Dual mechanisms of acid-catalyzed rearrangement of enol ester epoxides: Enantioselective formation of α-acyloxy ketones

Journal of the American Chemical Society

Volumn 121, Issue 16, 1999, Pages 4080-4081

  Zhu, Yuanming ^a   Manske, Karl J ^a   Shi, Yian ^a  

^a Department of Environmental and Radiological Health Sciences   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EPOXIDE; ESTER DERIVATIVE; KETONE;

ARTICLE; CATALYSIS; CHEMICAL STRUCTURE; ENANTIOMER; PROTON NUCLEAR MAGNETIC RESONANCE; REACTION ANALYSIS; STRUCTURE ANALYSIS; SYNTHESIS;

EID: 0033611957     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja990124f     Document Type: Article

References (33)

1. For leading reviews on enol ester epoxide rearrangements, see: (a) McDonald, R. N. Mech. Mol. Migr. 1971, 3, 67-107. (b) Riehl, J.-J.; Casara, P.; Fourgerousse, A. C. R. Acad. Sci. Paris, Ser. C 1974, 279, 79-82.
2. For leading reviews on enol ester epoxide rearrangements, see: (a) McDonald, R. N. Mech. Mol. Migr. 1971, 3, 67-107. (b) Riehl, J.-J.; Casara, P.; Fourgerousse, A. C. R. Acad. Sci. Paris, Ser. C 1974, 279, 79-82.
3. For examples of acid-catalyzed and thermal rearrangements of enol ester epoxides, see: (a) Soloway, A. H.; Considine, W. J.; Fukushima, D. K.; Gallagher, T. F. J. Am. Chem. Soc. 1954, 76, 2941-2943. (b) Leeds, N. S.; Fukushima, D. K.; Gallagher, T. F. J. Am. Chem. Soc. 1954, 76, 2943-2948. (c) Gardner, P. D. J. Am. Chem. Soc. 1956, 78, 3421-3424. (d) Johnson, W. S.; Gastambide, B.; Pappo, R. J. Am. Chem. Soc. 1957, 79, 1991-1994. (e) Shine, H. J.; Hunt, G. E. J. Am. Chem. Soc. 1958, 80, 2434-2435. (f) House, H. O.; Thompson, H. W. J. Org. Chem. 1961, 26, 3729-3734. (g) Williamson, K. L.; Johnson, W. S. J. Org. Chem. 1961, 26, 4563-4569. (h) Nambara, T.; Fishman, J. J. Org. Chem. 1962, 27, 2131-2135. (i) Draper, A. L.; Heilman, W. J.; Schaeffer, W. E.; Shine, H. J.; Shoolery, J. N. J. Org. Chem. 1962, 27, 2727-2729. (j) Riehl, J.-J.; Lehn, J.-M.; Hemmert, F. Bull Soc. Chim. Fr. 1963, 224-227. (k) Rhone, J. R.; Huffman, M. N. Tetrahedron Lett. 1965, 1395-1398. (l) Williamson, K. L.; Coburn, J. I.; Herr, M. F. J. Org. Chem. 1967, 32, 3934-3937 (m) McDonald, R. N.; Tabor, T. E. J. Am. Chem. Soc. 1967, 89, 6573-6578. (n) Smith, S. C.; Heathcock, C. H. J. Org. Chem. 1992, 57, 6379-6380.
4. For examples of acid-catalyzed and thermal rearrangements of enol ester epoxides, see: (a) Soloway, A. H.; Considine, W. J.; Fukushima, D. K.; Gallagher, T. F. J. Am. Chem. Soc. 1954, 76, 2941-2943. (b) Leeds, N. S.; Fukushima, D. K.; Gallagher, T. F. J. Am. Chem. Soc. 1954, 76, 2943-2948. (c) Gardner, P. D. J. Am. Chem. Soc. 1956, 78, 3421-3424. (d) Johnson, W. S.; Gastambide, B.; Pappo, R. J. Am. Chem. Soc. 1957, 79, 1991-1994. (e) Shine, H. J.; Hunt, G. E. J. Am. Chem. Soc. 1958, 80, 2434-2435. (f) House, H. O.; Thompson, H. W. J. Org. Chem. 1961, 26, 3729-3734. (g) Williamson, K. L.; Johnson, W. S. J. Org. Chem. 1961, 26, 4563-4569. (h) Nambara, T.; Fishman, J. J. Org. Chem. 1962, 27, 2131-2135. (i) Draper, A. L.; Heilman, W. J.; Schaeffer, W. E.; Shine, H. J.; Shoolery, J. N. J. Org. Chem. 1962, 27, 2727-2729. (j) Riehl, J.-J.; Lehn, J.-M.; Hemmert, F. Bull Soc. Chim. Fr. 1963, 224-227. (k) Rhone, J. R.; Huffman, M. N. Tetrahedron Lett. 1965, 1395-1398. (l) Williamson, K. L.; Coburn, J. I.; Herr, M. F. J. Org. Chem. 1967, 32, 3934-3937 (m) McDonald, R. N.; Tabor, T. E. J. Am. Chem. Soc. 1967, 89, 6573-6578. (n) Smith, S. C.; Heathcock, C. H. J. Org. Chem. 1992, 57, 6379-6380.
