Direct entry to optically pure 2-amino-2'-hydroxy-1,1'-binaphthyl (NOBIN) derivatives by an iron-catalyzed stereoselective oxidative cross-coupling reaction between 2-naphthol and 2-aminonaphthalene with a labile chiral auxiliary is reported. This efficient method offers entry to tailor-designed ( R )- and ( S)-NOBINs that are not accessible by any other means.

A selectivity-driven catalyst design approach was adopted to address chemoselectivity issues in the oxidative coupling of phenols. This approach was utilized for developing a Co­(II)­[salen]-catalyzed aerobic oxidative cross-coupling of phenols in a recyclable 1,1,1,3,3,3-hexafluoropropan-2-ol (HFIP) solvent. The waste-free conditions offer a sustainable entry to nonsymmetric biphenols via a mechanistic scheme that involves coupling of a liberated phenoxyl radical with a ligated 2-naphthoxyl radical.

A bioinspired iron-catalyzed consecutive oxidative cross-coupling reaction between a single phenolic unit and nucleophilic arenes was developed. This sustainable transformation offers a selective synthetic strategy for the preparation of complex polyaryl compounds directly from readily available phenols. With the aid of electron paramagnetic resonance spectroscopy, it was demonstrated that the groups ortho to the phenolic functionality (whether hydrogen, methyl, or methoxy) direct the regioselectivity (ortho, para, or meta via dienone-phenol rearrangement) and chemoselectivity (C-C coupling or C-O coupling) in this multistep process.

A novel type of chiral redox disulfonate iron complex for asymmetric catalysis is reported. The [Fe((R a )-BINSate)] + (BINSate = 1,1′binaphthalene-2,2′-disulfonate) complex effectively promotes the enantioselective oxidative cross-coupling between 2-naphthols (1) and 2-aminonaphthalene derivatives (2), affording optically enriched (R a )-2-amino-2′hydroxy-1,1′-binaphthyls (NOBINs) with exceptional yields and enantioselective ratios (up to 99% yield and 96:4 er). The [Fe((R a )-BINSate)] + catalyst was designed as a chiral version of FeCl 3 with multicoordination sites available for binding the two coupling partners 1 and 2 as well as the oxidant. Our structure−selectivity and activity study, which covered most of the important positions in the NOBIN scaffold, revealed the effect of different substitution patterns on the coupling efficiency and stereoselectivity.

Iron- and manganese-catalyzed para -selective oxidative amination of (4-R)phenols by primary and secondary anilines was developed. Depending on the identity of the R group, the products of this efficient reaction are either benzoquinone anils (C–N coupling) that are produced via a sequential oxidative amination/dehydrogenation (R = H), oxidative amination/elimination (R = OMe) steps, or N , O -biaryl compounds (C–C coupling) that are formed when R = alkyl through an oxidative amination/[3,3]-sigmatropic rearrangement (quinamine rearrangement) process.