promoted by Sm-BiCI3 8391 5.11. Synthesis of allyl sulfides 8391 5. 12. Formation of carbon-halogen bonds 8391 5.12.1. Synthesis of �-haloketones and esters 8391 5.12.2. Chlorination of alcohols catalyzed by bismuth(III) salts 8391 5.12.3. Synthesis of peracetylated glycosyl halides 8392 6. Reductions with bismuth compounds 8392 6.1. Selective reduction of nitro compounds to azoxy compounds 8392 6.2. Reduction of nitro compounds to amines 8392 6.3. Chemoselective reduction of a,�-unsaturated ethyl esters using BiCI3-NaBH 4 8392 6.4. Reduction of aromatic a-haloketones 8393 6.5. Miscellaneous reductions 8393 7. Rearrangements promoted by bismuth(III) salts 8393 7.1. Rearrangement of epoxides 8393 7.2. Allylic rearrangement of glycols (the Ferrier rearrangement) 8394 8. Conclusions

Reduced graphene oxide–bismuth oxide composite as electrode material for supercapacitors

“…Recently, the interest in poor metals and metalloids in energy storage devices is growing up. Among them, bismuth seems to be a good candidate because of nontoxic character in comparison to the neighbors from the periodic table, namely, lead and antimony [3]. Generally, bismuth chemistry is mainly focused on medical and catalytic applications.…”

“…Generally, bismuth chemistry is mainly focused on medical and catalytic applications. In medicine, bismuth compounds are most commonly used for treating gastrointestinal disorders [4] while in organic synthesis may be applied in Friedel-Crafts acylation, Michael reactions, synthesis of lactones, and oxidation of thiols [3]. Bismuth is a relatively inexpensive material, in comparison to most extensively studied ruthenium [5], and can be obtained as a byproduct in copper, lead, and tin mining.…”

Metal‐Triflate‐Catalyzed Synthesis of Polycyclic Tertiary Alcohols by Cyclization of γ‐Allenic Ketones

“…We first used the acyclic b-ketoester 1 bearing a pendant trisubstituted allene as a model and assessed its reactivity towards various metal triflate catalysts in nitromethane (Table 1, entries 1-4). A rapid screening highlighted nonexpensive bismuth(III) triflate [9,10] as a very active catalyst at low loading with the total conversion of 1 occurring at À20 8C. Switching solvents from nitromethane to CH 2 Cl 2 considerably slowed down the reaction rate and led to the isolation of the cyclopentadienes 2 b and 2 c in good yield (88 %) at room temperature by using only 1 mol % of bismuth(III) triflate (entry 5).…”

Synthesis, structural characterization, and reactivity of (thiolato)bismuth complexes as potential water-tolerant Lewis acid catalysts

“…6,7,8,9 However, these compounds are susceptible to hydrolysis and react preferentially with water rather than the substrates.…”