Total synthesis of the quinone epoxide dimer (+)-torreyanic acid: Application of a biomimetic oxidation/electrocyclization/Diels-Alder dimerization cascade

Journal of the American Chemical Society

Volumn 125, Issue 17, 2003, Pages 5095-5106

  Li, Chaomin ^a   Johnson, Richard P ^b   Porco Jr , John A ^a  

^a Boston University   (United States)

^b Univ of New Hampshire   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

DIMERIZATION; DIMERS; MONOMERS; OXIDATION; STEREOCHEMISTRY; SYNTHESIS (CHEMICAL);

EPOXIDE DIMERS;

CARBOXYLIC ACIDS;

AMBUIC ACID; CYCLOEPOXYDON; EPOXIDE; EPOXYQUINOL A; EPOXYQUINOL B; JESTERONE; NATURAL PRODUCT; QUINONE DERIVATIVE; TORREYANIC ACID; UNCLASSIFIED DRUG;

ARTICLE; ASYMMETRIC SYNTHESIS; CARBON NUCLEAR MAGNETIC RESONANCE; CHEMICAL REACTION; CHEMICAL STRUCTURE; CYCLIZATION; DIELS ALDER REACTION; DIMERIZATION; DRUG ISOLATION; EPOXIDATION; FUNGUS; NONHUMAN; PROTON NUCLEAR MAGNETIC RESONANCE; SYNTHESIS; TREE; UNITED STATES;

EID: 0242416942     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja021396c     Document Type: Article

References (98)