5. For examples of acid-catalyzed and thermal rearrangements of enol ester epoxides, see: (a) Soloway, A. H.; Considine, W. J.; Fukushima, D. K.; Gallagher, T. F. J. Am. Chem. Soc. 1954, 76, 2941-2943. (b) Leeds, N. S.; Fukushima, D. K.; Gallagher, T. F. J. Am. Chem. Soc. 1954, 76, 2943-2948. (c) Gardner, P. D. J. Am. Chem. Soc. 1956, 78, 3421-3424. (d) Johnson, W. S.; Gastambide, B.; Pappo, R. J. Am. Chem. Soc. 1957, 79, 1991-1994. (e) Shine, H. J.; Hunt, G. E. J. Am. Chem. Soc. 1958, 80, 2434-2435. (f) House, H. O.; Thompson, H. W. J. Org. Chem. 1961, 26, 3729-3734. (g) Williamson, K. L.; Johnson, W. S. J. Org. Chem. 1961, 26, 4563-4569. (h) Nambara, T.; Fishman, J. J. Org. Chem. 1962, 27, 2131-2135. (i) Draper, A. L.; Heilman, W. J.; Schaeffer, W. E.; Shine, H. J.; Shoolery, J. N. J. Org. Chem. 1962, 27, 2727-2729. (j) Riehl, J.-J.; Lehn, J.-M.; Hemmert, F. Bull Soc. Chim. Fr. 1963, 224-227. (k) Rhone, J. R.; Huffman, M. N. Tetrahedron Lett. 1965, 1395-1398. (l) Williamson, K. L.; Coburn, J. I.; Herr, M. F. J. Org. Chem. 1967, 32, 3934-3937 (m) McDonald, R. N.; Tabor, T. E. J. Am. Chem. Soc. 1967, 89, 6573-6578. (n) Smith, S. C.; Heathcock, C. H. J. Org. Chem. 1992, 57, 6379-6380.
6. For examples of acid-catalyzed and thermal rearrangements of enol ester epoxides, see: (a) Soloway, A. H.; Considine, W. J.; Fukushima, D. K.; Gallagher, T. F. J. Am. Chem. Soc. 1954, 76, 2941-2943. (b) Leeds, N. S.; Fukushima, D. K.; Gallagher, T. F. J. Am. Chem. Soc. 1954, 76, 2943-2948. (c) Gardner, P. D. J. Am. Chem. Soc. 1956, 78, 3421-3424. (d) Johnson, W. S.; Gastambide, B.; Pappo, R. J. Am. Chem. Soc. 1957, 79, 1991-1994. (e) Shine, H. J.; Hunt, G. E. J. Am. Chem. Soc. 1958, 80, 2434-2435. (f) House, H. O.; Thompson, H. W. J. Org. Chem. 1961, 26, 3729-3734. (g) Williamson, K. L.; Johnson, W. S. J. Org. Chem. 1961, 26, 4563-4569. (h) Nambara, T.; Fishman, J. J. Org. Chem. 1962, 27, 2131-2135. (i) Draper, A. L.; Heilman, W. J.; Schaeffer, W. E.; Shine, H. J.; Shoolery, J. N. J. Org. Chem. 1962, 27, 2727-2729. (j) Riehl, J.-J.; Lehn, J.-M.; Hemmert, F. Bull Soc. Chim. Fr. 1963, 224-227. (k) Rhone, J. R.; Huffman, M. N. Tetrahedron Lett. 1965, 1395-1398. (l) Williamson, K. L.; Coburn, J. I.; Herr, M. F. J. Org. Chem. 1967, 32, 3934-3937 (m) McDonald, R. N.; Tabor, T. E. J. Am. Chem. Soc. 1967, 89, 6573-6578. (n) Smith, S. C.; Heathcock, C. H. J. Org. Chem. 1992, 57, 6379-6380.
