H+, CH₃+, and R₃Si+ Carborane Reagents: When Triflates Fail

Citations Over TimeTop 1% of 2009 papers

Abstract

For decades, triflic acid, methyl triflate, and trialkylsilyl triflate reagents have served synthetic chemistry well as clean, strong electrophilic sources of H(+), CH(3)(+), and R(3)Si(+), respectively. However, a number of weakly basic substrates are unreactive toward these reagents. In addition, triflate anion can express undesired nucleophilicity toward electrophilically activated substrates. In this Account, we describe methods that replace triflate-based electrophilic reagents with carborane reagents. Using carborane anions of type CHB(11)R(5)X(6)(-) (R = H, Me, X; X = Br, Cl), members of a class of notably inert, weakly nucleophilic anions, significantly increases the electrophilicity of these reagents and shuts down subsequent nucleophilic chemistry of the anion. Thus, H(carborane) acids cleanly protonate benzene, phosphabenzene, C(60), etc., while triflic acid does not. Similarly, CH(3)(carborane) reagents can methylate substrates that are inert to boiling neat methyl triflate, including benzene, phosphabenzenes, phosphazenes, and the pentamethylhydrazinium ion, which forms the dipositive ethane analogue, Me(6)N(2)(2+). Methyl carboranes are also surprisingly effective in abstracting hydride from simple alkanes to give isolable carbocation salts, e.g., t-butyl cation. Trialkylsilyl carborane reagents, R(3)Si(carborane), abstract halides from substrates to produce cations of unprecedented reactivity. For example, fluoride is extracted from freons to form carbocations; chloride is extracted from IrCl(CO)(PPh(3))(2) to form a coordinatively unsaturated iridium cation that undergoes oxidative addition with chlorobenzene at room temperature; and silylation of cyclo-N(3)P(3)Cl(6) produces a catalyst for the polymerization of phosphazenes that functions at room temperature. Although currently too expensive for widespread use, carborane reagents are nevertheless of considerable interest as specialty reagents for making reactive cations and catalysts.

Related Papers

• → Hydrogen-Bonding and Ion−Ion Interactions in Solutions of Triflic Acid and 1-Ethyl-3-methylimidazolium Triflate(2009)32 cited
• → A Facile Route to Polysubstituted Naphthalenes and Benzofluorenols via Scandium Triflate‐ and Triflic Acid‐ Catalyzed Benzannulation of 2‐(2‐Alkynylarylidene)‐ 1,3‐Dicarbonyl Compounds(2010)36 cited
• → Molecular dynamics simulations of triflic acid and triflate ion/water mixtures: A proton conducting electrolytic component in fuel cells(2011)27 cited
• → Syntheses of (1,1-dihydroperfluoroalkyl)aryliodonium triflates and their analogues(1985)40 cited
• → Electrophilicity Scales for Carbocations(2004)49 cited