We subsequently explored substitution around the indole ring, and indoles bearing halogens such as fluorine or chlorine both undergo oxidation without incident to afford biaryls 3n (80% yield, 90:10 e.r.) and 3o (82% yield, 94:6 e.r.) respectively. We next examined C-5 substitution on the indole reactant. Electron donating groups such as methoxy are highly effective, affording biaryl 3p in 97% yield and 93:7 e.r. 5-Alkyl groups are also well tolerated, affording biaryl 3q in 78% yield and 93:7 e.r. We observed that electron withdrawing groups such as fluorine in this position led to lower conversions as in 3r (60% yield, 92:8 e.r.), and considered that this may provide some insight into the mechanism of this transformation. Consequently, we decided to study a series of different electron withdrawing groups in this position to evaluate the impact on the reaction. A 5-bromo substituent led to biaryl 3s in only 40% yield, but with a relatively high enantioselectivity (90:10 e.r.). More powerful electron withdrawing groups on the indole coupling partner led to the generation of biaryls bearing an ester 3t (40% yield, 85:15 e.r.), a trifluoromethyl group 3u (28% yield, 72:28 e.r.) or a cyano group 3v (13% yield, 85:15 e.r.) in lower yields and enantioselectivities; we also saw a reduction in chemoselectivity as manifested by the competitive formation of small quantities of the C2-symmetric BINOL product. It is clear that the electronic nature of the substituents on the indole has an impact on conversion and selectivity. C-6 substitution is tolerated albeit with slightly lower enantioselectivity: 6-methyl 3w (79% yield, 88:12 e.r.), 6-fluoro 3x (63% yield, 84:16 e.r.) and 6-chloro 3y (56% yield, 89:11 e.r.) are all effectively produced. An indole bearing a C-7 methyl group is also a competent partner in this reaction, leading to the corresponding biaryl 3z in 85% yield and 86:14 e.r. We next examined whether the introduction of different groups on the naphthol coupling partner was possible. A 6-bromo substituent coupled effectively to afford biaryl 3aa in 66% yield and 93:7 e.r.; a more conjugating group in 6-phenyl was also successful to afford 3ab with lower conversion (52% yield) and 90:10 e.r. We are able to accommodate groups on both coupling partners: a 6-methyl indole coupled with a 6-bromo naphthol to exclusively afford the hetero-coupled biaryl 3ac (67% yield; 88:12 e.r.). This principle can be extended to the formation of different biaryls such as 3ad (76% yield, 91:9 e.r.). Different substituents on the naphthol component can also be combined with different C-2 substituents on the indole component to afford an array of different products; these are exemplified by the formation of biaryl compounds bearing bromo 3ae (54% yield, 95:5 e.r.), methoxy 3af (82% yield, 92:8 e.r.), aryl 3ag (45% yield, 95:5 e.r.) and alkyl 3ah (66% yield, 93:7 e.r.) groups. The atropisomeric biaryl 3m contains a number of different functional groups, and to demonstrate their orthogonality, chemoselective derivatizations were implemented (Figure ). The C-3 ester on the naphthol 3m (97:3 e.r.), which is implicated in the observed selectivity in the cross-coupling process, can be transformed into tertiary alcohol 6 which is valuable in catalysis by O-functionalization followed by the addition of an excess of Grignard reagent. The C-3 ester group can also be conveniently removed by a palladium(II) catalysed reductive decarboxylation in the presence of stoichiometric triethylsilane to afford 7. Although this requires high temperatures, the magnitude of the barrier to rotation enables this to be performed without compromising enantiointegrity. The phenol in 7 can be simply transformed into triflate 8; the absolute configuration of this compound was confirmed by X-ray crystallography.