317830-84-5Relevant articles and documents
Scope of the palladium-catalyzed aryl borylation utilizing bis-boronic acid
Molander, Gary A.,Trice, Sarah L. J.,Kennedy, Steven M.,Dreher, Spencer D.,Tudge, Matthew T.
supporting information; experimental part, p. 11667 - 11673 (2012/09/05)
The Suzuki-Miyaura reaction has become one of the more useful tools for synthetic organic chemists. Until recently, there did not exist a direct way to make the most important component in the coupling reaction, namely the boronic acid. Current methods to make boronic acids often employ harsh or wasteful reagents to prepare boronic acid derivatives and require additional steps to afford the desired boronic acid. The scope of the previously reported palladium-catalyzed, direct boronic acid synthesis is unveiled, which includes a wide array of synthetically useful aryl electrophiles. It makes use of the newly available second generation Buchwald XPhos preformed palladium catalyst and bis-boronic acid. For ease of isolation and to preserve the often sensitive C-B bond, all boronic acids were readily converted to their more stable trifluoroborate counterparts.
Palladium-catalyzed borylation of aryl and heteroaryl halides utilizing tetrakis(dimethylamino)diboron: One step greener
Molander, Gary A.,Trice, Sarah L. J.,Kennedy, Steven M.
supporting information, p. 4814 - 4817,4 (2012/12/12)
The palladium-catalyzed borylation of aryl and heteroaryl halides with a novel borylating agent, tetrakis(dimethylamino)diboron [(Me2N) 2B-B(NMe2)2], is reported. The method is complementary to the previously reported method utilizing bis-boronic acid (BBA) in that certain substrates perform better under one set of optimized reaction conditions than the other. Because tetrakis(dimethylamino)diboron is the synthetic precursor to both BBA and bis(pinacolato)diboron (B 2Pin2), the new method represents a more atom-economical and efficient approach to current borylation methods.
FLUORINATION OF ORGANIC COMPOUNDS
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Page/Page column 85, (2010/07/10)
Methods for fluorinating organic compounds are described herein.
Fluorination of boronic acids mediated by silver(I) Triflate
Furuya, Takeru,Ritter, Toblas
supporting information; experimental part, p. 2860 - 2863 (2009/12/05)
A regiospecific Ag-mediated fluorination reaction of aryl- and alkenylboronic acids and esters Is reported. The fluorination reaction uses commercially available reagents, does not require the addition of exogenous ligands, and can be performed on a multigram scale. This report discloses the first practical reaction sequence from arylboronic acid to aryl fluorides.
Arylboronic acids and arylpinacolboronate esters in suzuki coupling reactions involving indoles. Partner role swapping and heterocycle protection
Prieto, Monica,Zurita, Esther,Rosa, Esmeralda,Munoz, Lourdes,Lloyd-Williams, Paul,Giralt, Ernest
, p. 6812 - 6820 (2007/10/03)
Yields of Suzuki couplings involving indoles depended upon (i) whether arylboronic acids or arylpinacolboronate esters were used, (ii) whether the heterocycle was the aryl halide or the arylboron coupling partner, and (iii) whether the heterocycle was protected or not. Highest yields, which were unaffected by incorporating Boc or Tos protection at the heterocyclic nitrogen, were obtained when indole bromides were reacted with phenylboronic acids. When indolylboronic acids were reacted with phenyl bromides, yields were somewhat lower and depended on the nitrogen substituent, being highest in the absence of protection, lower in the presence of the Boc group, and lowest of all with the Tos group. Arylpinacolboronate esters were less reactive than arylboronic acids. They required considerably longer reaction times and furnished generally lower yields of biaryl. Furthermore, irrespective of whether the heterocycle was the aryl bromide or the arylpinacolboronate ester, these yields were highest when it was protected with the Tos group. Yields were lower with the Boc group, and unprotected heterocycles gave only traces of biaryl. Careful selection of arylboron reagent, of coupling partner roles, and of protecting groups are essential to ensuring optimum results in these Suzuki couplings. These results may also be relevant to couplings involving other substrates.