7. For examples of acid-catalyzed and thermal rearrangements of enol ester epoxides, see: (a) Soloway, A. H.; Considine, W. J.; Fukushima, D. K.; Gallagher, T. F. J. Am. Chem. Soc. 1954, 76, 2941-2943. (b) Leeds, N. S.; Fukushima, D. K.; Gallagher, T. F. J. Am. Chem. Soc. 1954, 76, 2943-2948. (c) Gardner, P. D. J. Am. Chem. Soc. 1956, 78, 3421-3424. (d) Johnson, W. S.; Gastambide, B.; Pappo, R. J. Am. Chem. Soc. 1957, 79, 1991-1994. (e) Shine, H. J.; Hunt, G. E. J. Am. Chem. Soc. 1958, 80, 2434-2435. (f) House, H. O.; Thompson, H. W. J. Org. Chem. 1961, 26, 3729-3734. (g) Williamson, K. L.; Johnson, W. S. J. Org. Chem. 1961, 26, 4563-4569. (h) Nambara, T.; Fishman, J. J. Org. Chem. 1962, 27, 2131-2135. (i) Draper, A. L.; Heilman, W. J.; Schaeffer, W. E.; Shine, H. J.; Shoolery, J. N. J. Org. Chem. 1962, 27, 2727-2729. (j) Riehl, J.-J.; Lehn, J.-M.; Hemmert, F. Bull Soc. Chim. Fr. 1963, 224-227. (k) Rhone, J. R.; Huffman, M. N. Tetrahedron Lett. 1965, 1395-1398. (l) Williamson, K. L.; Coburn, J. I.; Herr, M. F. J. Org. Chem. 1967, 32, 3934-3937 (m) McDonald, R. N.; Tabor, T. E. J. Am. Chem. Soc. 1967, 89, 6573-6578. (n) Smith, S. C.; Heathcock, C. H. J. Org. Chem. 1992, 57, 6379-6380.
8. For examples of acid-catalyzed and thermal rearrangements of enol ester epoxides, see: (a) Soloway, A. H.; Considine, W. J.; Fukushima, D. K.; Gallagher, T. F. J. Am. Chem. Soc. 1954, 76, 2941-2943. (b) Leeds, N. S.; Fukushima, D. K.; Gallagher, T. F. J. Am. Chem. Soc. 1954, 76, 2943-2948. (c) Gardner, P. D. J. Am. Chem. Soc. 1956, 78, 3421-3424. (d) Johnson, W. S.; Gastambide, B.; Pappo, R. J. Am. Chem. Soc. 1957, 79, 1991-1994. (e) Shine, H. J.; Hunt, G. E. J. Am. Chem. Soc. 1958, 80, 2434-2435. (f) House, H. O.; Thompson, H. W. J. Org. Chem. 1961, 26, 3729-3734. (g) Williamson, K. L.; Johnson, W. S. J. Org. Chem. 1961, 26, 4563-4569. (h) Nambara, T.; Fishman, J. J. Org. Chem. 1962, 27, 2131-2135. (i) Draper, A. L.; Heilman, W. J.; Schaeffer, W. E.; Shine, H. J.; Shoolery, J. N. J. Org. Chem. 1962, 27, 2727-2729. (j) Riehl, J.-J.; Lehn, J.-M.; Hemmert, F. Bull Soc. Chim. Fr. 1963, 224-227. (k) Rhone, J. R.; Huffman, M. N. Tetrahedron Lett. 1965, 1395-1398. (l) Williamson, K. L.; Coburn, J. I.; Herr, M. F. J. Org. Chem. 1967, 32, 3934-3937 (m) McDonald, R. N.; Tabor, T. E. J. Am. Chem. Soc. 1967, 89, 6573-6578. (n) Smith, S. C.; Heathcock, C. H. J. Org. Chem. 1992, 57, 6379-6380.
