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0141472599
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note
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Our inability to form the hindered biaryl axis of biaryl (±)-1 by direct coupling previously led us to develop an indirect synthesis that proceeded via two sequential less hindered coupling reactions. See ref 9e.
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64
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0034614046
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Buchwald's phenanthryl ligand 4 was the only ligand that allowed coupling between bromopyridine 2 and boronic acid 3. See: (a) Yin, J.; Buchwald, S. L. J. Am. Chem. Soc. 2000, 122, 12051-12052; (b) Yin, J.; Rainka, M. P.; Zhang, X.-X.; Buchwald, S. L. J. Am. Chem. Soc. 2002, 124, 1162-1163.
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Buchwald's phenanthryl ligand 4 was the only ligand that allowed coupling between bromopyridine 2 and boronic acid 3. See: (a) Yin, J.; Buchwald, S. L. J. Am. Chem. Soc. 2000, 122, 12051-12052; (b) Yin, J.; Rainka, M. P.; Zhang, X.-X.; Buchwald, S. L. J. Am. Chem. Soc. 2002, 124, 1162-1163.
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note
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NAr.
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69
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0141472598
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and references therein
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For 4-halopyridine coupling see: Wolfe, J. P.; Tomori, H.; Sadighi, J. P.; Yin, J.; Buchwald, S. L. J. Org. Chem. 2000, 69, 1168-1174 and references therein.
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note
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The transformation of dihalopyridine 6 into aminopyridines 1 and 7 can be performed as a single step by employing s-BuLi (1.5 equiv) to effect bromine-lithium exchange at -78 °C (30 min), followed by addition of lithium diethylamide (3 equiv), warming to room temperature, and then refluxing for 16 h. However, in our hands this procedure gave a significantly less clean reaction and provided lower yields of the both products following tedious purification.
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72
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0033411291
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This method of resolving agent selection has been used previously to identify an appropriate chiral amine from a panel of chiral amines for resolution of a racemic carboxylic acid; see: Dyer, U. C.; Henderson, D. A.; Mitchell, M. B. Org. Proc. Res. Devel. 1999, 3, 161-165. This publication also provides a detailed description of the basis of the method and details of the Resolution Companion software package.
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0003942864
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Wiley: New York
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The fused benzenoid ring takes priority over the 2-phenyl substituent when assigning the naphthyl end of the biaryl axis by Cahn-Ingold-Prelog (CIP) priority rules; see: Eliel, E. L.; Wilen, S. H. Stereochemistry of Organic Compounds; Wiley: New York, 1994; p 107.
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74
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0141695864
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note
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a)-1 displays a negative Cotton-effect peak in its circular dichroism spectrum at 335 nm. The assignment of the absolute configuration oftopologically related atropisomeric catalyst structures is therefore possible by comparison of their Cotton-effect peaks in this region.
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78
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79
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note
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Interestingly, although many of the catalysts studied by Campbell (e.g. structure VI, Figure 1) are topologically closely related to the catalyst of Fuji (structure IV, Figure 1), H-bonding was postulated to be the dominant mediator of chirality transfer for this series of catalysts and no evidence for π-π stacking was found. See ref 7a.
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