Arylboronic 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. ... 

The cyclization can be carried out with halogenated amines, and substitution products of the new ring systems can also be obtained in the conventional way, by nitration, etc. Similar compounds can be prepared directly by using arylboron dichlorides in place of boron trichloride in the procedure indicated above. The parent borazarene derivatives, with hydrogen attached to boron, can be made from the B-hydroxy compounds with lithium aluminum hydride in the presence of aluminum chloride. N-Alkyl derivatives can be made either by using N-alkyl derivatives of the aminobiphenyls as starting materials, or by N-alkylation of the unsubstituted compounds via their N-lithio derivatives. Apart from their inherent interest, compounds of this type can serve as intermediates in various syntheses. Thus benzocinnolines and 2,2 -dihydroxybiphenyls can be obtained from derivatives of 2-aminobiphenyl. ... 

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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