Organobismuth Reagents: Synthesis, Properties and Applications in Organic Synthesis

Abstract

Organobismuth compounds are organometallic reagents that contain a C-Bi bond. These species, which are easily accessed from inexpensive and low-toxicity inorganic bismuth salts, are highly attractive in synthesis due to their unique properties and reactivity. A wide diversity of geometries have been found for organobismuth compounds, depending on the oxidation state of the bismuth, its charge, and the number of coordinated elements. Compounds where the bismuth bears a-1 charge (organobismuthate), a +1 (bismuthonium cation) and a +2 charge (bismuthonium dication) have been reported. Due to the presence of a lone pair, trivalent organobismuthines can act as Lewis bases in transition-metal complexes. In addition, organobismuth compounds can act as Lewis acids by forming hypervalent interactions with ligands and metals. Organobismuth compounds have been used as catalysts and reagents in a plethora of reactions. In this review, the synthesis and properties of organobismuth reagents and their use in organic reactions are reviewed. 1 Introduction 2 Synthesis of Trivalent Organobismuthines 3 Synthesis of Pentavalent Organobismuth Compounds 4 Structure, Hypervalency and Chirality 5 C-, N-, Oand S-Arylation Reactions 6 Palladium-Catalyzed Reactions 7 Other Reactions Involving Organobismuth Reagents 8 Conclusion

Synthesis of aryl cyclopropyl sulfides through copper-promoted S-cyclopropylation of thiophenols using cyclopropylboronic acid

“…Organobismuth compounds are organometallic reagents that possess a C–Bi bond and which can be synthesized from inexpensive and low-toxic bismuth salts [24–25]. Due to the borderline behavior of bismuth as a metal and a ligand, organobismuth species have been used as reagents and catalysts in a wide range of reactions.…”

Modular bismacycles for the selective C–H arylation of phenols and naphthols

“…1b). 27,28,29,30 This methodology benefits further from the low cost of Bi and its salts, and the high stability and low toxicity of triarylbismuth reagents (e.g., LD50(BiPh3) = 180 g/kg 31 ). However, despite these appealing attributes, the synthetic potential of both Bi(V) and Bi(III) 32 reagents for C-H arylation has been largely overlooked.…”

Synthesis and Molecular Structure of Pseudo‐Hexacoordinated Pnictines Bearing 2‐Phenylpyridine Ligands

“…In recent years, the chemistry of organoantimony and organobismuth compounds has seen significant progress [1][2][3][4][5][6] especially toward their use as Lewis-acid catalysts, [7][8][9][10][11][12][13][14][15][16][17] as anionsensing molecules, [18][19][20][21][22][23][24] and as non-innocent ligands for transition-metal complexes. [25][26][27][28][29][30] Heavy triorganopnictines of the type R 3 Pn (Pn = Sb and Bi) are well-known organopnictogen(III) compounds that obey the octet rule and that can be classified as 8-Pn-3 chemical species.…”

“…[31] In general, heavy pnictines adopt a trigonal pyramidal coordination geometry with three covalent bonds and a lone pair (LP) of electrons on the central atom. [2,4] Due to the diminished propensity toward hybridization of heavy atoms, the three covalent bonds and the LP consist predominantly of contributions from the p-and s-orbitals of the bonding atoms. In addition, the Allred-Rochow electronegativity values ( ) of antimony and bismuth ( Sb = 1.82; Bi = 1.67) are much smaller than that of carbon ( C = 2.50), which renders the central atom of the heavy pnictines cationic and means that the heavy pnictines form polarized Pn δ+ -C δbonds.…”