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Catalytic asymmetric dihydroxylation of α,β-unsaturated phosphonates as a key step: Y. Kobayashi, A. D. William, Y. Tokoro, J. Org. Chem. 2001, 66, 7903, and references therein.
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Recent general reviews on asymmetric epoxidations: a) Modern Oxidation Methods (Ed.: J. E. Bäckvall), Wiley-VCH, Weinheim, 2004;
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For recent general reviews on asymmetric epoxidation of electrondeficient C-C double bonds, see: a
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For recent general reviews on asymmetric epoxidation of electrondeficient C-C double bonds, see: a) M. J. Porter, J. Skidmore, Chem. Commun. 2000, 1215;
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21544444468
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The synthesis of functionalized chiral phosphane oxides is also useful owing to their potential use in asymmetric catalysis; see the review: a M. Kanai, N. Kato, E. Ichikawa, M. Shibasaki, Synlett 2005, 1491;
-
The synthesis of functionalized chiral phosphane oxides is also useful owing to their potential use in asymmetric catalysis; see the review: a) M. Kanai, N. Kato, E. Ichikawa, M. Shibasaki, Synlett 2005, 1491;
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17
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33845944635
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for selected recent examples, see also: b I. Fujimori, T. Mita, K. Maki, M. Shiro, A. Sato, S. Furusho, M. Kanai, M. Shibasaki, J. Am. Chem. Soc. 2006, 128, 16438;
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for selected recent examples, see also: b) I. Fujimori, T. Mita, K. Maki, M. Shiro, A. Sato, S. Furusho, M. Kanai, M. Shibasaki, J. Am. Chem. Soc. 2006, 128, 16438;
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Ogawa, C.1
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Kotani, S.1
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3/binol: a) M. Bougauchi, S. Watanabe, T. Arai, H. Sasai, M. Shibasaki, J. Am. Chem. Soc. 1997, 119, 2329;
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3/binol: a) M. Bougauchi, S. Watanabe, T. Arai, H. Sasai, M. Shibasaki, J. Am. Chem. Soc. 1997, 119, 2329;
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a) K. Daikai, M. Kamaura, J. Inanaga, Tetrahedron Lett. 1998, 39, 7321;
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a) R. Chen, C. Qian, J. G. de Vries, Tetrahedron 2001, 57, 9837;
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3/binol: a) T. Nemoto, H. Kakei, V. Gnanadesikan, S.-y. Tosaki, T. Ohshima, M. Shibasaki, J. Am. Chem. Soc. 2002, 124, 14544;
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3/binol: a) T. Nemoto, H. Kakei, V. Gnanadesikan, S.-y. Tosaki, T. Ohshima, M. Shibasaki, J. Am. Chem. Soc. 2002, 124, 14544;
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b) S.-y. Tosaki, R. Tsuji, T. Ohshima, M. Shibasaki, J. Am. Chem. Soc. 2005, 127, 2147;
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c) T. Nemoto, T. Ohshima, M. Shibasaki, J. Am. Chem. Soc. 2001, 123, 9474.
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8-binol: a) S. Matsunaga, T. Kinoshita, S. Okada, S. Harda, M. Shibasaki, J. Am. Chem. Soc. 2004, 126, 7559;
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8-binol: a) S. Matsunaga, T. Kinoshita, S. Okada, S. Harda, M. Shibasaki, J. Am. Chem. Soc. 2004, 126, 7559;
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35
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33744782373
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b) S. Matsunaga, H. Qin, M. Sugita, S. Okada, T. Kinoshita, N. Yamagiwa, M. Shibasaki, Tetrahedron 2006, 62, 6630.
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Matsunaga, S.1
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Shibasaki, M.7
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36
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34248189099
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3/binol: a) H. Kakei, R. Tsuji, T. Ohshima, H. Morimoto, S. Matsunaga, M. Shibasaki, Chem. Asian J. 2007, 2, 257;
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3/binol: a) H. Kakei, R. Tsuji, T. Ohshima, H. Morimoto, S. Matsunaga, M. Shibasaki, Chem. Asian J. 2007, 2, 257;
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37
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21244501222
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b) H. Kakei, R. Tsuji, T. Ohshima, M. Shibasaki, J. Am. Chem. Soc. 2005, 127, 8962.
