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Pd complex1
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Examination of electronic effects has become common practice in asymmetric catalysis. For some early examples of the electronic tuning of asymmetric catalysts, see: a
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For representative examples of the use of finely tuned phosphoramidites from various research groups, see: (a) Alexakis, A.; Polet, D.; Rosset, S.; March, S. J. Org. Chem. 2004, 69, 5660.
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(a) Smith, C. R.; RajanBabu, T. V. Org. Lett. 2008, 10, 1657. For a scalable procedure for the synthesis of phosphoramidites, see:
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63849297904
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To the best of our knowledge, ligand 87 has not been described in the literature. For a complete list of the phosphoramidites used in this study and its corresponding supporting information, see ref. 47.
-
To the best of our knowledge, ligand 87 has not been described in the literature. For a complete list of the phosphoramidites used in this study and its corresponding supporting information, see ref. 47.
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107
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63849268137
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Only naproxen is currently sold in an enantiomerically pure form. For a review of the practical aspects of the synthesis of 2-arylpropionic acids, see ref. 5a.
-
Only naproxen is currently sold in an enantiomerically pure form. For a review of the practical aspects of the synthesis of 2-arylpropionic acids, see ref. 5a.
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108
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and references cited therein, For reviews and a history of the problem, see: a
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Takemoto, T.; Sodeoka, M.; Sasai, H.; Shibasaki, M. J. Am. Chem. Soc. 1993, 115, 8477; corrigendum: J. Am. Chem. Soc. 1994, 116, 11207.
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(a) Zhang, A.; RajanBabu, T. V. J. Am. Chem. Soc. 2006, 128, 5620. For the use of another phosphoramidite, see:
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63849181367
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Dan Mans in our group has since completed the synthesis of a number of pseudopterosin aglycones by applying back-to-back enantioselective hydrovinylations of vinylarenes and dienes. This work will be reported in due course
-
(b) Dan Mans in our group has since completed the synthesis of a number of pseudopterosin aglycones by applying back-to-back enantioselective hydrovinylations of vinylarenes and dienes. This work will be reported in due course.
-
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121
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85026875962
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For a detailed procedure of this and other related hydrovinylation reactions, see
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For a detailed procedure of this and other related hydrovinylation reactions, see: Smith, C. R.; Zhang, A.; Mans, D. J.; RajanBabu, T. V. Org. Synth. 2008, 85, 248.
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For an early example (non-asymmetric) of the codimerization of ethylene and dienes, see: a
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For an early example (non-asymmetric) of the codimerization of ethylene and dienes, see: (a) Su, A. C. L. Adv. Organomet. Chem. 1979, 17, 269.
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63849325092
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Apart from Diels-Alder reactions, the asymmetric catalyzed carbon-carbon bond-forming reactions of acyclic 1,3-dienes give only moderate regio- and enantioselectivities. See the following examples. Cyclopropanation: (a) Doyle, M. In Catalytic Asymmetric Synthesis; Ojima, I., Ed.; Wiley-VCH: New York, 2000, 191-228. Ene reaction:
-
Apart from Diels-Alder reactions, the asymmetric catalyzed carbon-carbon bond-forming reactions of acyclic 1,3-dienes give only moderate regio- and enantioselectivities. See the following examples. Cyclopropanation: (a) Doyle, M. In Catalytic Asymmetric Synthesis; Ojima, I., Ed.; Wiley-VCH: New York, 2000, 191-228. Ene reaction:
-
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130
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Hydrocyanation
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(c) Horiuchi, T.; Ohta, T.; Shirakawa, E.; Nozaki, K.; Takaya, H. Tetrahedron 1997, 53, 7795. Hydrocyanation:
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For an extensive list of related references, see ref. 56.
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63849333139
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For reviews of the synthesis of 2-arylpropionic acids, see ref. 5
-
For reviews of the synthesis of 2-arylpropionic acids, see ref. 5.
-
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135
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33845282869
-
-
See the following for the best asymmetric routes to date [no useful catalytic asymmetric methods are known for other (5)-2-arylpropionic acid precursors]. Naproxen via Rucatalyzed asymmetric hydrogenation of 2-arylacrylic acids (98% ee): (a) Ohta, T.; Takaya, H.; Kitamura, M.; Nagai, K.; Noyori, R. J. Org. Chem. 1987, 52, 3174. Ni-catalyzed asymmetric hydrocyanation (95% ee):
-
See the following for the best asymmetric routes to date [no useful catalytic asymmetric methods are known for other (5)-2-arylpropionic acid precursors]. Naproxen via Rucatalyzed asymmetric hydrogenation of 2-arylacrylic acids (98% ee): (a) Ohta, T.; Takaya, H.; Kitamura, M.; Nagai, K.; Noyori, R. J. Org. Chem. 1987, 52, 3174. Ni-catalyzed asymmetric hydrocyanation (95% ee):
-
-
-
-
136
-
-
63849250059
-
-
See also ref. 38g; and references cited therein. Ibuprofen via Ru-catalyzed hydrogenation (97% ee):
-
(b) See also ref. 38g; and references cited therein. Ibuprofen via Ru-catalyzed hydrogenation (97% ee):
-
-
-
-
137
-
-
0000360958
-
-
Rh-catalyzed asymmetric hydroformylation 92% ee
-
(c) Uemura, T.; Zhang, X.; Matsumura, K.; Sayo, N.; Kumobayashi, H.; Ohta, T.; Nozaki, K.; Takaya, H. J. Org. Chem. 1996, 61, 5510. Rh-catalyzed asymmetric hydroformylation (92% ee):
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J. Org. Chem
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Uemura, T.1
Zhang, X.2
Matsumura, K.3
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Kumobayashi, H.5
Ohta, T.6
Nozaki, K.7
Takaya, H.8
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138
-
-
0030957928
-
-
Hydrovinylation 91% ee
-
(d)Nozaki, K.; Sakai, N.; Nanno, T.; Higashijima, T.; Mano, S.; Horiuchi, T.; Takaya, H. J. Am. Chem. Soc. 1997, 119, 4413. Hydrovinylation (91% ee):
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J. Am. Chem. Soc
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Nozaki, K.1
Sakai, N.2
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139
-
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63849231555
-
-
See ref. 40. Flurbiprofen via dynamic kinetic resolution:
-
(e) See ref. 40. Flurbiprofen via dynamic kinetic resolution:
-
-
-
-
140
-
-
63849200996
-
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Norinder, J.; Bogár, K.; Kaupp, L.; Backvall, J.-E. Org. Lett. 2007, 9, 5095. 167) Smith, C. R.; RajanBabu, T. V. J. Org. Chem. 2009, 74, in press. J68 For publications, see the following and references cited therein. Bisabolanes: (a) Hagiwara, H.; Okabe, T.; Ono, H.; Kamat, V. P.; Hoshi, T.; Suzuki, T.; Ando, M. J. Chem. Soc, Perkin Trans. 1 2002, 895.
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(f) Norinder, J.; Bogár, K.; Kaupp, L.; Backvall, J.-E. Org. Lett. 2007, 9, 5095. 167) Smith, C. R.; RajanBabu, T. V. J. Org. Chem. 2009, 74, in press. J68) For publications, see the following and references cited therein. Bisabolanes: (a) Hagiwara, H.; Okabe, T.; Ono, H.; Kamat, V. P.; Hoshi, T.; Suzuki, T.; Ando, M. J. Chem. Soc, Perkin Trans. 1 2002, 895.
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