Catalytic asymmetric dihydroxylation

Chemical Reviews

Volumn 94, Issue 8, 1994, Pages 2483-2547

  Kolb, Hartmuth C ^a,b   VanNieuwenhze, Michael S ^a,c   Sharpless, K Barry ^a  

^a SCRIPPS RESEARCH INSTITUTE   (United States)

^b CIBA GEIGY LTD   (Switzerland)

^c ELI LILLY AND COMPANY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 4444276636     PISSN: 00092665     EISSN: None     Source Type: Journal    
DOI: 10.1021/cr00032a009     Document Type: Article

References (464)

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7. (b) For mechanistic details, see: Woodard, S. S.; Finn, M. G.; Sharpless, K. B. J. Am. Chem. Soc. 1991, 113, 106.
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9. (d) Finn, M. G. Ph.D. Thesis, Massachusetts Institute of Technology, 1985.
10. For earlier reviews of the AD reaction, see: (a) Johnson, R. A.; Sharpless, K. B. Catalytic Asymmetric Dihydroxylation. In Catalytic Asymmetric Synthesis; Ojima, I., Ed.; VCH Publishers: New York, 1993; pp 227-272. (b) Lohray, B. B. Tetrahedron: Asymmetry 1992, 3, 1317-1349.
11. For earlier reviews of the AD reaction, see: (a) Johnson, R. A.; Sharpless, K. B. Catalytic Asymmetric Dihydroxylation. In Catalytic Asymmetric Synthesis; Ojima, I., Ed.; VCH Publishers: New York, 1993; pp 227-272. (b) Lohray, B. B. Tetrahedron: Asymmetry 1992, 3, 1317-1349.
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21. The [3 + 2] mechanism was originally proposed by Böseken (e) Böseken, J. Recl. Trav. Chim. 1922, 41, 199. For the [2 + 2] mechanism, see (f) Sharpless, K. B.; Teranishi, A. Y.; Bäckvall, J.-E. J. Am. Chem. Soc. 1977, 99, 3120. (g) Jorgensen, K. A.; Schiott, B. Chem. Rev. 1990, 90, 1483.
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50. 2, trans-5-decene was only partially (70%) converted to the corresponding diol after 3 days at 0 °C, whereas the diol was isolated in 97% yield after only 10 h at 0 °C in the presence of this additive, see ref 23a.
51. Göbel, T.; Sharpless, K. B. Angew. Chem., Int. Ed. Engl. 1993, 32, 1329.
52. (a) Sharpless, K. B.; Amberg, W.; Bennani, Y. L.; Crispino, G. A.; Hartung, J.; Jeong, K.-S.; Kwong, H.-L.; Morikawa, K.; Wang, Z.-M.; Xu, D.; Zhang, X.-L. J. Org. Chem. 1992, 57, 2768.
53. For simplified experimental procedures for the preparation of the phthalazine ligands as well as an X-ray crystal structure, see (b) Amberg, W.; Bennani, Y. L.; Chadha, R. K.; Crispino, G. A.; Davis, W. D.; Hartung, J.; Jeong, K.-S.; Ogino, Y.; Shibata, T.; Sharpless, K. B. J. Org. Chem. 1993, 58, 844.
54. Crispino, G. A.; Jeong, K.-S.; Kolb, H. C.; Wang, Z.-M.; Xu, D.; Sharpless, K. B. J. Org. Chem. 1993, 58, 3785.
55. Sharpless, K. B.; Amberg, W.; Beller, M.; Chen, H.; Hartung, J.; Kawanami, Y.; Lübben, D.; Manoury, E.; Ogino, Y.; Shibata, T.; Ukita, T. J. Org. Chem. 1991, 56, 4585.
56. Kolb, H. C.; Andersson, P. G.; Sharpless, K. B. J. Am. Chem. Soc. 1994, 116, 1278.
57. 4 with olefins, see (a) Norrby, P.-O.; Kolb, H. C.; Sharpless, K. B. Organometallics 1994, 13, 344. For a modified MM2 force field for the calculation of osmaoxetane complexes, see (b) Norrby, P.-O.; Kolb, H. C.; Sharpless, K. B. J. Am. Chem. Soc. 1994, 116, 8470. For Hartree-Fock calculations on Os complexes using a quasirelativistic effective core potential for Os, see (c) Veldkamp, A.; Frenking, G. J. Am. Chem. Soc. 1994, 116, 4937. For a molecular mechanics model for rationalizing the stereoselectivity of the AD with diamine ligands based on a [3 + 2] mechanism, see (d) Wu, Y.-D.; Wang, Y.; Houk, K. N. J. Org. Chem. 1992, 57, 1362.
58. 4 with olefins, see (a) Norrby, P.-O.; Kolb, H. C.; Sharpless, K. B. Organometallics 1994, 13, 344. For a modified MM2 force field for the calculation of osmaoxetane complexes, see (b) Norrby, P.-O.; Kolb, H. C.; Sharpless, K. B. J. Am. Chem. Soc. 1994, 116, 8470. For Hartree-Fock calculations on Os complexes using a quasirelativistic effective core potential for Os, see (c) Veldkamp, A.; Frenking, G. J. Am. Chem. Soc. 1994, 116, 4937. For a molecular mechanics model for rationalizing the stereoselectivity of the AD with diamine ligands based on a [3 + 2] mechanism, see (d) Wu, Y.-D.; Wang, Y.; Houk, K. N. J. Org. Chem. 1992, 57, 1362.
59. 4 with olefins, see (a) Norrby, P.-O.; Kolb, H. C.; Sharpless, K. B. Organometallics 1994, 13, 344. For a modified MM2 force field for the calculation of osmaoxetane complexes, see (b) Norrby, P.-O.; Kolb, H. C.; Sharpless, K. B. J. Am. Chem. Soc. 1994, 116, 8470. For Hartree-Fock calculations on Os complexes using a quasirelativistic effective core potential for Os, see (c) Veldkamp, A.; Frenking, G. J. Am. Chem. Soc. 1994, 116, 4937. For a molecular mechanics model for rationalizing the stereoselectivity of the AD with diamine ligands based on a [3 + 2] mechanism, see (d) Wu, Y.-D.; Wang, Y.; Houk, K. N. J. Org. Chem. 1992, 57, 1362.
60. 4 with olefins, see (a) Norrby, P.-O.; Kolb, H. C.; Sharpless, K. B. Organometallics 1994, 13, 344. For a modified MM2 force field for the calculation of osmaoxetane complexes, see (b) Norrby, P.-O.; Kolb, H. C.; Sharpless, K. B. J. Am. Chem. Soc. 1994, 116, 8470. For Hartree-Fock calculations on Os complexes using a quasirelativistic effective core potential for Os, see (c) Veldkamp, A.; Frenking, G. J. Am. Chem. Soc. 1994, 116, 4937. For a molecular mechanics model for rationalizing the stereoselectivity of the AD with diamine ligands based on a [3 + 2] mechanism, see (d) Wu, Y.-D.; Wang, Y.; Houk, K. N. J. Org. Chem. 1992, 57, 1362.
61. Hale, K. J.; Manaviazar, S.; Peak, S. A. Tetrahedron Lett. 1994, 35, 425.
62. Wang, L.; Sharpless, K. B. J. Am. Chem. Soc. 1992, 114, 7568.
63. Corey, E. J.; Noe, M. C.; Sarshar, S. J. Am. Chem. Soc. 1993, 115, 3828.
64. Lohray, B. B.; Bhushan, V. Tetrahedron Lett. 1992, 33, 5113. See also ref 111.
65. Both of the ligands in question were prepared and tested by the Sharpless group at MIT as part of the screening process. They were rejected due to the observed superiority of the phthalazine class of ligands in virtually all applications of the AD reaction: Hartung, J.; Jeong, K.-S.; Sharpless, K. B. Unpublished results. (The pyridazine ligands are included in MIT's U.S. Pat. Appl. No. 077/775, 683, Oct 10, 1991.)
66. Crispino, G. A.; Makita, A.; Wang, Z.-M.; Sharpless, K. B. Tetrahedron Lett. 1994, 35, 543.
67. 2-PYR, no. 41,897-8]. The cinchona alkaloids, needed for the preparation of these ligands are also sold by Aldrich [hydroquinidine, no. 35,934-3; hydroquinine, no. 33,771-4].
68. 4) species and proposed an alternative mechanism which involves sandwich-like stacking of the olefin between the two methoxyquinoline units of the "dimeric" ligand; see (b) Corey, E. J.; Noe, M. C. J. Am. Chem. Soc. 1993, 115, 12579. (c) Corey, E. J.; Noe, M. C.; Sarshar, S. Tetrahedron Lett. 1994, 35, 2861.
69. 4) species and proposed an alternative mechanism which involves sandwich-like stacking of the olefin between the two methoxyquinoline units of the "dimeric" ligand; see (b) Corey, E. J.; Noe, M. C. J. Am. Chem. Soc. 1993, 115, 12579. (c) Corey, E. J.; Noe, M. C.; Sarshar, S. Tetrahedron Lett. 1994, 35, 2861.
70. 4) species and proposed an alternative mechanism which involves sandwich-like stacking of the olefin between the two methoxyquinoline units of the "dimeric" ligand; see (b) Corey, E. J.; Noe, M. C. J. Am. Chem. Soc. 1993, 115, 12579. (c) Corey, E. J.; Noe, M. C.; Sarshar, S. Tetrahedron Lett. 1994, 35, 2861.
71. Becker, H.; Ho, P. T.; Kolb, H. C.; Loren, S.; Norrby, P.-O.; Sharpless, K. B. Tetrahedron Lett. 1994, 35, 7315.
72. Vanhessche, K. P. M.; Sharpless, K. B. Manuscript in preparation.
73. (a) Kolb, H. C.; Bennani, Y. L.; Sharpless, K. B. Tetrahedron: Asymmetry 1993, 4, 133.
74. (b) Arrington, M. P.; Bennani, Y. L.; Göbel, T.; Walsh, P. J.; Zhao, S.-H.; Sharpless, K. B. Tetrahedron Lett. 1993, 34, 7375.
75. Vanhessche, K. P. M.; Wang, Z.-M.; Sharpless, K. B. Tetrahedron Lett. 1994, 35, 3469.
76. (a) Okamoto, S.; Tani, K.; Sato, F.; Sharpless, K. B.; Zargarian, D. Tetrahedron Lett. 1993, 34, 2509.
77. (b) Soderquist, J. A.; Rane, A. M.; López, C. J. Tetrahedron Lett. 1993, 34, 1893.
