First comprehensive bakkane approach: Stereoselective and efficient dichloroketene-based total syntheses of (±)- and (-)-9-acetoxyfukinanolide, (±)- and (+)-bakkenolide a, (-)-bakkenolides III, B, C, H, L, V, and X, (±)- and (-)-homogynolide A, (±)-homogynolide B, and (±)-palmosalide C

Journal of the American Chemical Society

Volumn 124, Issue 51, 2002, Pages 15313-15325

  Brocksom, Timothy J ^a,b   Coelho, Fernando ^a,c   Deprés, Jean Pierre ^a   Greene, Andrew E ^a   Freire de Lima, Marco E ^a,d   Hamelin, Olivier ^a,e   Hartmann, Benoît ^a,f   Kanazawa, Alice M ^a   Wang, Yanyun ^a,g  

^a UNIVERSITÉ JOSEPH FOURIER   (France)

^b FEDERAL UNIVERSITY OF SÃO CARLOS   (Brazil)

^c UNIVERSITY OF CAMPINAS   (Brazil)

^d Rio de Janeiro Federal Rural University   (Brazil)

^e CEA GRENOBLE   (France)

^f BAYER CROPSCIENCE AG   (Germany)

^g UNIVERSITY OF GEORGIA   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ADDITION REACTIONS; CARBOXYLATION; ESTERS; ISOMERS; KETONES; SYNTHESIS (CHEMICAL);

BAKKANE APPROACH;

STEREOCHEMISTRY;

9 ACETOXYFUKINANOLIDE; BAKKANE DERIVATIVE; BAKKENOLIDE A; BAKKENOLIDE B; BAKKENOLIDE C; BAKKENOLIDE H; BAKKENOLIDE III; BAKKENOLIDE L; BAKKENOLIDE V; BAKKENOLIDE X; CYCLOHEXENE DERIVATIVE; DICHLOROKETENE; DIMETHYLCYCLOHEXENE; EPOXIDE; ESTER DERIVATIVE; HOMOGYNOLIDE A; HOMOGYNOLIDE B; KETENE DERIVATIVE; PALMOSALIDE C; UNCLASSIFIED DRUG;

ALDOL REACTION; ARTICLE; CHEMICAL REACTION; CYCLOADDITION; ISOMER; REACTION ANALYSIS; REDUCTION; STEREOCHEMISTRY; TRANSESTERIFICATION;

4-BUTYROLACTONE; CYCLOHEXANES; CYCLOHEXENES; DICHLOROETHYLENES; PETASITES; SESQUITERPENES; STEREOISOMERISM;

EID: 0037176279     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja0208456     Document Type: Article