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73. For select examples of Diels - Alder reactions catalyzed by montmorillonite K10 clay, see: a) Laszlo, P.; Lucchetti, J. Tetrahedron Lett. 1984, 25, 2147. b) Cativiela, C.; Figueras, F.; Fraile, J. M.; Garcia, J. I.; Mayoral. J. A. Tetrahedron: Asymmetry 1993, 4, 223. c) Chiba, K.; Hirano, T.; Kitano, Y.; Tada, M. Chem. Commun. 1999, 8, 691. d) Kamath, C. R.; Samant, S. D. Indian J. Chem., Sect. B 1999, 38B, 1214. For a review of recent advances in clay-catalyzed organic transformations, see: Nikalje, M. D.; Phukan, P.; Sudalai, A. Org. Prep. Proced. Int. 2000, 32, 1.
74. For select examples of Diels - Alder reactions catalyzed by montmorillonite K10 clay, see: a) Laszlo, P.; Lucchetti, J. Tetrahedron Lett. 1984, 25, 2147. b) Cativiela, C.; Figueras, F.; Fraile, J. M.; Garcia, J. I.; Mayoral. J. A. Tetrahedron: Asymmetry 1993, 4, 223. c) Chiba, K.; Hirano, T.; Kitano, Y.; Tada, M. Chem. Commun. 1999, 8, 691. d) Kamath, C. R.; Samant, S. D. Indian J. Chem., Sect. B 1999, 38B, 1214. For a review of recent advances in clay-catalyzed organic transformations, see: Nikalje, M. D.; Phukan, P.; Sudalai, A. Org. Prep. Proced. Int. 2000, 32, 1.
75. For select examples of Diels - Alder reactions catalyzed by montmorillonite K10 clay, see: a) Laszlo, P.; Lucchetti, J. Tetrahedron Lett. 1984, 25, 2147. b) Cativiela, C.; Figueras, F.; Fraile, J. M.; Garcia, J. I.; Mayoral. J. A. Tetrahedron: Asymmetry 1993, 4, 223. c) Chiba, K.; Hirano, T.; Kitano, Y.; Tada, M. Chem. Commun. 1999, 8, 691. d) Kamath, C. R.; Samant, S. D. Indian J. Chem., Sect. B 1999, 38B, 1214. For a review of recent advances in clay-catalyzed organic transformations, see: Nikalje, M. D.; Phukan, P.; Sudalai, A. Org. Prep. Proced. Int. 2000, 32, 1.
76. For select examples of Diels - Alder reactions catalyzed by montmorillonite K10 clay, see: a) Laszlo, P.; Lucchetti, J. Tetrahedron Lett. 1984, 25, 2147. b) Cativiela, C.; Figueras, F.; Fraile, J. M.; Garcia, J. I.; Mayoral. J. A. Tetrahedron: Asymmetry 1993, 4, 223. c) Chiba, K.; Hirano, T.; Kitano, Y.; Tada, M. Chem. Commun. 1999, 8, 691. d) Kamath, C. R.; Samant, S. D. Indian J. Chem., Sect. B 1999, 38B, 1214. For a review of recent advances in clay-catalyzed organic transformations, see: Nikalje, M. D.; Phukan, P.; Sudalai, A. Org. Prep. Proced. Int. 2000, 32, 1.
77. For an example of Diels - Alder cycloaddition with π-facial selectivity anti to the diene epoxide moiety. see: J. R. Gillard, M. J. Newlands, J. N. Bridson, D. J. Burnell, Can. J. Chem. 1991, 69, 1337.
78. All calculations were performed using Spartan 02 (Version 1.01, Wave-function, Inc., Irvine, CA.).
79. For recent theoretical calculations of Diels - Alder transition states, see: a) Ujaque, G.; Norton, J. E.; Houk, K. N. J. Org. Chem. 2002, 67, 7179. b) Cayzer, T. N.; Wong, L. S.-M.; Turner, P.; Paddon-Row: M. N.; Sherburn, M. S. Chem. Eur. J. 2002, 8, 739. c) Singleton, D. A.; Schulmeier, B. E.; Hang, C.; Thomas, A.; Leung, S.-W.; Merrigan, S. R. Tetrahedron 2001, 57, 5149. d) Paddon-Row: M. N.; Sherburn, M. S. Chem. Commun. 2000, 22, 2215. e) Bachmann, C.; Boeker, N.; Mondon, M.; Gesson, J.-P. J. Org. Chem. 2000, 65, 8089. f) Bradley, A. Z.; Kociolek, M. G.; Johnson, R. P. J. Org. Chem. 2000, 65, 7134.
80. For recent theoretical calculations of Diels - Alder transition states, see: a) Ujaque, G.; Norton, J. E.; Houk, K. N. J. Org. Chem. 2002, 67, 7179. b) Cayzer, T. N.; Wong, L. S.-M.; Turner, P.; Paddon-Row: M. N.; Sherburn, M. S. Chem. Eur. J. 2002, 8, 739. c) Singleton, D. A.; Schulmeier, B. E.; Hang, C.; Thomas, A.; Leung, S.-W.; Merrigan, S. R. Tetrahedron 2001, 57, 5149. d) Paddon-Row: M. N.; Sherburn, M. S. Chem. Commun. 2000, 22, 2215. e) Bachmann, C.; Boeker, N.; Mondon, M.; Gesson, J.-P. J. Org. Chem. 2000, 65, 8089. f) Bradley, A. Z.; Kociolek, M. G.; Johnson, R. P. J. Org. Chem. 2000, 65, 7134.