78. (c) Bassindale, A. R.; Taylor, P. G.; Xu, Y. J. Chem. Soc., Perkin Trans. 1 1994, 1061.
79. (a) Wang, Z.-M.; Zhang, X.-L.; Sharpless, K. B. Tetrahedron Lett. 1993, 34, 2267.
80. (b) Wang, Z.-M.; Sharpless, K. B. Unpublished results.
81. Hartung, J.; Loren, S.; Sharpless, K. B. Unpublished results. The enantiomeric excess was determined by HPLC analysis of the diol (Pirkle 1-A 25 cm × 10 mm, 2.5% i-PrOH in hexane, 1.5 mL/min, 254 nm).
82. (a) Walsh, P. J.; Ho, P. T.; King, S. B.; Sharpless, K. B. Tetrahedron Lett. 1994, 35, 5129.
83. (b) Sammakia, T.; Hurley, B.; Sammond, D.; Smith, R., University of Colorado, unpublished results.
84. The best enantiomeric excess is obtained with DHQD-PHN (86% ee, 96% ee after recrystallization) in this particular case; see: (a) Oi, R.; Sharpless, K. B. Tetrahedron Lett. 1992, 33, 2095. (b) Determination of the enantiomeric excess with phthalazine and pyrimidine ligands: Wang, Z.-M.; Sharpless, K. B. Unpublished results.
85. The best enantiomeric excess is obtained with DHQD-PHN (86% ee, 96% ee after recrystallization) in this particular case; see: (a) Oi, R.; Sharpless, K. B. Tetrahedron Lett. 1992, 33, 2095. (b) Determination of the enantiomeric excess with phthalazine and pyrimidine ligands: Wang, Z.-M.; Sharpless, K. B. Unpublished results.
86. A number of ee determinations with pyrimidine ligands have not been published (Wang, Z.-M.; Sharpless, K. B.).
87. The AD reactions were carried out with the AD-mixes at 0 °C under standard conditions. The enantiomeric excesses were determined by HPLC analysis of the bis[methoxy(trifluoromethyl)phenylacetate] esters (Pirkle 1-A 25 cm × 10 mm, 2.5% i-PrOH in hexane, 1 mL/min, 254 nm) (Zhang, X.-L.; Sharpless, K. B., unpublished results).
88. Wang, Z.-M.; Sharpless, K. B. Synlett 1993, 603.
89. The AD reactions of these two olefins were carried out under standard conditions at 0 °C using the AD-mixes; the enantiomeric excesses were determined by GLC analysis of the diols [(entry 7) J & W CDX-B (30 m × 0.32 mm i.d.), 120 °C, (entry 8) J & W CDX-B (30 m × 0.32 mm i.d.), 90 °C] (Morikawa, K.; Sharpless, K. B., unpublished results).
90. 4; the enantiomeric excess was determined by GC analysis of the bis(methoxy(trifluoromethyl)phenylacetate) esters (J & W DB-17 (30 m × 0.32 mm ID), 230 °C) (Wang, Z.-M.; Sharpless, K. B., unpublished results).
91. Kolb, H. C.; Sharpless, K. B. Tetrahedron 1992, 48, 10515.
92. Crispino, G. A.; Ho, P. T.; Sharpless, K. B. Science 1993, 259, 64.
93. (a) Ko, S. Y.; Malik, M. Tetrahedron Lett. 1993, 34, 4675.
94. (b) Ko, S. Y.; Malik, M.; Dickinson, A. F. J. Org. Chem. 1994, 59, 2570.
95. The AD reaction of this olefin was carried out with AD-mix-β at O °C; the enantiomeric excess was determined by GC analysis of the bis(methoxy(trifluoromethyl)phenylacetate) esters (J & W DB-5 (30 m × 0.32 mm ID), 160 °C) (Jeong, K.-S.; Sharpless, K. B., unpublished results).
96. 4 at 0 °C; the enantiomeric excess was determined by HPLC analysis of the cyclic carbonate (Chiralcel OD-H 25 cm × 4.6 mm, 2.5% i-PrOH in hexane, 0.8 mL/min, 254 nm) (Loren, S.; Sharpless, K. B., unpublished results).
97. 4 at O °C; the enantiomeric excess was determined by HPLC analysis of the cyclic carbonate [(entry 5) Chiralcel OD-H 25 cm × 4.6 mm, 2.5% i-PrOH in hexane, 0.8 mL/min, 254 nm] and by HPLC analysis of the diol (Chiralcel OD-H 25 cm × 4.6 mm, 10% J-PrOH in hexane (entry 6) and 30% i-PrOH in hexane [(entry 7) 0.5 mL/min, 254 nm] (Loren, S.; Sharpless, K. B., unpublished results).
98. Hashiyama, T.; Morikawa, K.; Sharpless, K. B. J. Org. Chem. 1992, 57, 5067.
99. Morikawa, K.; Park, J.; Andersson, P. G.; Hashiyama, T.; Sharpless, K. B. J. Am. Chem. Soc. 1993, 115, 8463.
100. Wang, Z.-M.; Sharpless, K. B. Unpublished results, also see ref 127.
101. Henderson, I.; Sharpless, K. B.; Wong, C.-H. J. Am. Chem. Soc. 1994, 116, 558.
102. 2O (36% ee) (Kolb, H. C.; Sharpless, K. B., unpublished results).
103. (a) Zhang, X.-L.; Sharpless, K. B. Unpublished results,
104. (b) Byun, H.-S.; Kumar, E. R.; Bittman, R. J. Org. Chem. 1994, 59, 2630.
105. 4 may be used in certain cases if one wishes to "optimize" the amounts of the key reagents for economic reasons in a large-scale process.
106. The procedure for the recovery and recycling of the ligand has been developed by Dr. Yun Gao of Sepracor for the large-scale AD of m-chlorostyrene (personal communication).
107. 3 (293.9 g), and finally mixed thoroughly in a blender for ca. 30 min. The resulting orange powder should be kept dry and is ready to use.
108. 3.
109. Bennani, Y. L.; Sharpless, K. B. Tetrahedron Lett. 1993, 34, 2079.
110. Walsh, P. J.; Sharpless, K. B. Synlett 1993, 605.
111. (a) Nahm, S.; Weinreb, S. M. Tetrahedron Lett. 1981, 22, 3815.
112. For a review, see (b) O'Neill, B. T. Nucleophilic Addition to Carboxylic Acid Derivatives. In Comprehensive Organic Synthesis; Fleming, I., Trost, B. M., Eds.; Pergamon Press: New York, 1991; Vol. 1, pp 397-458.
113. Kaldor, S. W.; Hammond, M. Tetrahedron Lett. 1991, 32, 5043.
114. 4-ligand complex responsible for dihydroxylation in the ferricyanide system and may give very different diastereoselectivity results (as well as different regioselectivity, etc., vide infra).
115. (a) Cha, J. K.; Christ, W. J.; Kishi, Y. Tetrahedron Lett. 1983, 24, 3943.
116. (b) Stork, G.; Kahn, M. Tetrahedron Lett. 1983, 24, 3951.
117. (c) Houk, K. N.; Moses, S. R.; Wu, Y.-D.; Rondan, N. G.; Jager, V.; Schohe, R.; Fronczek, F. R. J. Am. Chem. Soc. 1984, 106, 3880.
118. (d) Houk, K. N.; Paddon-Row, M. N.; Rondan, N. G.; Wu, Y.-D.; Brown, F. K.; Spellmeyer, D. C.; Metz, J. T.; Li, Y.; Loncharich, R. J. Science 1986, 231, 1108.
119. For an excellent review of double asymmetric synthesis, see: Masamune, S.; Choy, W.; Petersen, J. S.; Sita, L. R. Angew. Chem., Int. Ed. Engl. 1985, 24, 1.
120. Generally, the levels of matched and mismatched double diastereoselection observed in the asymmetric dihydroxylation of chiral monosubstituted olefins are not as high as those observed for the other olefin substitution classes.
121. For examples of doubly diastereoselective asymmetric dihydroxylations of monosubstituted olefins, see (a) Ireland, R. E.; Wipf, P.; Roper, T. D. J. Org. Chem. 1990, 55, 2284. (b) Jirousek, M. R.; Cheung, A. W.-H.; Babine, R. E.; Sass, P. M.; Schow, S. R.; Wick, M. M. Tetrahedron Lett. 1993, 34, 3671. (c) Sinha, S. C.; Keinan, E. J. Org. Chem. 1994, 59, 949. (d) Hoffmann, R. W.; Schlapbach, A. Tetrahedron Lett. 1993, 34, 7903. (e) Gurjar, M. K.; Mainkar, A. S.; Syamala, M. Tetrahedron: Asymmetry 1993, 4, 2343.
122. For examples of doubly diastereoselective asymmetric dihydroxylations of monosubstituted olefins, see (a) Ireland, R. E.; Wipf, P.; Roper, T. D. J. Org. Chem. 1990, 55, 2284. (b) Jirousek, M. R.; Cheung, A. W.-H.; Babine, R. E.; Sass, P. M.; Schow, S. R.; Wick, M. M. Tetrahedron Lett. 1993, 34, 3671. (c) Sinha, S. C.; Keinan, E. J. Org. Chem. 1994, 59, 949. (d) Hoffmann, R. W.; Schlapbach, A. Tetrahedron Lett. 1993, 34, 7903. (e) Gurjar, M. K.; Mainkar, A. S.; Syamala, M. Tetrahedron: Asymmetry 1993, 4, 2343.
123. For examples of doubly diastereoselective asymmetric dihydroxylations of monosubstituted olefins, see (a) Ireland, R. E.; Wipf, P.; Roper, T. D. J. Org. Chem. 1990, 55, 2284. (b) Jirousek, M. R.; Cheung, A. W.-H.; Babine, R. E.; Sass, P. M.; Schow, S. R.; Wick, M. M. Tetrahedron Lett. 1993, 34, 3671. (c) Sinha, S. C.; Keinan, E. J. Org. Chem. 1994, 59, 949. (d) Hoffmann, R. W.; Schlapbach, A. Tetrahedron Lett. 1993, 34, 7903. (e) Gurjar, M. K.; Mainkar, A. S.; Syamala, M. Tetrahedron: Asymmetry 1993, 4, 2343.