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85. While the overall yield remained relatively constant (ca. 75%), the ratio varied experimentally from 3:1 to 1:1.
86. See, for example: Bohlmann, F.; Tietze, B.-M. Chem. Ber. 1970, 103, 561-563. Hoskins, W. M.; Crout, D. H. G. J. Chem. Soc., Perkin Trans. 11977, 538-544. Beeby, P. J. Tetrahedron Lett. 1977, 3379-3382. Kubo, A.; Nakahara, S.; Inaba, K.; Kitahara, Y. Chem. Pharm. Bull. 1985, 33, 2582-2584. Kubo, A.; Nakahara, S.; Inaba, K.; Kitahara, Y. Chem. Pharm. Bull. 1986, 34, 4056-4068. Nakayama, J.; Nakamura, Y.; Tajiri, T.; Hoshino, M. Heterocycles 1986, 24, 637-640.Bal-Tembe, S.; Bhedi, D. N.; De Souza, N. J.; Rupp, R. H. Heterocycles 1987, 26, 1239-1249. Dev, V.; Bottini, A. T. J. Nat. Prod. 1987, 50, 968-971. Joseph-Nathan, P.; Cerda, C. M.; Roman, L. U.; Hernandez, J. D. J. Nat. Prod. 1989, 52, 481-496. For relevant studies of the problem of Z → E isomerization during esterification, see: Roush, W. R.; Blizzard, T. A. J. Org. Chem. 1984, 49, 1772-1783 and 4332-4339.
87. See, for example: Bohlmann, F.; Tietze, B.-M. Chem. Ber. 1970, 103, 561-563. Hoskins, W. M.; Crout, D. H. G. J. Chem. Soc., Perkin Trans. 11977, 538-544. Beeby, P. J. Tetrahedron Lett. 1977, 3379-3382. Kubo, A.; Nakahara, S.; Inaba, K.; Kitahara, Y. Chem. Pharm. Bull. 1985, 33, 2582-2584. Kubo, A.; Nakahara, S.; Inaba, K.; Kitahara, Y. Chem. Pharm. Bull. 1986, 34, 4056-4068. Nakayama, J.; Nakamura, Y.; Tajiri, T.; Hoshino, M. Heterocycles 1986, 24, 637-640.Bal-Tembe, S.; Bhedi, D. N.; De Souza, N. J.; Rupp, R. H. Heterocycles 1987, 26, 1239-1249. Dev, V.; Bottini, A. T. J. Nat. Prod. 1987, 50, 968-971. Joseph-Nathan, P.; Cerda, C. M.; Roman, L. U.; Hernandez, J. D. J. Nat. Prod. 1989, 52, 481-496. For relevant studies of the problem of Z → E isomerization during esterification, see: Roush, W. R.; Blizzard, T. A. J. Org. Chem. 1984, 49, 1772-1783 and 4332-4339.
88. See, for example: Bohlmann, F.; Tietze, B.-M. Chem. Ber. 1970, 103, 561-563. Hoskins, W. M.; Crout, D. H. G. J. Chem. Soc., Perkin Trans. 11977, 538-544. Beeby, P. J. Tetrahedron Lett. 1977, 3379-3382. Kubo, A.; Nakahara, S.; Inaba, K.; Kitahara, Y. Chem. Pharm. Bull. 1985, 33, 2582-2584. Kubo, A.; Nakahara, S.; Inaba, K.; Kitahara, Y. Chem. Pharm. Bull. 1986, 34, 4056-4068. Nakayama, J.; Nakamura, Y.; Tajiri, T.; Hoshino, M. Heterocycles 1986, 24, 637-640.Bal-Tembe, S.; Bhedi, D. N.; De Souza, N. J.; Rupp, R. H. Heterocycles 1987, 26, 1239-1249. Dev, V.; Bottini, A. T. J. Nat. Prod. 1987, 50, 968-971. Joseph-Nathan, P.; Cerda, C. M.; Roman, L. U.; Hernandez, J. D. J. Nat. Prod. 1989, 52, 481-496. For relevant studies of the problem of Z → E isomerization during esterification, see: Roush, W. R.; Blizzard, T. A. J. Org. Chem. 1984, 49, 1772-1783 and 4332-4339.
89. See, for example: Bohlmann, F.; Tietze, B.-M. Chem. Ber. 1970, 103, 561-563. Hoskins, W. M.; Crout, D. H. G. J. Chem. Soc., Perkin Trans. 11977, 538-544. Beeby, P. J. Tetrahedron Lett. 1977, 3379-3382. Kubo, A.; Nakahara, S.; Inaba, K.; Kitahara, Y. Chem. Pharm. Bull. 1985, 33, 2582-2584. Kubo, A.; Nakahara, S.; Inaba, K.; Kitahara, Y. Chem. Pharm. Bull. 1986, 34, 4056-4068. Nakayama, J.; Nakamura, Y.; Tajiri, T.; Hoshino, M. Heterocycles 1986, 24, 637-640.Bal-Tembe, S.; Bhedi, D. N.; De Souza, N. J.; Rupp, R. H. Heterocycles 1987, 26, 1239-1249. Dev, V.; Bottini, A. T. J. Nat. Prod. 1987, 50, 968-971. Joseph-Nathan, P.; Cerda, C. M.; Roman, L. U.; Hernandez, J. D. J. Nat. Prod. 1989, 52, 481-496. For relevant studies of the problem of Z → E isomerization during esterification, see: Roush, W. R.; Blizzard, T. A. J. Org. Chem. 1984, 49, 1772-1783 and 4332-4339.
