Palladium-Catalyzed Cross-Coupling Reaction of Heteroaryltriolborates with Aryl Halides for Synthesis of Biaryls

• Yamamoto, Yasunori

• Takizawa, Miho

• Yu, Xiao-Qiang

• Miyaura, Norio

Abstract

Cyclic triolborates possessing a heteroaromatic ring on the boron atom [ArB(OCH2)3CHCH3]M (M=K, Na, Li) were prepared in high yields from heteroarylboronic acids, 1,1,1-tris(hydroxymethyl)ethane (triol) and KOH or NaH. The corresponding lithium salts were synthesized from aryllithiums, B(OMe)3 and triol. They were air-stable white solids that were convenient for handling in air. High performance of these triolborates for metal-catalyzed bond-forming reactions was demonstrated in palladium-catalyzed cross-coupling reactions with haloarenes. Although the use of heteroarylboronic acids often results in very low yields due to competitive hydrolytic B-C bond cleavage with water under typical conditions using aqueous bases, triolborates possessing a 2-pyridyl, 3-pyridyl or 2-thiophenyl ring afforded biaryls in high yields at 50-120℃ in anhydrous DMF. There was a strong accelerating effect of CuI for reactions of 2- and 3-pyridylborate derivatives, whereas 2-thiophenyl derivatives reacted smoothly resulting in high yields in the absence of CuI.

Journal

• Heterocycles

  Heterocycles 80 (1), 359-368, 2010-01-01

  Japan Institute of Heterocyclic Chemistry

Keywords

• Cross-Coupling Reaction
• Organoboron Compound
• Heteroaryltriolborate
• Ate Complex
• Biaryl

Details

• CRID: 1050845763937368320
• NII Article ID: 120002834748
• NII Book ID: AA00663739
• HANDLE: 2115/45016
• NDL BIB ID: 10495688
• ISSN: 03855414
• Web Site: https://ndlsearch.ndl.go.jp/books/R000000004-I10495688
• Text Lang: en
• Article Type: journal article
• Data Source:
  • IRDB
  • NDL
  • CiNii Articles
  • KAKEN