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Kakei, H.1
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Shibasaki, M.4
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38
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54849409879
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3P(O) additive had beneficial effects on epoxidation, see: a) T. Kinoshita, S. Okada, S.-R. Park, S. Matsunaga, M. Shibasaki, Angew. Chem. 2003, 115, 4828;
-
3P(O) additive had beneficial effects on epoxidation, see: a) T. Kinoshita, S. Okada, S.-R. Park, S. Matsunaga, M. Shibasaki, Angew. Chem. 2003, 115, 4828;
-
-
-
-
40
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0000445631
-
-
for a general review of achiral additives for the improvement of chiral catalysts, see: b
-
for a general review of achiral additives for the improvement of chiral catalysts, see: b) E. M. Vogl, H. Gröger, M. Shibasaki, Angew. Chem. 1999, 111, 1672;
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(1999)
Angew. Chem
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Vogl, E.M.1
Gröger, H.2
Shibasaki, M.3
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42
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3142739528
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Steric and electronic modification of phosphane oxide additives have beneficial effects in rare-earth-metal-catalyzed epoxidation as well as other reactions; see, for epoxidation: a R. Kino, K. Daikai, T. Kawanami, H. Furuno, J. Inanaga, Org. Biomol. Chem. 2004, 2, 1822;
-
Steric and electronic modification of phosphane oxide additives have beneficial effects in rare-earth-metal-catalyzed epoxidation as well as other reactions; see, for epoxidation: a) R. Kino, K. Daikai, T. Kawanami, H. Furuno, J. Inanaga, Org. Biomol. Chem. 2004, 2, 1822;
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43
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33846473111
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b) Z. Chen, H. Morimoto, S. Matsunaga, M. Shibasaki, Synlett 2006, 3529;
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(2006)
Synlett
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Chen, Z.1
Morimoto, H.2
Matsunaga, S.3
Shibasaki, M.4
-
44
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0038108347
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for other reactions: c
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for other reactions: c) J. Tian, N. Yamagiwa, S. Matsunaga, M. Shibasaki, Angew. Chem. 2002, 114, 3788;
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(2002)
Angew. Chem
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, pp. 3788
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Tian, J.1
Yamagiwa, N.2
Matsunaga, S.3
Shibasaki, M.4
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46
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14944386585
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-
and references therein
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d) N. Yamagiwa, J. Tian, S. Matsunaga, M. Shibasaki, J. Am. Chem. Soc. 2005, 127, 3413, and references therein.
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(2005)
J. Am. Chem. Soc
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, pp. 3413
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Yamagiwa, N.1
Tian, J.2
Matsunaga, S.3
Shibasaki, M.4
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47
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1942436903
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Biphenyldiol 1a: a A. I. Meyers, T. D. Nelson, H. Moorlag, D. J. Rawson, A. Meier, Tetrahedron 2004, 60, 4459, and references therein;
-
Biphenyldiol 1a: a) A. I. Meyers, T. D. Nelson, H. Moorlag, D. J. Rawson, A. Meier, Tetrahedron 2004, 60, 4459, and references therein;
-
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-
-
48
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33748496246
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-
for the utility of biphenyldiol in other asymmetric reactions, see: b
-
for the utility of biphenyldiol in other asymmetric reactions, see: b) S.-y. Tosaki, K. Hara, V. Gnanadesikan, H. Morimoto, S. Harada, M. Sugita, N. Yamagiwa, S. Matsunaga, M. Shibasaki, J. Am. Chem. Soc. 2006, 128, 11776;
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(2006)
J. Am. Chem. Soc
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Tosaki, S.-Y.1
Hara, K.2
Gnanadesikan, V.3
Morimoto, H.4
Harada, S.5
Sugita, M.6
Yamagiwa, N.7
Matsunaga, S.8
Shibasaki, M.9
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49
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35948949568
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c) H. Kakei, T. Sone, Y. Sohtome, S. Matsunaga, M. Shibasaki, J. Am. Chem. Soc. 2007, 129, 13410;
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(2007)
J. Am. Chem. Soc
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Kakei, H.1
Sone, T.2
Sohtome, Y.3
Matsunaga, S.4
Shibasaki, M.5
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50
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34548154771
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d) A. Yamaguchi, N. Aoyama, S. Matsunaga, M. Shibasaki, Org. Lett. 2007, 9, 3387.
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(2007)
Org. Lett
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Yamaguchi, A.1
Aoyama, N.2
Matsunaga, S.3
Shibasaki, M.4
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51
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We selected Ph(2-MeO-C6H4)2P(O) as the best additive for further studies. When β-alkyl α,β-unsaturated phosphane oxide 2 f was used as a substrate, Ph(2-MeO-C6H 4)2P(O) also gave slightly better results than Ph 3P(O, Ph(2-MeO-C6H4)2P(O, 98% yield, 91% ee (see Table 2, Ph3PO, 80% yield, 87% ee
-
3P(O): 80% yield, 87% ee.
-
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52
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54849412075
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-
3As(O) has adverse effects on the reactivity of the rare-earth-metal catalyst; see references [10b] and [16].
-
3As(O) has adverse effects on the reactivity of the rare-earth-metal catalyst; see references [10b] and [16].
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53
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54849430725
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The absolute configurations of epoxides 3a and 3 f were determined to be S,S after epoxide ring opening; see Supporting Information for detailed information.
-
The absolute configurations of epoxides 3a and 3 f were determined to be S,S after epoxide ring opening; see Supporting Information for detailed information.
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55
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33646069329
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-
3 of the same quality is also available from Aldrich (Cat. No. 2172-12-5); see also: M. Shibasaki, M. Kanai, S. Matsunaga, Aldrichimica Acta 2006, 39, 31.
-
3 of the same quality is also available from Aldrich (Cat. No. 2172-12-5); see also: M. Shibasaki, M. Kanai, S. Matsunaga, Aldrichimica Acta 2006, 39, 31.
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