124. For examples of doubly diastereoselective asymmetric dihydroxylations of monosubstituted olefins, see (a) Ireland, R. E.; Wipf, P.; Roper, T. D. J. Org. Chem. 1990, 55, 2284. (b) Jirousek, M. R.; Cheung, A. W.-H.; Babine, R. E.; Sass, P. M.; Schow, S. R.; Wick, M. M. Tetrahedron Lett. 1993, 34, 3671. (c) Sinha, S. C.; Keinan, E. J. Org. Chem. 1994, 59, 949. (d) Hoffmann, R. W.; Schlapbach, A. Tetrahedron Lett. 1993, 34, 7903. (e) Gurjar, M. K.; Mainkar, A. S.; Syamala, M. Tetrahedron: Asymmetry 1993, 4, 2343.
125. For examples of doubly diastereoselective asymmetric dihydroxylations of monosubstituted olefins, see (a) Ireland, R. E.; Wipf, P.; Roper, T. D. J. Org. Chem. 1990, 55, 2284. (b) Jirousek, M. R.; Cheung, A. W.-H.; Babine, R. E.; Sass, P. M.; Schow, S. R.; Wick, M. M. Tetrahedron Lett. 1993, 34, 3671. (c) Sinha, S. C.; Keinan, E. J. Org. Chem. 1994, 59, 949. (d) Hoffmann, R. W.; Schlapbach, A. Tetrahedron Lett. 1993, 34, 7903. (e) Gurjar, M. K.; Mainkar, A. S.; Syamala, M. Tetrahedron: Asymmetry 1993, 4, 2343.
126. Wade, P. A.; Cole, D. T.; D'Ambrosio, S. G. Tetrahedron Lett. 1994, 35, 53.
127. Experiments in this laboratory have determined that it is possible to carry out the AD at room temperature if the amounts of ligand and potassium osmate are increased to 5 mol % and 1 mol %, respectively. We commonly refer to this as super AD-mix and have found that these revised concentrations and reaction temperatures do not adversely affect enantioselectivity.
128. Morikawa, K.; Sharpless, K. B. Tetrahedron Lett. 1993, 34, 5575.
129. 71a,b model for heteroatom-directed osmylation of olefins.
130. Kim, N.-S.; Choi, J.-R.; Cha, J. K. J. Org. Chem. 1993, 58, 7096.
131. Katsuki, T.; Sharpless, K. B. J. Am. Chem. Soc. 1980, 102, 5974.
132. For several recently published syntheses of castanospermine, see ref 79, footnote 5.
133. For an additional application of the AD in efforts directed toward the synthesis of indolizidines related to castanospermine and swainsonine, see ref 74b.
134. Abedel-Rahman, H.; Adams, J. P.; Boyes, A. L.; Kelly, M. J.; Mansfield, D. J.; Procopiou, P. A.; Roberts, S. M.; Slee, D. H.; Sidebottom, P. J.; Sik, V.; Watson, N. S. J. Chem. Soc., Chem. Commun. 1993, 1841.
135. Brimacombe, J. S.; McDonald, G.; Abdur Rahman, M. Carbohydr. Res. 1990, 205, 422.
136. The AD has also been used for the preparation of other higher carbon sugars. See ref 74e.
137. (a) Takatsuto, S.; Yazawa, N.; Ikekawa, N.; Morishita, T.; Abe, H. Phytochemistry 1983, 22, 1393.
138. (b) Takatsuto, S.; Yazawa, N.; Ikekawa, N.; Takematsu, T.; Takeuchi, Y.; Koguchi, M. Phytochemistry 1983, 22, 2437.
139. (a) Thompson, M. J.; Meudt, W. J.; Mandava, N.; Dutky, S. R.; Lusby, W. R.; Spauding, D. W. Steroids 1981, 38, 567.
140. (b) Thompson, M. J.; Mandava, N.; Meudt, W. J.; Lusby, W. R.; Spauding, D. W. Steroids 1982, 39, 89.
141. Zhou, W.-S.; Huang, L.-F.; Sun, L.-Q.; Pan, X.-F. Tetrahedron Lett. 1991, 32, 6745.
142. Sun, L.-Q.; Zhou, W.-S.; Pan, X.-F. Tetrahedron: Asymmetry 1991, 2, 973.
143. (a) Takatsuto, S.; Ikekawa, N. Chem. Pharm. Bull. 1984, 32, 2001.
144. (b) Ikekawa, N.; Zhao, Y.-J. In Brassinosteroids: Chemistry, Bioactivity, and Applications; Cutler, H. G., Yokota, T., Adam, G., Eds.; ACS Symposium Series 474; American Chemical Society: Washington, DC, 1990; Chapter 24, p 280.
145. 19,70,116b
146. McMorris, T. C.; Patil, P. A. J. Org. Chem. 1993, 58, 2338.
147. Honda, T.; Takada, H.; Miki, S.; Tsubuki, M. Tetrahedron Lett. 1993, 34, 8275.
148. For additional applications of double asymmetric dihydroxylations of steroidal olefins, see: Brosa, C.; Peracaula, R.; Puig, R.; Ventura, M. Tetrahedron Lett. 1992, 33, 7057 and ref 88.
149. (a) Ikekawa, N.; Fujimoto, Y. Personal communication.
150. (b) Morikawa, K.; Sharpless, K. B. Unpublished results.
151. Ikekawa, N.; Ishizuka, S. In Molecular Structure and Biological Activity of Steroids; Bohl, M., Duax, W. L., Eds.; CRC Press: Boca Raton, 1992; p 293.
152. VanNieuwenhze, M. S.; Sharpless, K. B. J. Am. Chem. Soc. 1993, 115, 7864.
153. This result is very curious since it would only be expected in cases where the substrate shows no intrinsic diastereofacial bias.
154. Hoffmann, R. W.; Schlapbach, A. Tetrahedron Lett. 1993, 34, 7903.
155. Rickards, R. W.; Thomas, R. D. Tetrahedron Lett. 1993, 34, 8369.
156. Barvian, M. R.; Greenberg, M. M. J. Org. Chem. 1993, 58, 6151.
157. (a) Finn, M. G.; Sharpless, K. B. In Asymmetric Synthesis; Morrison, J. D., Ed.; Academic Press: New York, 1985; Vol. 5, p 247.
158. (b) Martin, V. S.; Woodard, S. S.; Katsuki, T.; Yamada, Y.; Ikeda, M.; Sharpless, K. B. J. Am. Chem. Soc. 1981, 103, 6237.
159. Reviews of kinetic resolution: (a) Kagan, H. B.; Fiaud, J. C. Top. Stereochem. 1988, 18, 249. (b) El-Baba, S.; Nuzillard, J. M.; Poulin, J. C.; Kagan, H. B. Tetrahedron 1986, 42, 3851. (c) Chen, C.-S.; Sih, C. J. Angew. Chem., Int. Ed. Engl. 1989, 28, 695.
160. Reviews of kinetic resolution: (a) Kagan, H. B.; Fiaud, J. C. Top. Stereochem. 1988, 18, 249. (b) El-Baba, S.; Nuzillard, J. M.; Poulin, J. C.; Kagan, H. B. Tetrahedron 1986, 42, 3851. (c) Chen, C.-S.; Sih, C. J. Angew. Chem., Int. Ed. Engl. 1989, 28, 695.
161. Reviews of kinetic resolution: (a) Kagan, H. B.; Fiaud, J. C. Top. Stereochem. 1988, 18, 249. (b) El-Baba, S.; Nuzillard, J. M.; Poulin, J. C.; Kagan, H. B. Tetrahedron 1986, 42, 3851. (c) Chen, C.-S.; Sih, C. J. Angew. Chem., Int. Ed. Engl. 1989, 28, 695.
162. Hawkins, J. M.; Meyer, A. Science 1993, 260, 1918.
163. The enantiomeric excess reported at 95% conversion was >97%. This suggests the ratio of the relative rate constants to be ≈3.
164. Scheme 19 only shows results for benzylidene derivative 42. Experiments with ester 43 showed a much greater preference for axial dihydroxylation (i.e.; a single dihydroxylation product was isolated) in the presence of a chiral ligand. This is likely a result of the lower intrinsic diastereofacial preference of 43 as compared to 42.
165. Kakiuchi, K.; Park, J.; Soler, M.; Vanhessche, K.; VanNieuwenhze, M. Unpublished results.
166. s of 14.9.
167. s). Knowledge of any two of the reaction variables allows calculation of the third.
168. Balavoine, G.; Moradpour, A.; Kagan, H. B. J. Am. Chem. Soc. 1974, 96, 5152.
169. Lohray, B. B.; Bhushan, V. Tetrahedron Lett. 1993, 34, 3911.
170. s): 1 (2.9), 2 (5.2), 3 (4.1), 4 (10.7), 5 (9.8), 6 (2.8), 7 (3.3), 8 (3.8), 9 (2.9), 10 (4.2), 11 (1.3), 12 (1.3).
171. The presence of Fe(III) can be easily detected by carrying out a spot test with an aqueous solution of Fe(II). See: (a) Brown, D. B., Ed. Mixed Valence Compounds; Reidel, Dordrecht, 1980. (b) Ogura, K.; Takamagari, K. J. Chem. Soc., Dalton Trans. 1986, 1519.
172. The presence of Fe(III) can be easily detected by carrying out a spot test with an aqueous solution of Fe(II). See: (a) Brown, D. B., Ed. Mixed Valence Compounds; Reidel, Dordrecht, 1980. (b) Ogura, K.; Takamagari, K. J. Chem. Soc., Dalton Trans. 1986, 1519.
173. For an additional citation of the AD in a kinetic resolution application, see: Ward, R. A.; Procter, G. Tetrahedron Lett. 1992, 33, 3363.
174. Park, C. Y.; Kim, B. M.; Sharpless, K. B. Tetrahedron Lett. 1991, 32, 1003.
175. (a) Xu, D.; Crispino, G. A.; Sharpless, K. B. J. Am. Chem. Soc. 1992, 114, 7570.
176. (b) Park, C. Y. Ph.D. Thesis, Massachusetts Institute of Technology, 1991.
177. (c) For additional discussion of the AD with respect to the possible role of hydrogen bonds and their effect on reaction rates and stereoselectivities, see section 2.5 and references cited therein,
178. 4 proceeded with only 3:1 diastereoselectivity in favor of the anti diastereomer.
179. Becker, H. J.; Soler, M.; Sharpless, K. B. Tetrahedron, in press.
180. Vanhessche, K. P. M.; Sharpless, K. B. Unpublished results.
181. (a) Krabbenhoft, H. O. J. Org. Chem. 1979, 44, 4285.
182. (b) Garbisch, E. W., Jr. J. Org. Chem. 1965, 30, 2109.
