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For a recent highlight, see: D. Peña, D. Pérez, E. Guitián, Angew. Chem. 2006, 118, 3659-3661;
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Peña, D.1
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Angew. Chem. Int. Ed. 2006, 45, 3579-3581.
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3
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22244435422
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For an overview, see: a, Eds, Z. Rappoport, I. Marek, Wiley, Chichester
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For an overview, see: a) J. Clayden in Chemistry of Organolithium Compounds, Vol. 1 (Eds.: Z. Rappoport, I. Marek), Wiley, Chichester, 2004, pp. 495-646;
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Clayden, J.1
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4
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0033553109
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for advances on the use of this technology to prepare iodoarenes, see: b
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for advances on the use of this technology to prepare iodoarenes, see: b) Y. Kondo, M. Shilai, M. Uchiyama, T. Sakamoto, J. Am. Chem. Soc. 1999, 121, 3539-3540;
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J. Am. Chem. Soc
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Kondo, Y.1
Shilai, M.2
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6
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33746302162
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for recent mechanistic insight, see: d
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for recent mechanistic insight, see: d) W. Clegg, S. H. Dale, E. Hevia, G. W. Honeyman, R. E. Mulvey, Angew. Chem. 2006, 118, 2430-2434;
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Angew. Chem. Int. Ed. 2006, 45, 2370-2374.
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a) X. Wan, Z. Ma, B. Li, K. Zhang, S. Cao, S. Zhang, Z. Shi, J. Am. Chem. Soc. 2006, 128, 7416-7417;
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Wan, X.1
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33744928374
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b) K. L. Hull, W. Q. Anani, M. S. Sanford, J. Am. Chem. Soc. 2006, 128, 7134-7135;
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J. Am. Chem. Soc
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Hull, K.L.1
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33744786786
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c) X. Chen, X.-S. Hao, C. E. Goodhue, J.-Q. Yu, J. Am. Chem. Soc. 2006, 128, 6790-6791;
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J. Am. Chem. Soc
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d) D. Kalyani, A. R. Dick, W. Q. Anani, M. S. Sanford, Org. Lett. 2006, 8, 2523-2526;
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e) A. R. Dick, K. L. Hull, M. S. Sanford, J. Am. Chem. Soc. 2004, 126, 2300-2301;
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Dick, A.R.1
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14
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for a stoichiometric cyclometalation approach, see: g
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for a stoichiometric cyclometalation approach, see: g) J. Vicente, I. Saura-Llamas, D. Bautista, Organometallics 2005, 24, 6001-6004.
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Organometallics
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Vicente, J.1
Saura-Llamas, I.2
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15
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0001418448
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For seminal work on electrophilic ortho-thallation under kinetic control to give o-iodoarenes upon the reaction of the o-thallium derivatives with KI, see: E. C. Taylor, F. Kienzle, R. L. Robey, A. McKillop, J. D. Hunt, J. Am. Chem. Soc. 1971, 93, 4845-4850.
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For seminal work on electrophilic ortho-thallation under kinetic control to give o-iodoarenes upon the reaction of the o-thallium derivatives with KI, see: E. C. Taylor, F. Kienzle, R. L. Robey, A. McKillop, J. D. Hunt, J. Am. Chem. Soc. 1971, 93, 4845-4850.
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34250833101
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We reported previously an iodination reaction of phenylalanine in peptides that showed unusual ortho selectivity: G. Espuña, G. Arsequell, G. Valencia, J. Barluenga, J. M. Alvarez-Gutiérrez, A. Ballesteros, J. M. González, Angew. Chem. 2004, 116, 329-333;
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We reported previously an iodination reaction of phenylalanine in peptides that showed unusual ortho selectivity: G. Espuña, G. Arsequell, G. Valencia, J. Barluenga, J. M. Alvarez-Gutiérrez, A. Ballesteros, J. M. González, Angew. Chem. 2004, 116, 329-333;
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0346500649
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Angew. Chem. Int. Ed. 2004, 43, 325-329.
