The Behavior of Conjugated Systems Containing Aromatic Double Bonds towards Organometallic Reagents.

Radical Substitution In Aromatic Nuclei

“…No doubt some homolytic cleavage of such organometallic reagents does occur, especially when there is an acceptor for the radical (260). Yet it remains very uncertain whether to classify such alkylations and arylations as radical or as carbanion substitutions (149).…”

Nucleophilic Dearomatizing (DNAr) Reactions of Aromatic C,H-Systems. A Mature Paradigm in Organic Synthesis

“…Triple Grignard addition occurs in TNB 465. Protonation with acetic acid and bromination of the intermediate trinitronate 507 affords trialkylated cyclohexanes 271,272 508 (Table 35, entries [20][21][22][23][24] and 509, respectively, as a mixture of stereoisomers. Moreover, Mannich condensation of 507 with a mixture of formaldehyde and ammonium nitrate furnishes trialkyltrinitroazaadamantanes 510 in yields of about 15% (Scheme 76).…”

“…In contrast, the literature related to nucleophilic conjugate additions to non-metal-complexed aromatic nuclei has been treated in rather old reviews covering only partial aspects of this chemistry. The papers by Gaertner and Fuson provide an assessment of the scope and limitations of the reaction of organometallic reagents with aryl ketones up to the beginning of 1958. Bartoli reviewed the literature up to 1982 related to the addition of Grignard reagents to nitro compounds.…”

Unsymmetrical 1,6-Additions To Conjugated Systems

“…The addition of Grignard reagents to fuchsones and to highly hindered diaryl ketones provides the largest number of examples of a single type of 1,6-addition reaction. This subject has been reviewed (39) and is discussed in a recent book (44). A current example of the addition of Grignard reagents to hindered diaryl ketones had the possibility of two different 1,6-additions (38).…”