183. Crispino, G. A.; Sharpless, K. B. Tetrahedron Lett. 1992, 33, 4273.
184. Crispino, G. A.; Sharpless, K. B. Synthesis 1993, 777.
185. Vidari, G.; Giori, A.; Dapiaggi, A.; Lanfranchi, G. Tetrahedron Lett. 1993, 34, 6925.
186. Sinha, S. C.; Sinha-Bagchi, A.; Keinan, E. J. Org. Chem. 1993, 58, 7789.
187. Corey, E. J.; Noe, M. C.; Shieh, W.-C. Tetrahedron Lett. 1993, 34, 5995.
188. Andersson, P. G.; Sharpless, K. B. J. Am. Chem. Soc. 1993, 115, 7047.
189. Vidari, G.; Dapiaggi, A.; Zanoni, G.; Garlaschelli, L. Tetrahedron Lett. 1993, 34, 6485.
190. Wang, Z.-M.; Kakiuchi, K.; Sharpless, K. B. J. Org. Chem., in press.
191. (a) Takano, S.; Yoshimitsu, T.; Ogasawara, K. J. Org. Chem. 1994, 59, 54.
192. (b) Takano, S. Personal communication.
193. Jeong, K.-S.; Sjö, P.; Sharpless, K. B. Tetrahedron Lett. 1992, 33, 3833.
194. Bassignani, L.; Brandt, A.; Caciagli, V.; Re, L. J. Org. Chem. 1978, 43, 4245.
195. Tani, K.; Sato, Y.; Okamoto, S.; Sato, F. Tetrahedron Lett. 1993, 34, 4975.
196. For a recent review of substrate-directed reactions, see: Hoveyda, A. H.; Evans, D. A.; Fu, G. C. Chem. Rev. 1993, 93, 1307.
197. (a) Hauser, F. M.; Ellenberger, S. R.; Clardy, J. C.; Bass, L. S. J. Am. Chem. Soc. 1984, 106, 2458.
198. (b) Solladie, G.; Fréchou, C.; Demailly, G. Tetrahedron Lett. 1986, 27, 2867.
199. (c) Solladie, G.; Fréchou, C.; Hutt, J.; Demailly, G. Bull. Soc. Chim. Fr. 1987, 827.
200. (a) Johnson, C. R. Pure Appl. Chem. 1987, 59, 969.
201. (b) Johnson, C. R.; Barbachyn, M. R.; Meanwell, N. A.; Stark, C. J., Jr.; Zeller, J. R. Phosphorus Sulfur 1985, 24, 151.
202. (c) Johnson, C. R.; Barbachyn, M. R. J. Am. Chem. Soc. 1984, 106, 2459.
203. (a) Trost, B. M.; Kuo, G.-H.; Benneche, T. J. Am. Chem. Soc. 1988, 110, 621.
204. (b) Poli, G. Tetrahedron Lett. 1989, 30, 7385.
205. King, S. B.; Ganem, B. J. Am. Chem. Soc. 1991, 113, 5089.
206. Allylic Sulfides and sulfones provide no evidence of heteroatom-assisted dihydroxylation; see: Vedejs, E.; McClure, C. K. J. Am. Chem. Soc. 1986, 108, 1094.
207. Kon, K.; Isoe, S. Tetrahedron Lett. 1980, 21, 3399.
208. Smith, A. B., III; Boschelli, D. J. Org. Chem. 1983, 48, 1217.
209. A steric argument could also account for these results. For the homoallylic alcohol 60 it could be argued that dihydroxylation is occurring from the olefin diastereoface that is anti to the allylic methyl substituent. A similar situation exits for allylic alcohol 61 which has an allylic isopropyl group. In the case of silyl ether 62 preferential dihydroxylation from the convex face may be the result of the greater steric demands of the allylic silyl ether substituent.
210. Xu, D.; Park, C. Y.; Sharpless, K. B. Tetrahedron Lett. 1994, 35, 2495.
211. The directive effect of the allylic hydroxyl group is analogous to that seen in epoxidation of olefins. See, for example: (a) Henbest, H. B.; Wilson, R. A. L. J. Chem. Soc. 1957, 1958. (b) Sharpless, K. B.; Michaelson, R. C. J. Am. Chem. Soc. 1973, 95, 6136.
212. The directive effect of the allylic hydroxyl group is analogous to that seen in epoxidation of olefins. See, for example: (a) Henbest, H. B.; Wilson, R. A. L. J. Chem. Soc. 1957, 1958. (b) Sharpless, K. B.; Michaelson, R. C. J. Am. Chem. Soc. 1973, 95, 6136.
213. Xu, D.; Park, C. Y.; Sharpless, K. B. Unpublished results.
214. VanNieuwenhze, M. S.; Sharpless, K. B. Tetrahedron Lett. 1994, 35, 843.
215. 29
216. VanNieuwenhze, M. S.; Sharpless, K. B. Unpublished results.
217. Replacement of the hydroxyl group by a hydrogen atom would give a nonprochiral olefin and, therefore, a meso diol in the AD reaction.
218. Kolb, H. C.; VanNieuwenhze, M. S.; Sharpless, K. B. Unpublished results.
219. For example, the asymmetric dihydroxylation of trans-cinnamyl alcohol proceeded with 71% ee using DHQD-CLB while the dihydroxylation of the corresponding acetate proceeded with 91% ee. See, for example: (a) ref 141. (b) Lohray, B. B.; Kalantar, T. H.; Kim, B. M.; Park, C. Y.; Shibata, T.; Wai, J. S. M.; Sharpless, K. B. Tetrahedron Lett. 1989, 30, 2041.
220. For example, the asymmetric dihydroxylation of trans-cinnamyl alcohol proceeded with 71% ee using DHQD-CLB while the dihydroxylation of the corresponding acetate proceeded with 91% ee. See, for example: (a) ref 141. (b) Lohray, B. B.; Kalantar, T. H.; Kim, B. M.; Park, C. Y.; Shibata, T.; Wai, J. S. M.; Sharpless, K. B. Tetrahedron Lett. 1989, 30, 2041.
221. Hanessian, S. Total Synthesis of Natural Products: The "Chiron" Approach; Pergamon Press: Oxford, 1983.
222. For a recent review of protecting groups and their use for the differentiation of the hydroxyl groups of diols, see: Kunz, H.; Waldmann, H. Protecting Groups. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Ed.; Pergamon Press: New York, 1991; Vol. 6, pp 631-701.
223. For a recent review of acylation reactions, including the regioselective mono-acylation of polyols, see: Mulzer, J. Synthesis of Esters, Activated Esters and Lactones. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon Press: New York, 1991; Vol. 6, pp 323-380.
224. Fleming, P. R.; Sharpless, K. B. J. Org. Chem. 1991, 56, 2869.
225. (a) Denis, J.-N.; Correa, A.; Greene, A. E. J. Org. Chem. 1990, 55, 1957.
226. (b) Watson, K. G.; Fung, Y. M.; Gredley, M.; Bird, G. J.; Jackson, W. R.; Gountzos, H.; Matthews, B. R. J. Chem. Soc., Chem. Commun. 1990, 1018.
227. A recent study with methyl and ethyl arenesulfonates has shown that the methanolysis and aminolysis rate constants are ≥ 10 times larger with nosylates than with tosylates, see (a) Lee, I.; Choi, Y. H.; Rhyu, K. W.; Shim, C. S. J. Chem. Soc., Perkin Trans. 2 1989, 1881. For kinetic studies of the reaction of isopropyl arenesulfonates with various nucleophiles, see (b) Oh, H. K.; Kwon, Y. B.; Lee, I. J. Phys. Org. Chem. 1993, 6, 357. (c) Dietze, P. E.; Hariri, R.; Khattak, J. J. Org. Chem. 1989, 54, 3317. (d) Jacobsen, B. M.; Lewis, E. S. J. Org. Chem. 1988, 53, 446. For a review of some synthetic transformations using nosyloxy groups, see: (e) Hoffman, R. V. Tetrahedron 1991, 47, 1109. For the preparation of α-amino acids via α-nosyloxy acids, see (f) Hoffman, R. V.; Kim, H.-O. Tetrahedron 1992, 48, 3007 and references cited therein.
228. A recent study with methyl and ethyl arenesulfonates has shown that the methanolysis and aminolysis rate constants are ≥ 10 times larger with nosylates than with tosylates, see (a) Lee, I.; Choi, Y. H.; Rhyu, K. W.; Shim, C. S. J. Chem. Soc., Perkin Trans. 2 1989, 1881. For kinetic studies of the reaction of isopropyl arenesulfonates with various nucleophiles, see (b) Oh, H. K.; Kwon, Y. B.; Lee, I. J. Phys. Org. Chem. 1993, 6, 357. (c) Dietze, P. E.; Hariri, R.; Khattak, J. J. Org. Chem. 1989, 54, 3317. (d) Jacobsen, B. M.; Lewis, E. S. J. Org. Chem. 1988, 53, 446. For a review of some synthetic transformations using nosyloxy groups, see: (e) Hoffman, R. V. Tetrahedron 1991, 47, 1109. For the preparation of α-amino acids via α-nosyloxy acids, see (f) Hoffman, R. V.; Kim, H.-O. Tetrahedron 1992, 48, 3007 and references cited therein.
229. A recent study with methyl and ethyl arenesulfonates has shown that the methanolysis and aminolysis rate constants are ≥ 10 times larger with nosylates than with tosylates, see (a) Lee, I.; Choi, Y. H.; Rhyu, K. W.; Shim, C. S. J. Chem. Soc., Perkin Trans. 2 1989, 1881. For kinetic studies of the reaction of isopropyl arenesulfonates with various nucleophiles, see (b) Oh, H. K.; Kwon, Y. B.; Lee, I. J. Phys. Org. Chem. 1993, 6, 357. (c) Dietze, P. E.; Hariri, R.; Khattak, J. J. Org. Chem. 1989, 54, 3317. (d) Jacobsen, B. M.; Lewis, E. S. J. Org. Chem. 1988, 53, 446. For a review of some synthetic transformations using nosyloxy groups, see: (e) Hoffman, R. V. Tetrahedron 1991, 47, 1109. For the preparation of α-amino acids via α-nosyloxy acids, see (f) Hoffman, R. V.; Kim, H.-O. Tetrahedron 1992, 48, 3007 and references cited therein.