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Chem. Int. Ed
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We speculated that lipophilic groups capable of establishing dipolar contacts with iodonium ions could favor selective ortho iodination. Also, the incorporation and removal of this controlling unit must be simple. For a recent review on organofluorine compounds, see: M. Shimizu, T. Hiyama, Angew. Chem. 2005, 117, 218-234;
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We speculated that lipophilic groups capable of establishing dipolar contacts with iodonium ions could favor selective ortho iodination. Also, the incorporation and removal of this controlling unit must be simple. For a recent review on organofluorine compounds, see: M. Shimizu, T. Hiyama, Angew. Chem. 2005, 117, 218-234;
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Angew. Chem. Int. Ed. 2005, 44, 214-231.
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Chem. Int. Ed
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This selectivity is in sharp contrast to that observed in previous aromatic iodinations with this reagent: a T. Shimada, M. Suda, T. Nagano, K. Kakiuchi, J. Org. Chem. 2005, 70, 10178-10181;
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This selectivity is in sharp contrast to that observed in previous aromatic iodinations with this reagent: a) T. Shimada, M. Suda, T. Nagano, K. Kakiuchi, J. Org. Chem. 2005, 70, 10178-10181;
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0002387306
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3H: c J. Barluenga, M. A. García-Martín, J. M. González, P. Clapés, G. Valencia, Chem. Commun. 1996, 1505-1506.
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3H: c) J. Barluenga, M. A. García-Martín, J. M. González, P. Clapés, G. Valencia, Chem. Commun. 1996, 1505-1506.
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23
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Compound o-2c was formed as single enantiomer by the iodination of (S)-1c. Its stereochemical integrity was confirmed by HPLC on a chiral phase, by comparison with a sample of racemic o-2c.
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Compound o-2c was formed as single enantiomer by the iodination of (S)-1c. Its stereochemical integrity was confirmed by HPLC on a chiral phase, by comparison with a sample of racemic o-2c.
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For reaction times, experimental details, and characterization data, see the Supporting Information
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For reaction times, experimental details, and characterization data, see the Supporting Information.
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25
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2) cyclization reactions of these compounds, see, for example: a) A. Klapars, S. Parris, K. W. Anderson, S. L. Buchwald, J. Am. Chem. Soc. 2004, 126, 3529-3533;
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2) cyclization reactions of these compounds, see, for example: a) A. Klapars, S. Parris, K. W. Anderson, S. L. Buchwald, J. Am. Chem. Soc. 2004, 126, 3529-3533;
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0141853186
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b) R. Omar-Amrane, A. Thomas, E. Brenner, R. Schneider, Y. Fort, Org. Lett. 2003, 5, 2311-2314;
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0036170254
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c) K. Yamada, T. Kubo, H. Tokuyama, T. Fukuyama, Synlett 2002, 231-234;
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Yamada, K.1
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d) L. F. Tietze, K. Thede, R. Schimpf, F. Sannicolò, Chem. Commun. 2000, 583-584;
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for a biological-activity profile of related compounds, see: f
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for a biological-activity profile of related compounds, see: f) R. H. P. Porter, J. T. Greenamyre, J. Neurochem. 1995, 64, 614-623;
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g) W. S. Sun, Y. S. Park, J. Yoo, K. D. Park, S. H. Kim, J.-H. Kim, H.-J. Park, J. Med. Chem. 2003, 46, 5619-5627;
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Sun, W.S.1
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h) J. Sterling, Y. Herzig, T. Goren, N. Finkelstein, D. Lerner, W. Goldenberg, I. Miskolczi, S. Molnar, F. Rantal, T. Tamas, G. Toth, A. Zagyva, A. Zekany, G. Lavian, A. Gross, R. Friedman, M. Razin, W. Huang, B. Krais, M. Chorev, M. B. Youdim, M. Weinstock, J. Med. Chem. 2002, 45, 5260-5279.
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Sterling, J.1
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Goldenberg, W.6
Miskolczi, I.7
Molnar, S.8
Rantal, F.9
Tamas, T.10
Toth, G.11
Zagyva, A.12
Zekany, A.13
Lavian, G.14
Gross, A.15
Friedman, R.16
Razin, M.17
Huang, W.18
Krais, B.19
Chorev, M.20
Youdim, M.B.21
Weinstock, M.22
more..