90. See, for example: Bohlmann, F.; Tietze, B.-M. Chem. Ber. 1970, 103, 561-563. Hoskins, W. M.; Crout, D. H. G. J. Chem. Soc., Perkin Trans. 11977, 538-544. Beeby, P. J. Tetrahedron Lett. 1977, 3379-3382. Kubo, A.; Nakahara, S.; Inaba, K.; Kitahara, Y. Chem. Pharm. Bull. 1985, 33, 2582-2584. Kubo, A.; Nakahara, S.; Inaba, K.; Kitahara, Y. Chem. Pharm. Bull. 1986, 34, 4056-4068. Nakayama, J.; Nakamura, Y.; Tajiri, T.; Hoshino, M. Heterocycles 1986, 24, 637-640.Bal-Tembe, S.; Bhedi, D. N.; De Souza, N. J.; Rupp, R. H. Heterocycles 1987, 26, 1239-1249. Dev, V.; Bottini, A. T. J. Nat. Prod. 1987, 50, 968-971. Joseph-Nathan, P.; Cerda, C. M.; Roman, L. U.; Hernandez, J. D. J. Nat. Prod. 1989, 52, 481-496. For relevant studies of the problem of Z → E isomerization during esterification, see: Roush, W. R.; Blizzard, T. A. J. Org. Chem. 1984, 49, 1772-1783 and 4332-4339.
91. See, for example: Bohlmann, F.; Tietze, B.-M. Chem. Ber. 1970, 103, 561-563. Hoskins, W. M.; Crout, D. H. G. J. Chem. Soc., Perkin Trans. 11977, 538-544. Beeby, P. J. Tetrahedron Lett. 1977, 3379-3382. Kubo, A.; Nakahara, S.; Inaba, K.; Kitahara, Y. Chem. Pharm. Bull. 1985, 33, 2582-2584. Kubo, A.; Nakahara, S.; Inaba, K.; Kitahara, Y. Chem. Pharm. Bull. 1986, 34, 4056-4068. Nakayama, J.; Nakamura, Y.; Tajiri, T.; Hoshino, M. Heterocycles 1986, 24, 637-640.Bal-Tembe, S.; Bhedi, D. N.; De Souza, N. J.; Rupp, R. H. Heterocycles 1987, 26, 1239-1249. Dev, V.; Bottini, A. T. J. Nat. Prod. 1987, 50, 968-971. Joseph-Nathan, P.; Cerda, C. M.; Roman, L. U.; Hernandez, J. D. J. Nat. Prod. 1989, 52, 481-496. For relevant studies of the problem of Z → E isomerization during esterification, see: Roush, W. R.; Blizzard, T. A. J. Org. Chem. 1984, 49, 1772-1783 and 4332-4339.
92. See, for example: Bohlmann, F.; Tietze, B.-M. Chem. Ber. 1970, 103, 561-563. Hoskins, W. M.; Crout, D. H. G. J. Chem. Soc., Perkin Trans. 11977, 538-544. Beeby, P. J. Tetrahedron Lett. 1977, 3379-3382. Kubo, A.; Nakahara, S.; Inaba, K.; Kitahara, Y. Chem. Pharm. Bull. 1985, 33, 2582-2584. Kubo, A.; Nakahara, S.; Inaba, K.; Kitahara, Y. Chem. Pharm. Bull. 1986, 34, 4056-4068. Nakayama, J.; Nakamura, Y.; Tajiri, T.; Hoshino, M. Heterocycles 1986, 24, 637-640.Bal-Tembe, S.; Bhedi, D. N.; De Souza, N. J.; Rupp, R. H. Heterocycles 1987, 26, 1239-1249. Dev, V.; Bottini, A. T. J. Nat. Prod. 1987, 50, 968-971. Joseph-Nathan, P.; Cerda, C. M.; Roman, L. U.; Hernandez, J. D. J. Nat. Prod. 1989, 52, 481-496. For relevant studies of the problem of Z → E isomerization during esterification, see: Roush, W. R.; Blizzard, T. A. J. Org. Chem. 1984, 49, 1772-1783 and 4332-4339.
93. See, for example: Bohlmann, F.; Tietze, B.-M. Chem. Ber. 1970, 103, 561-563. Hoskins, W. M.; Crout, D. H. G. J. Chem. Soc., Perkin Trans. 11977, 538-544. Beeby, P. J. Tetrahedron Lett. 1977, 3379-3382. Kubo, A.; Nakahara, S.; Inaba, K.; Kitahara, Y. Chem. Pharm. Bull. 1985, 33, 2582-2584. Kubo, A.; Nakahara, S.; Inaba, K.; Kitahara, Y. Chem. Pharm. Bull. 1986, 34, 4056-4068. Nakayama, J.; Nakamura, Y.; Tajiri, T.; Hoshino, M. Heterocycles 1986, 24, 637-640.Bal-Tembe, S.; Bhedi, D. N.; De Souza, N. J.; Rupp, R. H. Heterocycles 1987, 26, 1239-1249. Dev, V.; Bottini, A. T. J. Nat. Prod. 1987, 50, 968-971. Joseph-Nathan, P.; Cerda, C. M.; Roman, L. U.; Hernandez, J. D. J. Nat. Prod. 1989, 52, 481-496. For relevant studies of the problem of Z → E isomerization during esterification, see: Roush, W. R.; Blizzard, T. A. J. Org. Chem. 1984, 49, 1772-1783 and 4332-4339.
94. See, for example: Bohlmann, F.; Tietze, B.-M. Chem. Ber. 1970, 103, 561-563. Hoskins, W. M.; Crout, D. H. G. J. Chem. Soc., Perkin Trans. 11977, 538-544. Beeby, P. J. Tetrahedron Lett. 1977, 3379-3382. Kubo, A.; Nakahara, S.; Inaba, K.; Kitahara, Y. Chem. Pharm. Bull. 1985, 33, 2582-2584. Kubo, A.; Nakahara, S.; Inaba, K.; Kitahara, Y. Chem. Pharm. Bull. 1986, 34, 4056-4068. Nakayama, J.; Nakamura, Y.; Tajiri, T.; Hoshino, M. Heterocycles 1986, 24, 637-640.Bal-Tembe, S.; Bhedi, D. N.; De Souza, N. J.; Rupp, R. H. Heterocycles 1987, 26, 1239-1249. Dev, V.; Bottini, A. T. J. Nat. Prod. 1987, 50, 968-971. Joseph-Nathan, P.; Cerda, C. M.; Roman, L. U.; Hernandez, J. D. J. Nat. Prod. 1989, 52, 481-496. For relevant studies of the problem of Z → E isomerization during esterification, see: Roush, W. R.; Blizzard, T. A. J. Org. Chem. 1984, 49, 1772-1783 and 4332-4339.
