One‐Pot Synthesis and Applications of N‐Heteroaryl Iodonium Salts

Abstract

An efficient one-pot synthesis of N-heteroaryl iodonium triflates from the corresponding N-heteroaryl iodide and arene has been developed. The reaction conditions resemble our previous one-pot syntheses, with suitable modifications to allow N-heteroaryl groups. The reaction time is only 30 min, and no anion exchange is required. The obtained iodonium salts were isolated in a protonated form, these salts can either be employed directly in applications or be deprotonated prior to use. The aryl groups were chosen to induce chemoselective transfer of the heteroaryl moiety to various nucleophiles. The reactivity and chemoselectivity of these iodonium salts were demonstrated by selectively introducing a pyridyl moiety onto both oxygen and carbon nucleophiles in good yields.

Cu-Mediated C–H 18F-Fluorination of Electron-Rich (Hetero)arenes

“…The 18 F-fluorination proceeded to afford the para -isomer with >99:1 selectivity. 12,13a−13d This high selectivity is fully consistent with that reported for S E Ar reactions between hypervalent iodine reagents and related electron-rich arene substrates. 12 Importantly, <2% of [ 18 F]fluoromesitylene was detected under any of the conditions examined.…”

Trimethoxyphenyl (TMP) as a Useful Auxiliary for in situ Formation and Reaction of Aryl(TMP)iodonium Salts: Synthesis of Diaryl Ethers

“…Classic nucleophilic substitution (S N Ar) of halogenated pyridines occur fastest at the 2-and 4-positions relative to the 3position. [17] In conclusion, we have developed a mild and efficient method to synthesize diaryl ethers from aryl iodides and phenols that takes advantage of aryl(TMP) iodonium salts as a key reaction intermediate. [15] Diaryl ethers containing a pyridyl group have been investigated for their antibacterial activity, [16] and copper-mediated coupling was used to form the diaryl ether CÀ O bond (Scheme 4).…”

Development of dual casein kinase 1δ/1ε (CK1δ/ε) inhibitors for treatment of breast cancer

“…25 The diaryliodonium salts were accessed via one-step procedures from aryl iodides 1 and arenes 2 or boronic acids 3 . 30 Subsequently, substituted benzimidazoles 9 and various amines were introduced at C6 and C2 of 6 , respectively. This procedure provided the targeted CK1δ/ε inhibitors with excellent regioselectivity and good yields (70–90%).…”

“…25, 28–29 Diaryliodonium salts 5 were prepared according to the reported procedures. 30 Compounds 11–76 were newly synthesized and described in the Supporting Information.…”