Arylboronic acids nitration

Arylboronic acids esterified with support-bound 1,2-diols undergo Suzuki reaction with aryl iodides, whereby biaryls are released into solution (Entry 13, Table 3.46). This technique has also been used to prepare (3-turn mimetics by simultaneous macro-cyclization and cleavage from the support [766]. Alternatively, the C-B bond of a resin-bound boronate may be converted to a C-H bond by treatment with aqueous silver ammonium nitrate (Entry 14, Table 3.46). 

Arylboronic acids have been shown to react with ammonium nitrate and trifluor-oacetic acid to give the corresponding nitrobenzene. ... 

Phenols arylboronic acids. Treatment of arylthallium bistrifluoroacetates with diborane in THF leads to an intermediate, possibly ArBHj, that is converted into arylboronic acids on treatment with water or into a phenol on treatment with alkaline hydrogen peroxide. Treatment of the intermediates with silver nitrate fails to produce biaryls. ... 

A new approach for direct arylation of pyridine W-oxides with arylboronic acids through C-H functionalization has been developed (Scheme 45) [99]. This reaction can be performed at room temperature using catalytic silver (I) nitrate in the presence of potassium persulfate, thus giving 2-aryl derivatives of pyridine W-oxides. 

Table 7. Synthesis of symmetrical biaryls via in situ generation of arylboronic acids from aryl iodides and bromides followed by the homo-coupling reaction with silver(I) nitrate [19,20]...

However, practical synthetic method for performing the homo-coupling of arylboronic acids to the respective symmetrical biaryls is accomplished with copperfll) nitrate as an ultimate oxidant in good to high yields, Table 8. 

Table 8. Palladium-catalysed homo-coupling reaction of arylboronic acids to symmetrical biaryls in the presence of copper(II) nitrate as an oxidant...

B(0H)2 group (Op = 0.12) directs electrophilic substitution at the meta position. Amino derivatives are prepared by a sequence of nitration and catalytic hydrogenation of arylboronic acids. ... 

SCHEME 3.112 Preparation of nitroarenes through nitration of arylboronic acids [118]. 

Arylboronic acids can be directly nitrated using bismuth(ni) nitrate [118]... 

For ipso-nitration of arylboronic acids, see S. Salzbmnn, J. Simon,... 

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