81. For recent theoretical calculations of Diels - Alder transition states, see: a) Ujaque, G.; Norton, J. E.; Houk, K. N. J. Org. Chem. 2002, 67, 7179. b) Cayzer, T. N.; Wong, L. S.-M.; Turner, P.; Paddon-Row: M. N.; Sherburn, M. S. Chem. Eur. J. 2002, 8, 739. c) Singleton, D. A.; Schulmeier, B. E.; Hang, C.; Thomas, A.; Leung, S.-W.; Merrigan, S. R. Tetrahedron 2001, 57, 5149. d) Paddon-Row: M. N.; Sherburn, M. S. Chem. Commun. 2000, 22, 2215. e) Bachmann, C.; Boeker, N.; Mondon, M.; Gesson, J.-P. J. Org. Chem. 2000, 65, 8089. f) Bradley, A. Z.; Kociolek, M. G.; Johnson, R. P. J. Org. Chem. 2000, 65, 7134.
82. For recent theoretical calculations of Diels - Alder transition states, see: a) Ujaque, G.; Norton, J. E.; Houk, K. N. J. Org. Chem. 2002, 67, 7179. b) Cayzer, T. N.; Wong, L. S.-M.; Turner, P.; Paddon-Row: M. N.; Sherburn, M. S. Chem. Eur. J. 2002, 8, 739. c) Singleton, D. A.; Schulmeier, B. E.; Hang, C.; Thomas, A.; Leung, S.-W.; Merrigan, S. R. Tetrahedron 2001, 57, 5149. d) Paddon-Row: M. N.; Sherburn, M. S. Chem. Commun. 2000, 22, 2215. e) Bachmann, C.; Boeker, N.; Mondon, M.; Gesson, J.-P. J. Org. Chem. 2000, 65, 8089. f) Bradley, A. Z.; Kociolek, M. G.; Johnson, R. P. J. Org. Chem. 2000, 65, 7134.
83. For recent theoretical calculations of Diels - Alder transition states, see: a) Ujaque, G.; Norton, J. E.; Houk, K. N. J. Org. Chem. 2002, 67, 7179. b) Cayzer, T. N.; Wong, L. S.-M.; Turner, P.; Paddon-Row: M. N.; Sherburn, M. S. Chem. Eur. J. 2002, 8, 739. c) Singleton, D. A.; Schulmeier, B. E.; Hang, C.; Thomas, A.; Leung, S.-W.; Merrigan, S. R. Tetrahedron 2001, 57, 5149. d) Paddon-Row: M. N.; Sherburn, M. S. Chem. Commun. 2000, 22, 2215. e) Bachmann, C.; Boeker, N.; Mondon, M.; Gesson, J.-P. J. Org. Chem. 2000, 65, 8089. f) Bradley, A. Z.; Kociolek, M. G.; Johnson, R. P. J. Org. Chem. 2000, 65, 7134.
84. For recent theoretical calculations of Diels - Alder transition states, see: a) Ujaque, G.; Norton, J. E.; Houk, K. N. J. Org. Chem. 2002, 67, 7179. b) Cayzer, T. N.; Wong, L. S.-M.; Turner, P.; Paddon-Row: M. N.; Sherburn, M. S. Chem. Eur. J. 2002, 8, 739. c) Singleton, D. A.; Schulmeier, B. E.; Hang, C.; Thomas, A.; Leung, S.-W.; Merrigan, S. R. Tetrahedron 2001, 57, 5149. d) Paddon-Row: M. N.; Sherburn, M. S. Chem. Commun. 2000, 22, 2215. e) Bachmann, C.; Boeker, N.; Mondon, M.; Gesson, J.-P. J. Org. Chem. 2000, 65, 8089. f) Bradley, A. Z.; Kociolek, M. G.; Johnson, R. P. J. Org. Chem. 2000, 65, 7134.
85. This method is denoted as B3LYP/6-31G*//AM1(+ZPVE). Selected DFT optimizations were carried out to validate this method. For example, the barrier to closure for the trans-dienal to syn-pyran 31 (epoxide and pentyl chain syn refer to the pyran-fused quinone plane) was calculated to be 10.2 kcal/mol at the DFT//AM1 level and 12.6 kcal/mol with B3LYP/6-31G* theory. The parent dienal cyclization has a predicted barrier of ca. 22 kcal/ mol, see ref 18.
86. On the basis of heats of formation, the parent [4 + 2] reaction is exothermic by 40 kcal/mol which is reduced in bicyclic structures, cf.: Wilsey, S.; Houk, K. N.; Zewail, A. H. J. Am. Chem. Soc. 1999, 121, 5772.
87. Another possible mechanism for the production of alcohol 36 involves an ene reaction of 38 leading to a vinyl cyclobutene intermediate that either opens to 39 or 40, or undergoes a vinyl cyclobutane rearrangement directly to 36. We thank a reviewer for pointing out this possibility.