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For examples of cooperative weak interactions based on close contacts, see (CF⋯CH, a) S. C. F. Kui, N. Zhu, M. C. W. Chan, Angew. Chem. 2003, 115, 1666-1670;
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For examples of cooperative weak interactions based on close contacts, see (CF⋯CH): a) S. C. F. Kui, N. Zhu, M. C. W. Chan, Angew. Chem. 2003, 115, 1666-1670;
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Angew. Chem. Int. Ed. 2003, 42, 1628-1632;
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1642376356
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(CF⋯Si): b) S.-Y Kim, A. Saxena, G. Kwak, M. Fujiki, Y. Kawakami, Chem. Commun. 2004, 538-539;
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(CF⋯Si): b) S.-Y Kim, A. Saxena, G. Kwak, M. Fujiki, Y. Kawakami, Chem. Commun. 2004, 538-539;
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36
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20444479110
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for the notion of halogen bonding, see: c
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for the notion of halogen bonding, see: c) P. Metrangolo, H. Neukirch, T. Pilati, G. Resnati, Acc. Chem. Res. 2005, 38, 386-395;
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Acc. Chem. Res
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Metrangolo, P.1
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Resnati, G.4
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37
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d) P. Auffinger, F. A. Hays, E. Westhof, P. S. Ho, Proc. Natl. Acad. Sci. USA 2004,101, 16789-16794.
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Auffinger, P.1
Hays, F.A.2
Westhof, E.3
Ho, P.S.4
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0037008930
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Similar derivatives were synthesized previously by using an indirect strategy to access the required ortho-halogenated precursor: W. Wang, M. Cai, C. Xiong, J. Zhang, D. Trivedi, V J. Hruby, Tetrahedron 2002, 58, 7365-7374
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Similar derivatives were synthesized previously by using an indirect strategy to access the required ortho-halogenated precursor: W. Wang, M. Cai, C. Xiong, J. Zhang, D. Trivedi, V J. Hruby, Tetrahedron 2002, 58, 7365-7374.
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33646137411
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For some remarkable examples of the metal-catalyzed arylation of aromatic C-H bonds, see: a
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For some remarkable examples of the metal-catalyzed arylation of aromatic C-H bonds, see: a) N. R. Deprez, D. Kalyani, A. Krause, M. S. Sanford, J. Am. Chem. Soc. 2006, 128, 4972-4973;
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J. Am. Chem. Soc
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Deprez, N.R.1
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b) L.-C. Campeau, M. Parisien, A. Jean, K. Fagnou, J. Am. Chem. Soc. 2006, 128, 581-590;
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Campeau, L.-C.1
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c) L.-C. Campeau, S. Rousseaux, K. Fagnou, J. Am. Chem. Soc. 2005, 127, 18020-18021;
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Campeau, L.-C.1
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Angew. Chem. Int. Ed. 2005, 44, 4046-4048;
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Chem. Int. Ed
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e) D. Kalyani, N. R. Deprez, L. V. Desai, M. S. Sanford, J. Am. Chem. Soc. 2005, 127, 7330-7331;
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f) X. Wang, B. S. Lane, D. Sames, J. Am. Chem. Soc. 2005, 127, 4996-4997.
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Wang, X.1
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The reaction conditions were adapted from those reported in: S. Kohta, K. Lahiri, Bioorg. Med. Chem. Lett. 2001, 11, 2887-2890.
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The reaction conditions were adapted from those reported in: S. Kohta, K. Lahiri, Bioorg. Med. Chem. Lett. 2001, 11, 2887-2890.
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47
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HPLC analysis of 3 on a chiral phase proved that it was formed as single enantiomer (> 98% ee). Compound 6 was formed as a mixture of two diastereomers, each with > 97 % ee.
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HPLC analysis of 3 on a chiral phase proved that it was formed as single enantiomer (> 98% ee). Compound 6 was formed as a mixture of two diastereomers, each with > 97 % ee.
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