9. For examples of acid-catalyzed and thermal rearrangements of enol ester epoxides, see: (a) Soloway, A. H.; Considine, W. J.; Fukushima, D. K.; Gallagher, T. F. J. Am. Chem. Soc. 1954, 76, 2941-2943. (b) Leeds, N. S.; Fukushima, D. K.; Gallagher, T. F. J. Am. Chem. Soc. 1954, 76, 2943-2948. (c) Gardner, P. D. J. Am. Chem. Soc. 1956, 78, 3421-3424. (d) Johnson, W. S.; Gastambide, B.; Pappo, R. J. Am. Chem. Soc. 1957, 79, 1991-1994. (e) Shine, H. J.; Hunt, G. E. J. Am. Chem. Soc. 1958, 80, 2434-2435. (f) House, H. O.; Thompson, H. W. J. Org. Chem. 1961, 26, 3729-3734. (g) Williamson, K. L.; Johnson, W. S. J. Org. Chem. 1961, 26, 4563-4569. (h) Nambara, T.; Fishman, J. J. Org. Chem. 1962, 27, 2131-2135. (i) Draper, A. L.; Heilman, W. J.; Schaeffer, W. E.; Shine, H. J.; Shoolery, J. N. J. Org. Chem. 1962, 27, 2727-2729. (j) Riehl, J.-J.; Lehn, J.-M.; Hemmert, F. Bull Soc. Chim. Fr. 1963, 224-227. (k) Rhone, J. R.; Huffman, M. N. Tetrahedron Lett. 1965, 1395-1398. (l) Williamson, K. L.; Coburn, J. I.; Herr, M. F. J. Org. Chem. 1967, 32, 3934-3937 (m) McDonald, R. N.; Tabor, T. E. J. Am. Chem. Soc. 1967, 89, 6573-6578. (n) Smith, S. C.; Heathcock, C. H. J. Org. Chem. 1992, 57, 6379-6380.
10. For examples of acid-catalyzed and thermal rearrangements of enol ester epoxides, see: (a) Soloway, A. H.; Considine, W. J.; Fukushima, D. K.; Gallagher, T. F. J. Am. Chem. Soc. 1954, 76, 2941-2943. (b) Leeds, N. S.; Fukushima, D. K.; Gallagher, T. F. J. Am. Chem. Soc. 1954, 76, 2943-2948. (c) Gardner, P. D. J. Am. Chem. Soc. 1956, 78, 3421-3424. (d) Johnson, W. S.; Gastambide, B.; Pappo, R. J. Am. Chem. Soc. 1957, 79, 1991-1994. (e) Shine, H. J.; Hunt, G. E. J. Am. Chem. Soc. 1958, 80, 2434-2435. (f) House, H. O.; Thompson, H. W. J. Org. Chem. 1961, 26, 3729-3734. (g) Williamson, K. L.; Johnson, W. S. J. Org. Chem. 1961, 26, 4563-4569. (h) Nambara, T.; Fishman, J. J. Org. Chem. 1962, 27, 2131-2135. (i) Draper, A. L.; Heilman, W. J.; Schaeffer, W. E.; Shine, H. J.; Shoolery, J. N. J. Org. Chem. 1962, 27, 2727-2729. (j) Riehl, J.-J.; Lehn, J.-M.; Hemmert, F. Bull Soc. Chim. Fr. 1963, 224-227. (k) Rhone, J. R.; Huffman, M. N. Tetrahedron Lett. 1965, 1395-1398. (l) Williamson, K. L.; Coburn, J. I.; Herr, M. F. J. Org. Chem. 1967, 32, 3934-3937 (m) McDonald, R. N.; Tabor, T. E. J. Am. Chem. Soc. 1967, 89, 6573-6578. (n) Smith, S. C.; Heathcock, C. H. J. Org. Chem. 1992, 57, 6379-6380.
11. For examples of acid-catalyzed and thermal rearrangements of enol ester epoxides, see: (a) Soloway, A. H.; Considine, W. J.; Fukushima, D. K.; Gallagher, T. F. J. Am. Chem. Soc. 1954, 76, 2941-2943. (b) Leeds, N. S.; Fukushima, D. K.; Gallagher, T. F. J. Am. Chem. Soc. 1954, 76, 2943-2948. (c) Gardner, P. D. J. Am. Chem. Soc. 1956, 78, 3421-3424. (d) Johnson, W. S.; Gastambide, B.; Pappo, R. J. Am. Chem. Soc. 1957, 79, 1991-1994. (e) Shine, H. J.; Hunt, G. E. J. Am. Chem. Soc. 1958, 80, 2434-2435. (f) House, H. O.; Thompson, H. W. J. Org. Chem. 1961, 26, 3729-3734. (g) Williamson, K. L.; Johnson, W. S. J. Org. Chem. 1961, 26, 4563-4569. (h) Nambara, T.; Fishman, J. J. Org. Chem. 1962, 27, 2131-2135. (i) Draper, A. L.; Heilman, W. J.; Schaeffer, W. E.; Shine, H. J.; Shoolery, J. N. J. Org. Chem. 1962, 27, 2727-2729. (j) Riehl, J.-J.; Lehn, J.-M.; Hemmert, F. Bull Soc. Chim. Fr. 1963, 224-227. (k) Rhone, J. R.; Huffman, M. N. Tetrahedron Lett. 1965, 1395-1398. (l) Williamson, K. L.; Coburn, J. I.; Herr, M. F. J. Org. Chem. 1967, 32, 3934-3937 (m) McDonald, R. N.; Tabor, T. E. J. Am. Chem. Soc. 1967, 89, 6573-6578. (n) Smith, S. C.; Heathcock, C. H. J. Org. Chem. 1992, 57, 6379-6380.