95. See, for example: Bohlmann, F.; Tietze, B.-M. Chem. Ber. 1970, 103, 561-563. Hoskins, W. M.; Crout, D. H. G. J. Chem. Soc., Perkin Trans. 11977, 538-544. Beeby, P. J. Tetrahedron Lett. 1977, 3379-3382. Kubo, A.; Nakahara, S.; Inaba, K.; Kitahara, Y. Chem. Pharm. Bull. 1985, 33, 2582-2584. Kubo, A.; Nakahara, S.; Inaba, K.; Kitahara, Y. Chem. Pharm. Bull. 1986, 34, 4056-4068. Nakayama, J.; Nakamura, Y.; Tajiri, T.; Hoshino, M. Heterocycles 1986, 24, 637-640.Bal-Tembe, S.; Bhedi, D. N.; De Souza, N. J.; Rupp, R. H. Heterocycles 1987, 26, 1239-1249. Dev, V.; Bottini, A. T. J. Nat. Prod. 1987, 50, 968-971. Joseph-Nathan, P.; Cerda, C. M.; Roman, L. U.; Hernandez, J. D. J. Nat. Prod. 1989, 52, 481-496. For relevant studies of the problem of Z → E isomerization during esterification, see: Roush, W. R.; Blizzard, T. A. J. Org. Chem. 1984, 49, 1772-1783 and 4332-4339.
96. See: Inanaga, J.; Hirata, K.; Saeki, H.; Katsuki, T.; Yamaguchi, M. Bull. Chem. Soc. Jpn. 1979, 52, 1989-1993. The mixed anhydride formed with trifluoroacetic anhydride has been reported to convert -2-methyl-2-butenol to its angelate ester in only 21% yield. See: Rücker, G.; Mayer, R.; Lee, K. R. Arch. Pharm. (Weinheim, Ger.) 1989, 322, 821-826.
97. See: Inanaga, J.; Hirata, K.; Saeki, H.; Katsuki, T.; Yamaguchi, M. Bull. Chem. Soc. Jpn. 1979, 52, 1989-1993. The mixed anhydride formed with trifluoroacetic anhydride has been reported to convert -2-methyl-2-butenol to its angelate ester in only 21% yield. See: Rücker, G.; Mayer, R.; Lee, K. R. Arch. Pharm. (Weinheim, Ger.) 1989, 322, 821-826.
98. Hartmann, B.; Kanazawa, A.; Deprés, J.-P.; Greene, A. E. Tetrahedron Lett. 1991, 32, 5077-5080.
99. For the use of carvone in synthesis, see: Ho, T.-L. Enantioselective Synthesis; John Wiley-Interscience: New York, 1992; Chapter 6 and references therein.
100. Luche, J.-L.; Rodriguez-Hahn, L.; Crabbé, P. J. Chem. Soc., Chem. Commun. 1978, 601-602.
101. Posner, G. H. Org. React. 1972, 19, 1-113.
102. Criegee, R.; Kaspar, R. J. Liebigs Ann. Chem. 1948, 560, 127-135. Criegee, R. Angew. Chem., Int. Ed. Engl. 1975, 14, 745-752. For some applications, see: Schreiber, S. L.; Liew, W.-F. Tetrahedron Lett. 1983, 24, 2363-2366. Okamura, W. H.; Aurrecoechea, J.-M.; Gibbs, R. A.; Norman, A. W. J. Org. Chem. 1989, 54, 4072-4083.
103. Criegee, R.; Kaspar, R. J. Liebigs Ann. Chem. 1948, 560, 127-135. Criegee, R. Angew. Chem., Int. Ed. Engl. 1975, 14, 745-752. For some applications, see: Schreiber, S. L.; Liew, W.-F. Tetrahedron Lett. 1983, 24, 2363-2366. Okamura, W. H.; Aurrecoechea, J.-M.; Gibbs, R. A.; Norman, A. W. J. Org. Chem. 1989, 54, 4072-4083.
104. Criegee, R.; Kaspar, R. J. Liebigs Ann. Chem. 1948, 560, 127-135. Criegee, R. Angew. Chem., Int. Ed. Engl. 1975, 14, 745-752. For some applications, see: Schreiber, S. L.; Liew, W.-F. Tetrahedron Lett. 1983, 24, 2363-2366. Okamura, W. H.; Aurrecoechea, J.-M.; Gibbs, R. A.; Norman, A. W. J. Org. Chem. 1989, 54, 4072-4083.
105. Criegee, R.; Kaspar, R. J. Liebigs Ann. Chem. 1948, 560, 127-135. Criegee, R. Angew. Chem., Int. Ed. Engl. 1975, 14, 745-752. For some applications, see: Schreiber, S. L.; Liew, W.-F. Tetrahedron Lett. 1983, 24, 2363-2366. Okamura, W. H.; Aurrecoechea, J.-M.; Gibbs, R. A.; Norman, A. W. J. Org. Chem. 1989, 54, 4072-4083.
106. The diiodo alcohol 30a*, however, subjected to the Noe acetal technique (91% efficiency) to remove the ca. 8% of enantiomeric material that originated from cis conjugate addition to (+)-carvone. Noe, C. R. Chem. Ber. 1982, 115, 1591-1606.
107. (a) Schram, T. J.; Cardellina, J. H., II, J. Org. Chem. 1985, 50, 4155-4157.
108. (b) Takeda, R.; Naoki, H.; Iwashita, T.; Mizukawa, K.; Hirose, Y.; Isida, T.; Inoue, M. Bull. Chem. Soc. Jpn. 1983, 56, 1125-1132.
109. (c) Iguchi, K.; Mori, K.; Matsushima, M.; Yamada, Y. Chem. Pharm. Bull. 1987, 35, 3532-3533.
110. (d) Tori, M.; Arbiyanti, H.; Taira, Z.; Asakawa, Y. Tetrahedron Lett. 1992. 33, 4011-4012.