230. A recent study with methyl and ethyl arenesulfonates has shown that the methanolysis and aminolysis rate constants are ≥ 10 times larger with nosylates than with tosylates, see (a) Lee, I.; Choi, Y. H.; Rhyu, K. W.; Shim, C. S. J. Chem. Soc., Perkin Trans. 2 1989, 1881. For kinetic studies of the reaction of isopropyl arenesulfonates with various nucleophiles, see (b) Oh, H. K.; Kwon, Y. B.; Lee, I. J. Phys. Org. Chem. 1993, 6, 357. (c) Dietze, P. E.; Hariri, R.; Khattak, J. J. Org. Chem. 1989, 54, 3317. (d) Jacobsen, B. M.; Lewis, E. S. J. Org. Chem. 1988, 53, 446. For a review of some synthetic transformations using nosyloxy groups, see: (e) Hoffman, R. V. Tetrahedron 1991, 47, 1109. For the preparation of α-amino acids via α-nosyloxy acids, see (f) Hoffman, R. V.; Kim, H.-O. Tetrahedron 1992, 48, 3007 and references cited therein.
231. A recent study with methyl and ethyl arenesulfonates has shown that the methanolysis and aminolysis rate constants are ≥ 10 times larger with nosylates than with tosylates, see (a) Lee, I.; Choi, Y. H.; Rhyu, K. W.; Shim, C. S. J. Chem. Soc., Perkin Trans. 2 1989, 1881. For kinetic studies of the reaction of isopropyl arenesulfonates with various nucleophiles, see (b) Oh, H. K.; Kwon, Y. B.; Lee, I. J. Phys. Org. Chem. 1993, 6, 357. (c) Dietze, P. E.; Hariri, R.; Khattak, J. J. Org. Chem. 1989, 54, 3317. (d) Jacobsen, B. M.; Lewis, E. S. J. Org. Chem. 1988, 53, 446. For a review of some synthetic transformations using nosyloxy groups, see: (e) Hoffman, R. V. Tetrahedron 1991, 47, 1109. For the preparation of α-amino acids via α-nosyloxy acids, see (f) Hoffman, R. V.; Kim, H.-O. Tetrahedron 1992, 48, 3007 and references cited therein.
232. A recent study with methyl and ethyl arenesulfonates has shown that the methanolysis and aminolysis rate constants are ≥ 10 times larger with nosylates than with tosylates, see (a) Lee, I.; Choi, Y. H.; Rhyu, K. W.; Shim, C. S. J. Chem. Soc., Perkin Trans. 2 1989, 1881. For kinetic studies of the reaction of isopropyl arenesulfonates with various nucleophiles, see (b) Oh, H. K.; Kwon, Y. B.; Lee, I. J. Phys. Org. Chem. 1993, 6, 357. (c) Dietze, P. E.; Hariri, R.; Khattak, J. J. Org. Chem. 1989, 54, 3317. (d) Jacobsen, B. M.; Lewis, E. S. J. Org. Chem. 1988, 53, 446. For a review of some synthetic transformations using nosyloxy groups, see: (e) Hoffman, R. V. Tetrahedron 1991, 47, 1109. For the preparation of α-amino acids via α-nosyloxy acids, see (f) Hoffman, R. V.; Kim, H.-O. Tetrahedron 1992, 48, 3007 and references cited therein.
233. Kolb, H. C.; Sharpless, K. B. Unpublished results.
234. (a) Creasey, S. E.; Guthrie, R. D. J. Chem. Soc., Perkin Trans. 1 1974, 1373.
235. (b) For synthetic applications of mesitylene-sulfonates, see for example: (b) Kocienski, P. J.; Yeates, C.; Street, S. D. A.; Campbell, S. F. J. Chem. Soc., Perkin Trans, 1 1987, 2183.
236. (c) Tadano, K.-I.; Iimura, Y.; Ohmori, T.; Ueno, Y.; Suami, T. J. Carbohydr. Chem. 1986, 5, 423.
237. For synthetic applications of 2,4,6-triisopropylbenzenesulfonates, see for example: (d) Knapp, S.; Lal, G. S.; Sahai, D. J. Org. Chem. 1986, 51, 380. (e) Behling, J.; Farid, P.; Medich, J. R.; Scaros, M. G.; Prunier, M.; Weier, R. M.; Khanna, I. Synth. Commun. 1991, 21, 1383. (f) Prasit, P.; Rokach, J. J. Org. Chem. 1988, 53, 4421. (g) Hanessian, S.; Sahoo, S. P.; Botta, M. Tetrahedron Lett. 1987, 28, 1147. (h) Hanessian, S.; Murray, P. J. Can. J. Chem. 1986, 64, 2231.
238. For synthetic applications of 2,4,6-triisopropylbenzenesulfonates, see for example: (d) Knapp, S.; Lal, G. S.; Sahai, D. J. Org. Chem. 1986, 51, 380. (e) Behling, J.; Farid, P.; Medich, J. R.; Scaros, M. G.; Prunier, M.; Weier, R. M.; Khanna, I. Synth. Commun. 1991, 21, 1383. (f) Prasit, P.; Rokach, J. J. Org. Chem. 1988, 53, 4421. (g) Hanessian, S.; Sahoo, S. P.; Botta, M. Tetrahedron Lett. 1987, 28, 1147. (h) Hanessian, S.; Murray, P. J. Can. J. Chem. 1986, 64, 2231.
239. For synthetic applications of 2,4,6-triisopropylbenzenesulfonates, see for example: (d) Knapp, S.; Lal, G. S.; Sahai, D. J. Org. Chem. 1986, 51, 380. (e) Behling, J.; Farid, P.; Medich, J. R.; Scaros, M. G.; Prunier, M.; Weier, R. M.; Khanna, I. Synth. Commun. 1991, 21, 1383. (f) Prasit, P.; Rokach, J. J. Org. Chem. 1988, 53, 4421. (g) Hanessian, S.; Sahoo, S. P.; Botta, M. Tetrahedron Lett. 1987, 28, 1147. (h) Hanessian, S.; Murray, P. J. Can. J. Chem. 1986, 64, 2231.
240. For synthetic applications of 2,4,6-triisopropylbenzenesulfonates, see for example: (d) Knapp, S.; Lal, G. S.; Sahai, D. J. Org. Chem. 1986, 51, 380. (e) Behling, J.; Farid, P.; Medich, J. R.; Scaros, M. G.; Prunier, M.; Weier, R. M.; Khanna, I. Synth. Commun. 1991, 21, 1383. (f) Prasit, P.; Rokach, J. J. Org. Chem. 1988, 53, 4421. (g) Hanessian, S.; Sahoo, S. P.; Botta, M. Tetrahedron Lett. 1987, 28, 1147. (h) Hanessian, S.; Murray, P. J. Can. J. Chem. 1986, 64, 2231.
241. For synthetic applications of 2,4,6-triisopropylbenzenesulfonates, see for example: (d) Knapp, S.; Lal, G. S.; Sahai, D. J. Org. Chem. 1986, 51, 380. (e) Behling, J.; Farid, P.; Medich, J. R.; Scaros, M. G.; Prunier, M.; Weier, R. M.; Khanna, I. Synth. Commun. 1991, 21, 1383. (f) Prasit, P.; Rokach, J. J. Org. Chem. 1988, 53, 4421. (g) Hanessian, S.; Sahoo, S. P.; Botta, M. Tetrahedron Lett. 1987, 28, 1147. (h) Hanessian, S.; Murray, P. J. Can. J. Chem. 1986, 64, 2231.
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283. Enantioselective epoxidation using stoichiometric amounts of chiral reagents, see: (a) Davis, F. A.; Harakal, M. E.; Awad, S. B. J. Am. Chem. Soc. 1983, 105, 3123. (b) Davis, F. A.; Chattopadhyay, S. Tetrahedron Lett. 1986, 27, 5079. (c) Davis, F. A.; Sheppard, A. C. Tetrahedron 1989,45, 5703. (d) Hassine, B.; Gorsane, M.; Geerts-Evrard, F.; Pecher, J.; Martin, R. H.; Castelet, D. Bull. Soc. Chim. Belg. 1986, 95, 547. (e) Schurig, V.; Hintzer, K.; Leyrer, U.; Mark, C.; Pitchen, P.; Kagan, H. B. J. Organomet. Chem. 1989, 370, 81. Catalytic asymmetric epoxidation, see ref 4 for a recent review; also see (f) Zhang, W.; Loebach, J. L.; Wilson, S. R.; Jacobsen, E. N. J. Am. Chem. Soc. 1990, 112, 2801. (g) Zhang, W.; Jacobsen, E. N. J. Org. Chem. 1991, 56, 2296. (h) Jacobsen, E. N.; Zhang, W.; Güler, M. L. J. Am. Chem. Soc. 1991, 113, 6703. (i) Jacobsen, E. N.; Zhang, W.; Muci, A. R.; Ecker, J. R.; Deng, L. J. Am. Chem. Soc. 1991, 113, 7063. (j) Chang, S.; Heid, R. M.; Jacobsen, E. N. Tetrahedron Lett. 1994, 35, 669. (k) Zhang, W.; Lee, N. H.; Jacobsen, E. N. J. Am. Chem. Soc. 1994, 116, 425. (l) Larrow, J. F.; Jacobsen, E. N.; Gao, Y.; Hong, Y.; Nie, X.; Zepp, C. M. J. Org. Chem. 1994, 59, 1939. (m) Irie, R.; Noda, K.; Ito, Y.; Matsumoto, N.; Katsuki, T. Tetrahedron Lett. 1990, 31, 7345. (n) Irie, R.; Noda, K.; Ito, Y.; Katsuki, T. Tetrahedron Lett. 1991, 32, 1055. (o) Irie, R.; Noda, K.; Ito, Y.; Matsumoto, N.; Katsuki, T. Tetrahedron: Asymmetry 1991, 2, 481. (p) Groves, J. T.; Viski, P. J. Org. Chem. 1990, 55, 3628. (q) Naruta, Y.; Tani, F.; Maruyama, K. Chem. Lett. 1989, 1269. (r) O'Malley, S.; Kodadek, T. J. Am. Chem. Soc. 1989, 111, 9116.
