KINETICS OF NUCLEOPHILIC ATTACK ON COORDINATED ORGANIC MOIETIES. PART 32.∗ SYNTHETIC AND MECHANISTIC STUDIES OF THE REACTION OF IODINE ION WITH [(η⁵-DIENYL)Fe(CO)₃]⁺CATIONS (DIENYL = C₆H₇, 2-MeOC₆H₆, C₇H₉)

Selective Iron-Mediated C- and O-Addition of Phenolic Nucleophiles to a Cyclohexadiene Scaffold Using Renewable Precursors

“…Once formed, the complex can react with a wide range of nucleophiles, including alcohols, 19 amines, 26 amides, 27 azide, 16 hydride, 16 carbamate, 17 thiols, 28 enolates 26 and malonates, 29 allyl silanes, 30 electron rich aromatics 31 and heterocycles, 30 organocuprates, 26 organolithium reagents, 20 organozinc reagents, 32 Grignard reagents, 26 phosphines, 33 phosphites, 34 and halides. 35 At the outset of our investigation, we aimed to perform the selective C-and O-addition of phenolic nucleophiles to cationic η 5 iron carbonyl cyclohexadienyl complex 1 (Scheme 2). The development of green reaction conditions was also an important criterion.…”

“…We opted for the second of these strategies in the preparation of the initial cationic iron complex. Once formed, the complex can react with a wide range of nucleophiles, including alcohols, amines, amides, azide, hydride, carbamate, thiols, enolates and malonates, allyl silanes, electron rich aromatics and heterocycles, organocuprates, organolithium reagents, organozinc reagents, Grignard reagents, phosphines, phosphites, and halides …”