111. (e) For the synthesis of a nonnatural spiro β-γ-epoxy-γ-butyrolactone, see: Solaja, B.; Huguet, J.; Karpf, M.; Dreiding, A. S. Tetrahedron 1987, 43, 4875-4886. For examples of diterpenes with this lactone function, see: Cardenas, J.; Pavon, T.; Esquivel, B.; Toscano, A.; Rodriguez-Hahn, L. Tetrahedron Lett. 1992, 33, 581-584.
112. (e) For the synthesis of a nonnatural spiro β-γ-epoxy-γ-butyrolactone, see: Solaja, B.; Huguet, J.; Karpf, M.; Dreiding, A. S. Tetrahedron 1987, 43, 4875-4886. For examples of diterpenes with this lactone function, see: Cardenas, J.; Pavon, T.; Esquivel, B.; Toscano, A.; Rodriguez-Hahn, L. Tetrahedron Lett. 1992, 33, 581-584.
113. Sharpless, K. B.; Lauer, R. F.; Teranishi, A. Y. J. Am. Chem. Soc. 1973, 95, 6137-6139. Iodination, followed by treatment with DBU, also yielded 38a, but less efficiently.
114. See: Collington, E. W.; Meyers, A. I. J. Org. Chem. 1971, 36, 3044-3045. See also: Bishop, C. E.; Morrow, G. W. J. Org. Chem. 1983. 48, 657-660. Majetich, G.; Song, J. S.; Ringold, C.; Nemeth, G. A.; Newton, M. G. J. Org. Chem. 1991, 56, 3973-3988.
115. See: Collington, E. W.; Meyers, A. I. J. Org. Chem. 1971, 36, 3044-3045. See also: Bishop, C. E.; Morrow, G. W. J. Org. Chem. 1983. 48, 657-660. Majetich, G.; Song, J. S.; Ringold, C.; Nemeth, G. A.; Newton, M. G. J. Org. Chem. 1991, 56, 3973-3988.
116. See: Collington, E. W.; Meyers, A. I. J. Org. Chem. 1971, 36, 3044-3045. See also: Bishop, C. E.; Morrow, G. W. J. Org. Chem. 1983. 48, 657-660. Majetich, G.; Song, J. S.; Ringold, C.; Nemeth, G. A.; Newton, M. G. J. Org. Chem. 1991, 56, 3973-3988.
117. Pattenden, G.; Gedge, D. R. Tetrahedron Lett, 1977, 4443-4446. The α-carbomethoxy derivative also failed to give satisfactory results.
118. Kuwajima, I.; Doi, Y. Tetrahedron Lett. 1972, 1163-1166.
119. Müller, P.; Siegfried, B. Tetrahedron Lett. 1973, 3565-3568.
120. 11(12) isomer that corresponded to that of bakkenolide A was demonstrated by hydrogenation of each to a mixture of the same dihydro derivatives.
121. Mander, L. N.; Sethi, S. P. Tetrahedron Lett. 1983, 24, 5425-5428.
122. See: Smith, A. B., III; Dieter, R. K. Tetrahedron 1981, 37, 2407-2439. Miller, R. D.; Theis, W. Tetrahedron Lett. 1987, 28, 1039-1042.
123. See: Smith, A. B., III; Dieter, R. K. Tetrahedron 1981, 37, 2407-2439. Miller, R. D.; Theis, W. Tetrahedron Lett. 1987, 28, 1039-1042.
124. (a) Barton, D. H. R.; Bashiardes, G.; Fourrey, J.-L. Tetrahedron Lett. 1983, 24, 1605-1608. Paquette, L. A.; Bellamy, F.; Wells, G. J.; Böhm, M. C.; Gleiter, R. J. Am. Chem. Soc. 1981, 103, 7122-7133. Stille, J. K. Angew. Chem., Int. Ed. Engl. 1986, 25, 508-524.
125. (a) Barton, D. H. R.; Bashiardes, G.; Fourrey, J.-L. Tetrahedron Lett. 1983, 24, 1605-1608. Paquette, L. A.; Bellamy, F.; Wells, G. J.; Böhm, M. C.; Gleiter, R. J. Am. Chem. Soc. 1981, 103, 7122-7133. Stille, J. K. Angew. Chem., Int. Ed. Engl. 1986, 25, 508-524.
126. (a) Barton, D. H. R.; Bashiardes, G.; Fourrey, J.-L. Tetrahedron Lett. 1983, 24, 1605-1608. Paquette, L. A.; Bellamy, F.; Wells, G. J.; Böhm, M. C.; Gleiter, R. J. Am. Chem. Soc. 1981, 103, 7122-7133. Stille, J. K. Angew. Chem., Int. Ed. Engl. 1986, 25, 508-524.
127. (b) Hayashi, T.; Katsuro, Y.; Kumada, M. Tetrahedron Lett. 1980, 21, 3915-3918. Brownbridge, P. Synthesis 1983, 1-28.
128. (b) Hayashi, T.; Katsuro, Y.; Kumada, M. Tetrahedron Lett. 1980, 21, 3915-3918. Brownbridge, P. Synthesis 1983, 1-28.
129. (c) Takai, K.; Oshima, K.; Nozaki, H. Tetrahedron Lett. 1980, 21, 2531-2534. Takai, K.; Sato, K.; Oshima, K.; Nozaki, H. Bull. Chem. Soc. Jpn. 1984, 57, 108-115.
130. (c) Takai, K.; Oshima, K.; Nozaki, H. Tetrahedron Lett. 1980, 21, 2531-2534. Takai, K.; Sato, K.; Oshima, K.; Nozaki, H. Bull. Chem. Soc. Jpn. 1984, 57, 108-115.
131. (d) Stang, P. J.; Hanack, M.; Subramaniam, L. R. Synthesis 1982, 85-126. Scott, W. J.; McMurry, J. E. Acc. Chem. Res. 1988, 21, 47-54. Farina, V.; Krishnamurthy, V.; Scott, W. J. Org. React. 1997, 50, 1-652.
132. (d) Stang, P. J.; Hanack, M.; Subramaniam, L. R. Synthesis 1982, 85-126. Scott, W. J.; McMurry, J. E. Acc. Chem. Res. 1988, 21, 47-54. Farina, V.; Krishnamurthy, V.; Scott, W. J. Org. React. 1997, 50, 1-652.