284. Enantioselective epoxidation using stoichiometric amounts of chiral reagents, see: (a) Davis, F. A.; Harakal, M. E.; Awad, S. B. J. Am. Chem. Soc. 1983, 105, 3123. (b) Davis, F. A.; Chattopadhyay, S. Tetrahedron Lett. 1986, 27, 5079. (c) Davis, F. A.; Sheppard, A. C. Tetrahedron 1989,45, 5703. (d) Hassine, B.; Gorsane, M.; Geerts-Evrard, F.; Pecher, J.; Martin, R. H.; Castelet, D. Bull. Soc. Chim. Belg. 1986, 95, 547. (e) Schurig, V.; Hintzer, K.; Leyrer, U.; Mark, C.; Pitchen, P.; Kagan, H. B. J. Organomet. Chem. 1989, 370, 81. Catalytic asymmetric epoxidation, see ref 4 for a recent review; also see (f) Zhang, W.; Loebach, J. L.; Wilson, S. R.; Jacobsen, E. N. J. Am. Chem. Soc. 1990, 112, 2801. (g) Zhang, W.; Jacobsen, E. N. J. Org. Chem. 1991, 56, 2296. (h) Jacobsen, E. N.; Zhang, W.; Güler, M. L. J. Am. Chem. Soc. 1991, 113, 6703. (i) Jacobsen, E. N.; Zhang, W.; Muci, A. R.; Ecker, J. R.; Deng, L. J. Am. Chem. Soc. 1991, 113, 7063. (j) Chang, S.; Heid, R. M.; Jacobsen, E. N. Tetrahedron Lett. 1994, 35, 669. (k) Zhang, W.; Lee, N. H.; Jacobsen, E. N. J. Am. Chem. Soc. 1994, 116, 425. (l) Larrow, J. F.; Jacobsen, E. N.; Gao, Y.; Hong, Y.; Nie, X.; Zepp, C. M. J. Org. Chem. 1994, 59, 1939. (m) Irie, R.; Noda, K.; Ito, Y.; Matsumoto, N.; Katsuki, T. Tetrahedron Lett. 1990, 31, 7345. (n) Irie, R.; Noda, K.; Ito, Y.; Katsuki, T. Tetrahedron Lett. 1991, 32, 1055. (o) Irie, R.; Noda, K.; Ito, Y.; Matsumoto, N.; Katsuki, T. Tetrahedron: Asymmetry 1991, 2, 481. (p) Groves, J. T.; Viski, P. J. Org. Chem. 1990, 55, 3628. (q) Naruta, Y.; Tani, F.; Maruyama, K. Chem. Lett. 1989, 1269. (r) O'Malley, S.; Kodadek, T. J. Am. Chem. Soc. 1989, 111, 9116.
285. Enantioselective epoxidation using stoichiometric amounts of chiral reagents, see: (a) Davis, F. A.; Harakal, M. E.; Awad, S. B. J. Am. Chem. Soc. 1983, 105, 3123. (b) Davis, F. A.; Chattopadhyay, S. Tetrahedron Lett. 1986, 27, 5079. (c) Davis, F. A.; Sheppard, A. C. Tetrahedron 1989,45, 5703. (d) Hassine, B.; Gorsane, M.; Geerts-Evrard, F.; Pecher, J.; Martin, R. H.; Castelet, D. Bull. Soc. Chim. Belg. 1986, 95, 547. (e) Schurig, V.; Hintzer, K.; Leyrer, U.; Mark, C.; Pitchen, P.; Kagan, H. B. J. Organomet. Chem. 1989, 370, 81. Catalytic asymmetric epoxidation, see ref 4 for a recent review; also see (f) Zhang, W.; Loebach, J. L.; Wilson, S. R.; Jacobsen, E. N. J. Am. Chem. Soc. 1990, 112, 2801. (g) Zhang, W.; Jacobsen, E. N. J. Org. Chem. 1991, 56, 2296. (h) Jacobsen, E. N.; Zhang, W.; Güler, M. L. J. Am. Chem. Soc. 1991, 113, 6703. (i) Jacobsen, E. N.; Zhang, W.; Muci, A. R.; Ecker, J. R.; Deng, L. J. Am. Chem. Soc. 1991, 113, 7063. (j) Chang, S.; Heid, R. M.; Jacobsen, E. N. Tetrahedron Lett. 1994, 35, 669. (k) Zhang, W.; Lee, N. H.; Jacobsen, E. N. J. Am. Chem. Soc. 1994, 116, 425. (l) Larrow, J. F.; Jacobsen, E. N.; Gao, Y.; Hong, Y.; Nie, X.; Zepp, C. M. J. Org. Chem. 1994, 59, 1939. (m) Irie, R.; Noda, K.; Ito, Y.; Matsumoto, N.; Katsuki, T. Tetrahedron Lett. 1990, 31, 7345. (n) Irie, R.; Noda, K.; Ito, Y.; Katsuki, T. Tetrahedron Lett. 1991, 32, 1055. (o) Irie, R.; Noda, K.; Ito, Y.; Matsumoto, N.; Katsuki, T. Tetrahedron: Asymmetry 1991, 2, 481. (p) Groves, J. T.; Viski, P. J. Org. Chem. 1990, 55, 3628. (q) Naruta, Y.; Tani, F.; Maruyama, K. Chem. Lett. 1989, 1269. (r) O'Malley, S.; Kodadek, T. J. Am. Chem. Soc. 1989, 111, 9116.
286. Enantioselective epoxidation using stoichiometric amounts of chiral reagents, see: (a) Davis, F. A.; Harakal, M. E.; Awad, S. B. J. Am. Chem. Soc. 1983, 105, 3123. (b) Davis, F. A.; Chattopadhyay, S. Tetrahedron Lett. 1986, 27, 5079. (c) Davis, F. A.; Sheppard, A. C. Tetrahedron 1989,45, 5703. (d) Hassine, B.; Gorsane, M.; Geerts-Evrard, F.; Pecher, J.; Martin, R. H.; Castelet, D. Bull. Soc. Chim. Belg. 1986, 95, 547. (e) Schurig, V.; Hintzer, K.; Leyrer, U.; Mark, C.; Pitchen, P.; Kagan, H. B. J. Organomet. Chem. 1989, 370, 81. Catalytic asymmetric epoxidation, see ref 4 for a recent review; also see (f) Zhang, W.; Loebach, J. L.; Wilson, S. R.; Jacobsen, E. N. J. Am. Chem. Soc. 1990, 112, 2801. (g) Zhang, W.; Jacobsen, E. N. J. Org. Chem. 1991, 56, 2296. (h) Jacobsen, E. N.; Zhang, W.; Güler, M. L. J. Am. Chem. Soc. 1991, 113, 6703. (i) Jacobsen, E. N.; Zhang, W.; Muci, A. R.; Ecker, J. R.; Deng, L. J. Am. Chem. Soc. 1991, 113, 7063. (j) Chang, S.; Heid, R. M.; Jacobsen, E. N. Tetrahedron Lett. 1994, 35, 669. (k) Zhang, W.; Lee, N. H.; Jacobsen, E. N. J. Am. Chem. Soc. 1994, 116, 425. (l) Larrow, J. F.; Jacobsen, E. N.; Gao, Y.; Hong, Y.; Nie, X.; Zepp, C. M. J. Org. Chem. 1994, 59, 1939. (m) Irie, R.; Noda, K.; Ito, Y.; Matsumoto, N.; Katsuki, T. Tetrahedron Lett. 1990, 31, 7345. (n) Irie, R.; Noda, K.; Ito, Y.; Katsuki, T. Tetrahedron Lett. 1991, 32, 1055. (o) Irie, R.; Noda, K.; Ito, Y.; Matsumoto, N.; Katsuki, T. Tetrahedron: Asymmetry 1991, 2, 481. (p) Groves, J. T.; Viski, P. J. Org. Chem. 1990, 55, 3628. (q) Naruta, Y.; Tani, F.; Maruyama, K. Chem. Lett. 1989, 1269. (r) O'Malley, S.; Kodadek, T. J. Am. Chem. Soc. 1989, 111, 9116.
287. Enantioselective epoxidation using stoichiometric amounts of chiral reagents, see: (a) Davis, F. A.; Harakal, M. E.; Awad, S. B. J. Am. Chem. Soc. 1983, 105, 3123. (b) Davis, F. A.; Chattopadhyay, S. Tetrahedron Lett. 1986, 27, 5079. (c) Davis, F. A.; Sheppard, A. C. Tetrahedron 1989,45, 5703. (d) Hassine, B.; Gorsane, M.; Geerts-Evrard, F.; Pecher, J.; Martin, R. H.; Castelet, D. Bull. Soc. Chim. Belg. 1986, 95, 547. (e) Schurig, V.; Hintzer, K.; Leyrer, U.; Mark, C.; Pitchen, P.; Kagan, H. B. J. Organomet. Chem. 1989, 370, 81. Catalytic asymmetric epoxidation, see ref 4 for a recent review; also see (f) Zhang, W.; Loebach, J. L.; Wilson, S. R.; Jacobsen, E. N. J. Am. Chem. Soc. 1990, 112, 2801. (g) Zhang, W.; Jacobsen, E. N. J. Org. Chem. 1991, 56, 2296. (h) Jacobsen, E. N.; Zhang, W.; Güler, M. L. J. Am. Chem. Soc. 1991, 113, 6703. (i) Jacobsen, E. N.; Zhang, W.; Muci, A. R.; Ecker, J. R.; Deng, L. J. Am. Chem. Soc. 1991, 113, 7063. (j) Chang, S.; Heid, R. M.; Jacobsen, E. N. Tetrahedron Lett. 1994, 35, 669. (k) Zhang, W.; Lee, N. H.; Jacobsen, E. N. J. Am. Chem. Soc. 1994, 116, 425. (l) Larrow, J. F.; Jacobsen, E. N.; Gao, Y.; Hong, Y.; Nie, X.; Zepp, C. M. J. Org. Chem. 1994, 59, 1939. (m) Irie, R.; Noda, K.; Ito, Y.; Matsumoto, N.; Katsuki, T. Tetrahedron Lett. 1990, 31, 7345. (n) Irie, R.; Noda, K.; Ito, Y.; Katsuki, T. Tetrahedron Lett. 1991, 32, 1055. (o) Irie, R.; Noda, K.; Ito, Y.; Matsumoto, N.; Katsuki, T. Tetrahedron: Asymmetry 1991, 2, 481. (p) Groves, J. T.; Viski, P. J. Org. Chem. 1990, 55, 3628. (q) Naruta, Y.; Tani, F.; Maruyama, K. Chem. Lett. 1989, 1269. (r) O'Malley, S.; Kodadek, T. J. Am. Chem. Soc. 1989, 111, 9116.
