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The increased selectivity for position d when using 1a in 2-MeTHF may be based on the increased polarity of the solvent relative to DCM and the resultant increase in competition between substrate and solvent for coordination to iridium. Coordination of the amide carbonyl and labelling via a 5-membered metallacycle (position d) is more facile than via the 6-membered metallacycle (position c; see ref. 9 for details). Additionally, coordination through the nitro group (for labelling at a and b) is presumed to be weaker than for the amide. For a recent discussion on the use of coordinating additives to increase reaction chemoselectivity, see
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