133. (d) Stang, P. J.; Hanack, M.; Subramaniam, L. R. Synthesis 1982, 85-126. Scott, W. J.; McMurry, J. E. Acc. Chem. Res. 1988, 21, 47-54. Farina, V.; Krishnamurthy, V.; Scott, W. J. Org. React. 1997, 50, 1-652.
134. On hydrogenation followed by dehydration, the tertiary alcohols afforded, in addition to the endocyclic olefin, the previously prepared 7-epibakkenolide A, thereby confirming the presumed C-7 configuration in malonate 39b.
135. 2 in pyridine at 60 °C gave the best endo/exo ratio (1/1.2).
136. Poutsma, M. L. J. Am. Chem. Soc. 1965, 87, 4285-4293. Bulliard, M.; Balme, G.; Goré, J. Tetrahedron Lett. 1989, 30, 5767-5770. Chlorine or iodobenzene dichloride could also be used for this purpose. For other examples of ene-type chlorination, see: Rodriguez, J.; Dulcère, J.-P. Synlett 1991, 477-478 and references therein.
137. Poutsma, M. L. J. Am. Chem. Soc. 1965, 87, 4285-4293. Bulliard, M.; Balme, G.; Goré, J. Tetrahedron Lett. 1989, 30, 5767-5770. Chlorine or iodobenzene dichloride could also be used for this purpose. For other examples of ene-type chlorination, see: Rodriguez, J.; Dulcère, J.-P. Synlett 1991, 477-478 and references therein.
138. Poutsma, M. L. J. Am. Chem. Soc. 1965, 87, 4285-4293. Bulliard, M.; Balme, G.; Goré, J. Tetrahedron Lett. 1989, 30, 5767-5770. Chlorine or iodobenzene dichloride could also be used for this purpose. For other examples of ene-type chlorination, see: Rodriguez, J.; Dulcère, J.-P. Synlett 1991, 477-478 and references therein.
139. Williard, P. G.; de Laszlo, S. E. J. Org. Chem. 1985, 50, 3738-3749. Selective formation of a dibromo (or similar) derivative for double bond protection could not be achieved.
140. The minor epoxide isomer (42c) on similar treatment produced material distinctly different from the natural product.
141. In an earlier approach based on the cycloalkylation of acrylate 13 with 10c, in which a formyl or a chloroformyl group replaces the C-10 (bakkane numbering) iodomethyl, only the formation of the undesired tetrahydrofuran derivatives from internal alkylation on oxygen was observed regardless of the experimental conditions.
142. 14i
143. 14i
144. 14i
145. Cossy, J.; Leblanc, C. Tetrahedron Lett. 1989, 30, 4531-4534. Cossy, J.; Bouzide, A.; Leblanc, C. J. Org. Chem. 2000, 65, 7257-7265.
146. Cossy, J.; Leblanc, C. Tetrahedron Lett. 1989, 30, 4531-4534. Cossy, J.; Bouzide, A.; Leblanc, C. J. Org. Chem. 2000, 65, 7257-7265.
147. Snider, B. B. Chem. Rev. 1996, 96, 339-363 and references therein.
148. Oumar-Mahamat, H.; Moustrou, C.; Surzur, J. M.; Bertrand, M. P. J. Org. Chem. 1989, 54, 5684-5688. For a catalytic approach, see: Hirase, K.; Iwahama, T.; Sakaguchi, S.; Ishii, Y. J. Org. Chem. 2002, 67, 970-973. For related protocols for effecting free-radical spiro lactonization, see: Back. T. G.; Gladstone, P. L.; Parvez, M. J. Org. Chem. 1996, 61, 3806-3814 and ref 76. See also: Clive, D. L. J.; Tao, Y.; Khodabocus, A.; Wu, Y.-J.; Angoh, A. G.; Bennett, S. M.; Boddy, C. N.; Bordeleau, L.; Keller, D.; Kleiner, G.; Middleton, D. S.; Nichols, C. J.; Richardson, S. R.; Vernon, P. G. J. Am. Chem. Soc. 1994, 116, 11275-11286. For a review of the various methods for preparing β-methylene-γ-butyrolactones, see ref 1b.
149. Oumar-Mahamat, H.; Moustrou, C.; Surzur, J. M.; Bertrand, M. P. J. Org. Chem. 1989, 54, 5684-5688. For a catalytic approach, see: Hirase, K.; Iwahama, T.; Sakaguchi, S.; Ishii, Y. J. Org. Chem. 2002, 67, 970-973. For related protocols for effecting free-radical spiro lactonization, see: Back. T. G.; Gladstone, P. L.; Parvez, M. J. Org. Chem. 1996, 61, 3806-3814 and ref 76. See also: Clive, D. L. J.; Tao, Y.; Khodabocus, A.; Wu, Y.-J.; Angoh, A. G.; Bennett, S. M.; Boddy, C. N.; Bordeleau, L.; Keller, D.; Kleiner, G.; Middleton, D. S.; Nichols, C. J.; Richardson, S. R.; Vernon, P. G. J. Am. Chem. Soc. 1994, 116, 11275-11286. For a review of the various methods for preparing β-methylene-γ-butyrolactones, see ref 1b.