288. Enantioselective epoxidation using stoichiometric amounts of chiral reagents, see: (a) Davis, F. A.; Harakal, M. E.; Awad, S. B. J. Am. Chem. Soc. 1983, 105, 3123. (b) Davis, F. A.; Chattopadhyay, S. Tetrahedron Lett. 1986, 27, 5079. (c) Davis, F. A.; Sheppard, A. C. Tetrahedron 1989,45, 5703. (d) Hassine, B.; Gorsane, M.; Geerts-Evrard, F.; Pecher, J.; Martin, R. H.; Castelet, D. Bull. Soc. Chim. Belg. 1986, 95, 547. (e) Schurig, V.; Hintzer, K.; Leyrer, U.; Mark, C.; Pitchen, P.; Kagan, H. B. J. Organomet. Chem. 1989, 370, 81. Catalytic asymmetric epoxidation, see ref 4 for a recent review; also see (f) Zhang, W.; Loebach, J. L.; Wilson, S. R.; Jacobsen, E. N. J. Am. Chem. Soc. 1990, 112, 2801. (g) Zhang, W.; Jacobsen, E. N. J. Org. Chem. 1991, 56, 2296. (h) Jacobsen, E. N.; Zhang, W.; Güler, M. L. J. Am. Chem. Soc. 1991, 113, 6703. (i) Jacobsen, E. N.; Zhang, W.; Muci, A. R.; Ecker, J. R.; Deng, L. J. Am. Chem. Soc. 1991, 113, 7063. (j) Chang, S.; Heid, R. M.; Jacobsen, E. N. Tetrahedron Lett. 1994, 35, 669. (k) Zhang, W.; Lee, N. H.; Jacobsen, E. N. J. Am. Chem. Soc. 1994, 116, 425. (l) Larrow, J. F.; Jacobsen, E. N.; Gao, Y.; Hong, Y.; Nie, X.; Zepp, C. M. J. Org. Chem. 1994, 59, 1939. (m) Irie, R.; Noda, K.; Ito, Y.; Matsumoto, N.; Katsuki, T. Tetrahedron Lett. 1990, 31, 7345. (n) Irie, R.; Noda, K.; Ito, Y.; Katsuki, T. Tetrahedron Lett. 1991, 32, 1055. (o) Irie, R.; Noda, K.; Ito, Y.; Matsumoto, N.; Katsuki, T. Tetrahedron: Asymmetry 1991, 2, 481. (p) Groves, J. T.; Viski, P. J. Org. Chem. 1990, 55, 3628. (q) Naruta, Y.; Tani, F.; Maruyama, K. Chem. Lett. 1989, 1269. (r) O'Malley, S.; Kodadek, T. J. Am. Chem. Soc. 1989, 111, 9116.
289. Enantioselective epoxidation using stoichiometric amounts of chiral reagents, see: (a) Davis, F. A.; Harakal, M. E.; Awad, S. B. J. Am. Chem. Soc. 1983, 105, 3123. (b) Davis, F. A.; Chattopadhyay, S. Tetrahedron Lett. 1986, 27, 5079. (c) Davis, F. A.; Sheppard, A. C. Tetrahedron 1989,45, 5703. (d) Hassine, B.; Gorsane, M.; Geerts-Evrard, F.; Pecher, J.; Martin, R. H.; Castelet, D. Bull. Soc. Chim. Belg. 1986, 95, 547. (e) Schurig, V.; Hintzer, K.; Leyrer, U.; Mark, C.; Pitchen, P.; Kagan, H. B. J. Organomet. Chem. 1989, 370, 81. Catalytic asymmetric epoxidation, see ref 4 for a recent review; also see (f) Zhang, W.; Loebach, J. L.; Wilson, S. R.; Jacobsen, E. N. J. Am. Chem. Soc. 1990, 112, 2801. (g) Zhang, W.; Jacobsen, E. N. J. Org. Chem. 1991, 56, 2296. (h) Jacobsen, E. N.; Zhang, W.; Güler, M. L. J. Am. Chem. Soc. 1991, 113, 6703. (i) Jacobsen, E. N.; Zhang, W.; Muci, A. R.; Ecker, J. R.; Deng, L. J. Am. Chem. Soc. 1991, 113, 7063. (j) Chang, S.; Heid, R. M.; Jacobsen, E. N. Tetrahedron Lett. 1994, 35, 669. (k) Zhang, W.; Lee, N. H.; Jacobsen, E. N. J. Am. Chem. Soc. 1994, 116, 425. (l) Larrow, J. F.; Jacobsen, E. N.; Gao, Y.; Hong, Y.; Nie, X.; Zepp, C. M. J. Org. Chem. 1994, 59, 1939. (m) Irie, R.; Noda, K.; Ito, Y.; Matsumoto, N.; Katsuki, T. Tetrahedron Lett. 1990, 31, 7345. (n) Irie, R.; Noda, K.; Ito, Y.; Katsuki, T. Tetrahedron Lett. 1991, 32, 1055. (o) Irie, R.; Noda, K.; Ito, Y.; Matsumoto, N.; Katsuki, T. Tetrahedron: Asymmetry 1991, 2, 481. (p) Groves, J. T.; Viski, P. J. Org. Chem. 1990, 55, 3628. (q) Naruta, Y.; Tani, F.; Maruyama, K. Chem. Lett. 1989, 1269. (r) O'Malley, S.; Kodadek, T. J. Am. Chem. Soc. 1989, 111, 9116.
290. Enantioselective epoxidation using stoichiometric amounts of chiral reagents, see: (a) Davis, F. A.; Harakal, M. E.; Awad, S. B. J. Am. Chem. Soc. 1983, 105, 3123. (b) Davis, F. A.; Chattopadhyay, S. Tetrahedron Lett. 1986, 27, 5079. (c) Davis, F. A.; Sheppard, A. C. Tetrahedron 1989,45, 5703. (d) Hassine, B.; Gorsane, M.; Geerts-Evrard, F.; Pecher, J.; Martin, R. H.; Castelet, D. Bull. Soc. Chim. Belg. 1986, 95, 547. (e) Schurig, V.; Hintzer, K.; Leyrer, U.; Mark, C.; Pitchen, P.; Kagan, H. B. J. Organomet. Chem. 1989, 370, 81. Catalytic asymmetric epoxidation, see ref 4 for a recent review; also see (f) Zhang, W.; Loebach, J. L.; Wilson, S. R.; Jacobsen, E. N. J. Am. Chem. Soc. 1990, 112, 2801. (g) Zhang, W.; Jacobsen, E. N. J. Org. Chem. 1991, 56, 2296. (h) Jacobsen, E. N.; Zhang, W.; Güler, M. L. J. Am. Chem. Soc. 1991, 113, 6703. (i) Jacobsen, E. N.; Zhang, W.; Muci, A. R.; Ecker, J. R.; Deng, L. J. Am. Chem. Soc. 1991, 113, 7063. (j) Chang, S.; Heid, R. M.; Jacobsen, E. N. Tetrahedron Lett. 1994, 35, 669. (k) Zhang, W.; Lee, N. H.; Jacobsen, E. N. J. Am. Chem. Soc. 1994, 116, 425. (l) Larrow, J. F.; Jacobsen, E. N.; Gao, Y.; Hong, Y.; Nie, X.; Zepp, C. M. J. Org. Chem. 1994, 59, 1939. (m) Irie, R.; Noda, K.; Ito, Y.; Matsumoto, N.; Katsuki, T. Tetrahedron Lett. 1990, 31, 7345. (n) Irie, R.; Noda, K.; Ito, Y.; Katsuki, T. Tetrahedron Lett. 1991, 32, 1055. (o) Irie, R.; Noda, K.; Ito, Y.; Matsumoto, N.; Katsuki, T. Tetrahedron: Asymmetry 1991, 2, 481. (p) Groves, J. T.; Viski, P. J. Org. Chem. 1990, 55, 3628. (q) Naruta, Y.; Tani, F.; Maruyama, K. Chem. Lett. 1989, 1269. (r) O'Malley, S.; Kodadek, T. J. Am. Chem. Soc. 1989, 111, 9116.
291. Enantioselective epoxidation using stoichiometric amounts of chiral reagents, see: (a) Davis, F. A.; Harakal, M. E.; Awad, S. B. J. Am. Chem. Soc. 1983, 105, 3123. (b) Davis, F. A.; Chattopadhyay, S. Tetrahedron Lett. 1986, 27, 5079. (c) Davis, F. A.; Sheppard, A. C. Tetrahedron 1989,45, 5703. (d) Hassine, B.; Gorsane, M.; Geerts-Evrard, F.; Pecher, J.; Martin, R. H.; Castelet, D. Bull. Soc. Chim. Belg. 1986, 95, 547. (e) Schurig, V.; Hintzer, K.; Leyrer, U.; Mark, C.; Pitchen, P.; Kagan, H. B. J. Organomet. Chem. 1989, 370, 81. Catalytic asymmetric epoxidation, see ref 4 for a recent review; also see (f) Zhang, W.; Loebach, J. L.; Wilson, S. R.; Jacobsen, E. N. J. Am. Chem. Soc. 1990, 112, 2801. (g) Zhang, W.; Jacobsen, E. N. J. Org. Chem. 1991, 56, 2296. (h) Jacobsen, E. N.; Zhang, W.; Güler, M. L. J. Am. Chem. Soc. 1991, 113, 6703. (i) Jacobsen, E. N.; Zhang, W.; Muci, A. R.; Ecker, J. R.; Deng, L. J. Am. Chem. Soc. 1991, 113, 7063. (j) Chang, S.; Heid, R. M.; Jacobsen, E. N. Tetrahedron Lett. 1994, 35, 669. (k) Zhang, W.; Lee, N. H.; Jacobsen, E. N. J. Am. Chem. Soc. 1994, 116, 425. (l) Larrow, J. F.; Jacobsen, E. N.; Gao, Y.; Hong, Y.; Nie, X.; Zepp, C. M. J. Org. Chem. 1994, 59, 1939. (m) Irie, R.; Noda, K.; Ito, Y.; Matsumoto, N.; Katsuki, T. Tetrahedron Lett. 1990, 31, 7345. (n) Irie, R.; Noda, K.; Ito, Y.; Katsuki, T. Tetrahedron Lett. 1991, 32, 1055. (o) Irie, R.; Noda, K.; Ito, Y.; Matsumoto, N.; Katsuki, T. Tetrahedron: Asymmetry 1991, 2, 481. (p) Groves, J. T.; Viski, P. J. Org. Chem. 1990, 55, 3628. (q) Naruta, Y.; Tani, F.; Maruyama, K. Chem. Lett. 1989, 1269. (r) O'Malley, S.; Kodadek, T. J. Am. Chem. Soc. 1989, 111, 9116.