88. The geometric requirements for antarafacial [1,7] sigmatropic shifts are well-known, see: a) Jiao, H.; Schleyer, P. v. R. Angew. Chem., Int. Ed. Engl. 1993, 32, 1763. b) Enas, J. D.; Shen, G. Y.; Okamura, W. H. J. Am. Chem. Soc. 1991, 113, 3873. c) Shimizu, M.; Iwasaki, Y.; Ohno, A.; Yamada, S. Chem. Pharm. Bull. 2000, 48, 1484. d) Millar, J. G. Tetrahedron Lett. 1997, 38, 7971. e) Daniel, D.; Middleton, R.; Henry, H. L.; Okamura, W. H. J. Org. Chem. 1996, 61, 5617. f) Pohnert, G.; Boland, W. Tetrahedron 1994, 50, 10235.
89. The geometric requirements for antarafacial [1,7] sigmatropic shifts are well-known, see: a) Jiao, H.; Schleyer, P. v. R. Angew. Chem., Int. Ed. Engl. 1993, 32, 1763. b) Enas, J. D.; Shen, G. Y.; Okamura, W. H. J. Am. Chem. Soc. 1991, 113, 3873. c) Shimizu, M.; Iwasaki, Y.; Ohno, A.; Yamada, S. Chem. Pharm. Bull. 2000, 48, 1484. d) Millar, J. G. Tetrahedron Lett. 1997, 38, 7971. e) Daniel, D.; Middleton, R.; Henry, H. L.; Okamura, W. H. J. Org. Chem. 1996, 61, 5617. f) Pohnert, G.; Boland, W. Tetrahedron 1994, 50, 10235.
90. The geometric requirements for antarafacial [1,7] sigmatropic shifts are well-known, see: a) Jiao, H.; Schleyer, P. v. R. Angew. Chem., Int. Ed. Engl. 1993, 32, 1763. b) Enas, J. D.; Shen, G. Y.; Okamura, W. H. J. Am. Chem. Soc. 1991, 113, 3873. c) Shimizu, M.; Iwasaki, Y.; Ohno, A.; Yamada, S. Chem. Pharm. Bull. 2000, 48, 1484. d) Millar, J. G. Tetrahedron Lett. 1997, 38, 7971. e) Daniel, D.; Middleton, R.; Henry, H. L.; Okamura, W. H. J. Org. Chem. 1996, 61, 5617. f) Pohnert, G.; Boland, W. Tetrahedron 1994, 50, 10235.
91. The geometric requirements for antarafacial [1,7] sigmatropic shifts are well-known, see: a) Jiao, H.; Schleyer, P. v. R. Angew. Chem., Int. Ed. Engl. 1993, 32, 1763. b) Enas, J. D.; Shen, G. Y.; Okamura, W. H. J. Am. Chem. Soc. 1991, 113, 3873. c) Shimizu, M.; Iwasaki, Y.; Ohno, A.; Yamada, S. Chem. Pharm. Bull. 2000, 48, 1484. d) Millar, J. G. Tetrahedron Lett. 1997, 38, 7971. e) Daniel, D.; Middleton, R.; Henry, H. L.; Okamura, W. H. J. Org. Chem. 1996, 61, 5617. f) Pohnert, G.; Boland, W. Tetrahedron 1994, 50, 10235.
92. The geometric requirements for antarafacial [1,7] sigmatropic shifts are well-known, see: a) Jiao, H.; Schleyer, P. v. R. Angew. Chem., Int. Ed. Engl. 1993, 32, 1763. b) Enas, J. D.; Shen, G. Y.; Okamura, W. H. J. Am. Chem. Soc. 1991, 113, 3873. c) Shimizu, M.; Iwasaki, Y.; Ohno, A.; Yamada, S. Chem. Pharm. Bull. 2000, 48, 1484. d) Millar, J. G. Tetrahedron Lett. 1997, 38, 7971. e) Daniel, D.; Middleton, R.; Henry, H. L.; Okamura, W. H. J. Org. Chem. 1996, 61, 5617. f) Pohnert, G.; Boland, W. Tetrahedron 1994, 50, 10235.
93. The geometric requirements for antarafacial [1,7] sigmatropic shifts are well-known, see: a) Jiao, H.; Schleyer, P. v. R. Angew. Chem., Int. Ed. Engl. 1993, 32, 1763. b) Enas, J. D.; Shen, G. Y.; Okamura, W. H. J. Am. Chem. Soc. 1991, 113, 3873. c) Shimizu, M.; Iwasaki, Y.; Ohno, A.; Yamada, S. Chem. Pharm. Bull. 2000, 48, 1484. d) Millar, J. G. Tetrahedron Lett. 1997, 38, 7971. e) Daniel, D.; Middleton, R.; Henry, H. L.; Okamura, W. H. J. Org. Chem. 1996, 61, 5617. f) Pohnert, G.; Boland, W. Tetrahedron 1994, 50, 10235.
94. For a recent review of asymmetric epoxidation of electron-deficient olefins, see: Porter, M. J.; Skidmore, J. Chem. Commun. 2000, 14, 1215.
95. For recent example of hydroxyl-directed nucleophilic epoxidation of an enone, see: Evarts, J. B., Jr.; Fuchs, P. L. Tetrahedron Lett. 1999, 40, 2703.
96. Andrews, G. C. Tetrahedron Lett. 1980, 21, 697.
97. Chen, K.-M.; Hardmann, G. E.; Prasad, K.; Repic, O.; Shapiro, M. J. Tetrahedron Lett. 1987, 28, 155.
98. Harper, J. K.; Barich, D. H.; Hu, J. Z.; Strobel, G. A.; Grant, D. M. J. Org. Chem. 2003, 68; ASAP, Web Release Date: January 24, 2003.