150. Oumar-Mahamat, H.; Moustrou, C.; Surzur, J. M.; Bertrand, M. P. J. Org. Chem. 1989, 54, 5684-5688. For a catalytic approach, see: Hirase, K.; Iwahama, T.; Sakaguchi, S.; Ishii, Y. J. Org. Chem. 2002, 67, 970-973. For related protocols for effecting free-radical spiro lactonization, see: Back. T. G.; Gladstone, P. L.; Parvez, M. J. Org. Chem. 1996, 61, 3806-3814 and ref 76. See also: Clive, D. L. J.; Tao, Y.; Khodabocus, A.; Wu, Y.-J.; Angoh, A. G.; Bennett, S. M.; Boddy, C. N.; Bordeleau, L.; Keller, D.; Kleiner, G.; Middleton, D. S.; Nichols, C. J.; Richardson, S. R.; Vernon, P. G. J. Am. Chem. Soc. 1994, 116, 11275-11286. For a review of the various methods for preparing β-methylene-γ-butyrolactones, see ref 1b.
151. Oumar-Mahamat, H.; Moustrou, C.; Surzur, J. M.; Bertrand, M. P. J. Org. Chem. 1989, 54, 5684-5688. For a catalytic approach, see: Hirase, K.; Iwahama, T.; Sakaguchi, S.; Ishii, Y. J. Org. Chem. 2002, 67, 970-973. For related protocols for effecting free-radical spiro lactonization, see: Back. T. G.; Gladstone, P. L.; Parvez, M. J. Org. Chem. 1996, 61, 3806-3814 and ref 76. See also: Clive, D. L. J.; Tao, Y.; Khodabocus, A.; Wu, Y.-J.; Angoh, A. G.; Bennett, S. M.; Boddy, C. N.; Bordeleau, L.; Keller, D.; Kleiner, G.; Middleton, D. S.; Nichols, C. J.; Richardson, S. R.; Vernon, P. G. J. Am. Chem. Soc. 1994, 116, 11275-11286. For a review of the various methods for preparing β-methylene-γ-butyrolactones, see ref 1b.
152. For a review on transesterification, see: Otera, J. Chem. Rev. 1993, 93, 1449-1470.
153. Mottet, C.; Hamelin, O.; Garavel, G. D.; Deprés, J.-P.; Greene, A. E. J. Org. Chem. 1999, 64, 1380-1382. For the basis of this work, see: Bader, A. R.; Cummings, L. O.; Vogel, H. A. J. Am. Chem. Soc. 1951, 73, 4195-4197. Bader, A. R.; Vogel, H. A. J. Am. Chem. Soc. 1952, 74, 3992-3994. For a mechanistic study, see: Campbell, D. S.; Lawrie, C. W. J. Chem. Soc., Chem. Commun. 1971, 355-356.
154. Mottet, C.; Hamelin, O.; Garavel, G. D.; Deprés, J.-P.; Greene, A. E. J. Org. Chem. 1999, 64, 1380-1382. For the basis of this work, see: Bader, A. R.; Cummings, L. O.; Vogel, H. A. J. Am. Chem. Soc. 1951, 73, 4195-4197. Bader, A. R.; Vogel, H. A. J. Am. Chem. Soc. 1952, 74, 3992-3994. For a mechanistic study, see: Campbell, D. S.; Lawrie, C. W. J. Chem. Soc., Chem. Commun. 1971, 355-356.
155. Mottet, C.; Hamelin, O.; Garavel, G. D.; Deprés, J.-P.; Greene, A. E. J. Org. Chem. 1999, 64, 1380-1382. For the basis of this work, see: Bader, A. R.; Cummings, L. O.; Vogel, H. A. J. Am. Chem. Soc. 1951, 73, 4195-4197. Bader, A. R.; Vogel, H. A. J. Am. Chem. Soc. 1952, 74, 3992-3994. For a mechanistic study, see: Campbell, D. S.; Lawrie, C. W. J. Chem. Soc., Chem. Commun. 1971, 355-356.
156. Mottet, C.; Hamelin, O.; Garavel, G. D.; Deprés, J.-P.; Greene, A. E. J. Org. Chem. 1999, 64, 1380-1382. For the basis of this work, see: Bader, A. R.; Cummings, L. O.; Vogel, H. A. J. Am. Chem. Soc. 1951, 73, 4195-4197. Bader, A. R.; Vogel, H. A. J. Am. Chem. Soc. 1952, 74, 3992-3994. For a mechanistic study, see: Campbell, D. S.; Lawrie, C. W. J. Chem. Soc., Chem. Commun. 1971, 355-356.
157. Initially, the β-keto ester was refluxed in toluene in the presence of a catalytic amount of p-toluenesulfonic acid and with slow distillation; however, the present method has been found much superior.
158. max range 2.08-29.96°, 5604 measured reflections. 3877 [R(int) = 0.03610] independent reflections, R [1 > 2σ(I) 1 = 0.0482, wR2 [all data] = 0.592, GOF (all data) = 1.967.
159. Srikrishna, A.; Nagaraju, S.; Sharma, G. V. R. J. Chem. Soc., Chem. Commun. 1993. 285-288 and refs 15a-d,f.
160. Molander, G. A. Chem. Rev. 1992, 92, 29-68. Molander, G. A. Org. React. 1994, 46, 211-367. Molander, G. A.; Harris, C. R. Chem. Rev. 1996, 96, 307-338. Krief, A.; Laval, A.-M. Chem. Rev. 1999, 99, 745-777. For a similar reduction problem and an alternative solution, see: Wang, T.-Z.; Pinard, E.: Paquette, L. A. J. Am. Chem. Soc. 1996, 118, 1309-1318.