292. Enantioselective epoxidation using stoichiometric amounts of chiral reagents, see: (a) Davis, F. A.; Harakal, M. E.; Awad, S. B. J. Am. Chem. Soc. 1983, 105, 3123. (b) Davis, F. A.; Chattopadhyay, S. Tetrahedron Lett. 1986, 27, 5079. (c) Davis, F. A.; Sheppard, A. C. Tetrahedron 1989,45, 5703. (d) Hassine, B.; Gorsane, M.; Geerts-Evrard, F.; Pecher, J.; Martin, R. H.; Castelet, D. Bull. Soc. Chim. Belg. 1986, 95, 547. (e) Schurig, V.; Hintzer, K.; Leyrer, U.; Mark, C.; Pitchen, P.; Kagan, H. B. J. Organomet. Chem. 1989, 370, 81. Catalytic asymmetric epoxidation, see ref 4 for a recent review; also see (f) Zhang, W.; Loebach, J. L.; Wilson, S. R.; Jacobsen, E. N. J. Am. Chem. Soc. 1990, 112, 2801. (g) Zhang, W.; Jacobsen, E. N. J. Org. Chem. 1991, 56, 2296. (h) Jacobsen, E. N.; Zhang, W.; Güler, M. L. J. Am. Chem. Soc. 1991, 113, 6703. (i) Jacobsen, E. N.; Zhang, W.; Muci, A. R.; Ecker, J. R.; Deng, L. J. Am. Chem. Soc. 1991, 113, 7063. (j) Chang, S.; Heid, R. M.; Jacobsen, E. N. Tetrahedron Lett. 1994, 35, 669. (k) Zhang, W.; Lee, N. H.; Jacobsen, E. N. J. Am. Chem. Soc. 1994, 116, 425. (l) Larrow, J. F.; Jacobsen, E. N.; Gao, Y.; Hong, Y.; Nie, X.; Zepp, C. M. J. Org. Chem. 1994, 59, 1939. (m) Irie, R.; Noda, K.; Ito, Y.; Matsumoto, N.; Katsuki, T. Tetrahedron Lett. 1990, 31, 7345. (n) Irie, R.; Noda, K.; Ito, Y.; Katsuki, T. Tetrahedron Lett. 1991, 32, 1055. (o) Irie, R.; Noda, K.; Ito, Y.; Matsumoto, N.; Katsuki, T. Tetrahedron: Asymmetry 1991, 2, 481. (p) Groves, J. T.; Viski, P. J. Org. Chem. 1990, 55, 3628. (q) Naruta, Y.; Tani, F.; Maruyama, K. Chem. Lett. 1989, 1269. (r) O'Malley, S.; Kodadek, T. J. Am. Chem. Soc. 1989, 111, 9116.
293. Enantioselective epoxidation using stoichiometric amounts of chiral reagents, see: (a) Davis, F. A.; Harakal, M. E.; Awad, S. B. J. Am. Chem. Soc. 1983, 105, 3123. (b) Davis, F. A.; Chattopadhyay, S. Tetrahedron Lett. 1986, 27, 5079. (c) Davis, F. A.; Sheppard, A. C. Tetrahedron 1989,45, 5703. (d) Hassine, B.; Gorsane, M.; Geerts-Evrard, F.; Pecher, J.; Martin, R. H.; Castelet, D. Bull. Soc. Chim. Belg. 1986, 95, 547. (e) Schurig, V.; Hintzer, K.; Leyrer, U.; Mark, C.; Pitchen, P.; Kagan, H. B. J. Organomet. Chem. 1989, 370, 81. Catalytic asymmetric epoxidation, see ref 4 for a recent review; also see (f) Zhang, W.; Loebach, J. L.; Wilson, S. R.; Jacobsen, E. N. J. Am. Chem. Soc. 1990, 112, 2801. (g) Zhang, W.; Jacobsen, E. N. J. Org. Chem. 1991, 56, 2296. (h) Jacobsen, E. N.; Zhang, W.; Güler, M. L. J. Am. Chem. Soc. 1991, 113, 6703. (i) Jacobsen, E. N.; Zhang, W.; Muci, A. R.; Ecker, J. R.; Deng, L. J. Am. Chem. Soc. 1991, 113, 7063. (j) Chang, S.; Heid, R. M.; Jacobsen, E. N. Tetrahedron Lett. 1994, 35, 669. (k) Zhang, W.; Lee, N. H.; Jacobsen, E. N. J. Am. Chem. Soc. 1994, 116, 425. (l) Larrow, J. F.; Jacobsen, E. N.; Gao, Y.; Hong, Y.; Nie, X.; Zepp, C. M. J. Org. Chem. 1994, 59, 1939. (m) Irie, R.; Noda, K.; Ito, Y.; Matsumoto, N.; Katsuki, T. Tetrahedron Lett. 1990, 31, 7345. (n) Irie, R.; Noda, K.; Ito, Y.; Katsuki, T. Tetrahedron Lett. 1991, 32, 1055. (o) Irie, R.; Noda, K.; Ito, Y.; Matsumoto, N.; Katsuki, T. Tetrahedron: Asymmetry 1991, 2, 481. (p) Groves, J. T.; Viski, P. J. Org. Chem. 1990, 55, 3628. (q) Naruta, Y.; Tani, F.; Maruyama, K. Chem. Lett. 1989, 1269. (r) O'Malley, S.; Kodadek, T. J. Am. Chem. Soc. 1989, 111, 9116.
294. Enantioselective epoxidation using stoichiometric amounts of chiral reagents, see: (a) Davis, F. A.; Harakal, M. E.; Awad, S. B. J. Am. Chem. Soc. 1983, 105, 3123. (b) Davis, F. A.; Chattopadhyay, S. Tetrahedron Lett. 1986, 27, 5079. (c) Davis, F. A.; Sheppard, A. C. Tetrahedron 1989,45, 5703. (d) Hassine, B.; Gorsane, M.; Geerts-Evrard, F.; Pecher, J.; Martin, R. H.; Castelet, D. Bull. Soc. Chim. Belg. 1986, 95, 547. (e) Schurig, V.; Hintzer, K.; Leyrer, U.; Mark, C.; Pitchen, P.; Kagan, H. B. J. Organomet. Chem. 1989, 370, 81. Catalytic asymmetric epoxidation, see ref 4 for a recent review; also see (f) Zhang, W.; Loebach, J. L.; Wilson, S. R.; Jacobsen, E. N. J. Am. Chem. Soc. 1990, 112, 2801. (g) Zhang, W.; Jacobsen, E. N. J. Org. Chem. 1991, 56, 2296. (h) Jacobsen, E. N.; Zhang, W.; Güler, M. L. J. Am. Chem. Soc. 1991, 113, 6703. (i) Jacobsen, E. N.; Zhang, W.; Muci, A. R.; Ecker, J. R.; Deng, L. J. Am. Chem. Soc. 1991, 113, 7063. (j) Chang, S.; Heid, R. M.; Jacobsen, E. N. Tetrahedron Lett. 1994, 35, 669. (k) Zhang, W.; Lee, N. H.; Jacobsen, E. N. J. Am. Chem. Soc. 1994, 116, 425. (l) Larrow, J. F.; Jacobsen, E. N.; Gao, Y.; Hong, Y.; Nie, X.; Zepp, C. M. J. Org. Chem. 1994, 59, 1939. (m) Irie, R.; Noda, K.; Ito, Y.; Matsumoto, N.; Katsuki, T. Tetrahedron Lett. 1990, 31, 7345. (n) Irie, R.; Noda, K.; Ito, Y.; Katsuki, T. Tetrahedron Lett. 1991, 32, 1055. (o) Irie, R.; Noda, K.; Ito, Y.; Matsumoto, N.; Katsuki, T. Tetrahedron: Asymmetry 1991, 2, 481. (p) Groves, J. T.; Viski, P. J. Org. Chem. 1990, 55, 3628. (q) Naruta, Y.; Tani, F.; Maruyama, K. Chem. Lett. 1989, 1269. (r) O'Malley, S.; Kodadek, T. J. Am. Chem. Soc. 1989, 111, 9116.
295. Enantioselective epoxidation using stoichiometric amounts of chiral reagents, see: (a) Davis, F. A.; Harakal, M. E.; Awad, S. B. J. Am. Chem. Soc. 1983, 105, 3123. (b) Davis, F. A.; Chattopadhyay, S. Tetrahedron Lett. 1986, 27, 5079. (c) Davis, F. A.; Sheppard, A. C. Tetrahedron 1989,45, 5703. (d) Hassine, B.; Gorsane, M.; Geerts-Evrard, F.; Pecher, J.; Martin, R. H.; Castelet, D. Bull. Soc. Chim. Belg. 1986, 95, 547. (e) Schurig, V.; Hintzer, K.; Leyrer, U.; Mark, C.; Pitchen, P.; Kagan, H. B. J. Organomet. Chem. 1989, 370, 81. Catalytic asymmetric epoxidation, see ref 4 for a recent review; also see (f) Zhang, W.; Loebach, J. L.; Wilson, S. R.; Jacobsen, E. N. J. Am. Chem. Soc. 1990, 112, 2801. (g) Zhang, W.; Jacobsen, E. N. J. Org. Chem. 1991, 56, 2296. (h) Jacobsen, E. N.; Zhang, W.; Güler, M. L. J. Am. Chem. Soc. 1991, 113, 6703. (i) Jacobsen, E. N.; Zhang, W.; Muci, A. R.; Ecker, J. R.; Deng, L. J. Am. Chem. Soc. 1991, 113, 7063. (j) Chang, S.; Heid, R. M.; Jacobsen, E. N. Tetrahedron Lett. 1994, 35, 669. (k) Zhang, W.; Lee, N. H.; Jacobsen, E. N. J. Am. Chem. Soc. 1994, 116, 425. (l) Larrow, J. F.; Jacobsen, E. N.; Gao, Y.; Hong, Y.; Nie, X.; Zepp, C. M. J. Org. Chem. 1994, 59, 1939. (m) Irie, R.; Noda, K.; Ito, Y.; Matsumoto, N.; Katsuki, T. Tetrahedron Lett. 1990, 31, 7345. (n) Irie, R.; Noda, K.; Ito, Y.; Katsuki, T. Tetrahedron Lett. 1991, 32, 1055. (o) Irie, R.; Noda, K.; Ito, Y.; Matsumoto, N.; Katsuki, T. Tetrahedron: Asymmetry 1991, 2, 481. (p) Groves, J. T.; Viski, P. J. Org. Chem. 1990, 55, 3628. (q) Naruta, Y.; Tani, F.; Maruyama, K. Chem. Lett. 1989, 1269. (r) O'Malley, S.; Kodadek, T. J. Am. Chem. Soc. 1989, 111, 9116.
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459. Several additional cyclic enol ethers were tested. Generally, 5-membered enol ethers did not perform as well as 6-membered enol ethers in the AD. Yields, however, were excellent in all cases.
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461. The enantiomeric purity of 179 could be increased to >95% by recrystallization from tert-butyl methyl ether.
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