161. For reviews, see: Molander, G. A. Chem. Rev. 1992, 92, 29-68. Molander, G. A. Org. React. 1994, 46, 211-367. Molander, G. A.; Harris, C. R. Chem. Rev. 1996, 96, 307-338. Krief, A.; Laval, A.-M. Chem. Rev. 1999, 99, 745-777. For a similar reduction problem and an alternative solution, see: Wang, T.-Z.; Pinard, E.: Paquette, L. A. J. Am. Chem. Soc. 1996, 118, 1309-1318.
162. For reviews, see: Molander, G. A. Chem. Rev. 1992, 92, 29-68. Molander, G. A. Org. React. 1994, 46, 211-367. Molander, G. A.; Harris, C. R. Chem. Rev. 1996, 96, 307-338. Krief, A.; Laval, A.-M. Chem. Rev. 1999, 99, 745-777. For a similar reduction problem and an alternative solution, see: Wang, T.-Z.; Pinard, E.: Paquette, L. A. J. Am. Chem. Soc. 1996, 118, 1309-1318.
163. For reviews, see: Molander, G. A. Chem. Rev. 1992, 92, 29-68. Molander, G. A. Org. React. 1994, 46, 211-367. Molander, G. A.; Harris, C. R. Chem. Rev. 1996, 96, 307-338. Krief, A.; Laval, A.-M. Chem. Rev. 1999, 99, 745-777. For a similar reduction problem and an alternative solution, see: Wang, T.-Z.; Pinard, E.: Paquette, L. A. J. Am. Chem. Soc. 1996, 118, 1309-1318.
164. For reviews, see: Molander, G. A. Chem. Rev. 1992, 92, 29-68. Molander, G. A. Org. React. 1994, 46, 211-367. Molander, G. A.; Harris, C. R. Chem. Rev. 1996, 96, 307-338. Krief, A.; Laval, A.-M. Chem. Rev. 1999, 99, 745-777. For a similar reduction problem and an alternative solution, see: Wang, T.-Z.; Pinard, E.: Paquette, L. A. J. Am. Chem. Soc. 1996, 118, 1309-1318.
165. NMR experiments for the purpose of assigning stereochemistry again were not unequivocable.
166. Barton, D. H. R.; McCombie, S. W. J. Chem. Soc., Perkin Trans. 1 1975. 1574-1585. Hartwig, W. Tetrahedron 1983, 39, 2609-2645.
167. Barton, D. H. R.; McCombie, S. W. J. Chem. Soc., Perkin Trans. 1 1975. 1574-1585. Hartwig, W. Tetrahedron 1983, 39, 2609-2645.
168. For a related example, see: White, J. D.; Cutshall, N. S.; Kim, T.-S.; Shin, H. J. Am. Chem. Soc. 1995, 117, 9780-9781.
169. Molecular modeling was performed on a Silicon Graphics MD25G workstation running Insight II Discover, version 2.3.0 (Biosym Technologies, San Diego). The structures were energy minimized with the force field cvff.frc, and the minimization algorithm VA09A. Diastereomer 48, 39.4 kcal/mol; 47, 40.5 kcal/mol; 9-epi-48, 41.7 kcal/mol;-7-epi,9-epi-48, 42.3 kcal/mol.
170. Ito, Y.; Hirao, T.; Saegusa, T. J. Org. Chem. 1978, 43, 1011-1013.
171. Reich, H. J.; Wollowitz, S. Org. React. 1993, 44, 1-296.
172. Calculations were performed on an IBM RS 6000 workstation running Insight II Discover 98.0 (MSI, San Diego). The structures were energy minimized with the force field cvff.frc. and the minimization algorithm VA09A. Diastereomer 5a*, 39.2 kcal/mol; 53*, 40.0 kcal/mol; 7-epi,9-epi-5a*, 42.0 kcal/mol; 9-epi-5az.ast;, 44.3 kcal/mol.
173. Cf.; Krief, A.; Surleraux, D.; Ropson, N. Tetrahedron: Asymmetry 1993, 4, 289-292.
174. For a closely related (postulated) example in mass spectrometry, see ref 3b.
175. Itoh, T.; Jitsukawa, K.; Kaneda, K.; Teranishi, S. J. Am. Chem. Soc. 1979, 101, 159-169. For reviews, see: Sharpless, K. B.; Verhoeven, T. R. Aldrichimica Acta 1979, 12, 63-74. Jørgensen, K. A. Chem. Rev. 1989, 89, 431-458.
176. Itoh, T.; Jitsukawa, K.; Kaneda, K.; Teranishi, S. J. Am. Chem. Soc. 1979, 101, 159-169. For reviews, see: Sharpless, K. B.; Verhoeven, T. R. Aldrichimica Acta 1979, 12, 63-74. Jørgensen, K. A. Chem. Rev. 1989, 89, 431-458.
177. Itoh, T.; Jitsukawa, K.; Kaneda, K.; Teranishi, S. J. Am. Chem. Soc. 1979, 101, 159-169. For reviews, see: Sharpless, K. B.; Verhoeven, T. R. Aldrichimica Acta 1979, 12, 63-74. Jørgensen, K. A. Chem. Rev. 1989, 89, 431-458.
178. Devreese, A. A.; Demuynck, M.; De Clercq, P. J.; Vandewalle, M. Tetrahedron 1983, 39, 3039-3048. Swindell, C. S.; deSolms, S. J. Tetrahedron Lett. 1984, 25, 3801-3804.
179. Devreese, A. A.; Demuynck, M.; De Clercq, P. J.; Vandewalle, M. Tetrahedron 1983, 39, 3039-3048. Swindell, C. S.; deSolms, S. J. Tetrahedron Lett. 1984, 25, 3801-3804.