12. For examples of acid-catalyzed and thermal rearrangements of enol ester epoxides, see: (a) Soloway, A. H.; Considine, W. J.; Fukushima, D. K.; Gallagher, T. F. J. Am. Chem. Soc. 1954, 76, 2941-2943. (b) Leeds, N. S.; Fukushima, D. K.; Gallagher, T. F. J. Am. Chem. Soc. 1954, 76, 2943-2948. (c) Gardner, P. D. J. Am. Chem. Soc. 1956, 78, 3421-3424. (d) Johnson, W. S.; Gastambide, B.; Pappo, R. J. Am. Chem. Soc. 1957, 79, 1991-1994. (e) Shine, H. J.; Hunt, G. E. J. Am. Chem. Soc. 1958, 80, 2434-2435. (f) House, H. O.; Thompson, H. W. J. Org. Chem. 1961, 26, 3729-3734. (g) Williamson, K. L.; Johnson, W. S. J. Org. Chem. 1961, 26, 4563-4569. (h) Nambara, T.; Fishman, J. J. Org. Chem. 1962, 27, 2131-2135. (i) Draper, A. L.; Heilman, W. J.; Schaeffer, W. E.; Shine, H. J.; Shoolery, J. N. J. Org. Chem. 1962, 27, 2727-2729. (j) Riehl, J.-J.; Lehn, J.-M.; Hemmert, F. Bull Soc. Chim. Fr. 1963, 224-227. (k) Rhone, J. R.; Huffman, M. N. Tetrahedron Lett. 1965, 1395-1398. (l) Williamson, K. L.; Coburn, J. I.; Herr, M. F. J. Org. Chem. 1967, 32, 3934-3937 (m) McDonald, R. N.; Tabor, T. E. J. Am. Chem. Soc. 1967, 89, 6573-6578. (n) Smith, S. C.; Heathcock, C. H. J. Org. Chem. 1992, 57, 6379-6380.
13. For examples of acid-catalyzed and thermal rearrangements of enol ester epoxides, see: (a) Soloway, A. H.; Considine, W. J.; Fukushima, D. K.; Gallagher, T. F. J. Am. Chem. Soc. 1954, 76, 2941-2943. (b) Leeds, N. S.; Fukushima, D. K.; Gallagher, T. F. J. Am. Chem. Soc. 1954, 76, 2943-2948. (c) Gardner, P. D. J. Am. Chem. Soc. 1956, 78, 3421-3424. (d) Johnson, W. S.; Gastambide, B.; Pappo, R. J. Am. Chem. Soc. 1957, 79, 1991-1994. (e) Shine, H. J.; Hunt, G. E. J. Am. Chem. Soc. 1958, 80, 2434-2435. (f) House, H. O.; Thompson, H. W. J. Org. Chem. 1961, 26, 3729-3734. (g) Williamson, K. L.; Johnson, W. S. J. Org. Chem. 1961, 26, 4563-4569. (h) Nambara, T.; Fishman, J. J. Org. Chem. 1962, 27, 2131-2135. (i) Draper, A. L.; Heilman, W. J.; Schaeffer, W. E.; Shine, H. J.; Shoolery, J. N. J. Org. Chem. 1962, 27, 2727-2729. (j) Riehl, J.-J.; Lehn, J.-M.; Hemmert, F. Bull Soc. Chim. Fr. 1963, 224-227. (k) Rhone, J. R.; Huffman, M. N. Tetrahedron Lett. 1965, 1395-1398. (l) Williamson, K. L.; Coburn, J. I.; Herr, M. F. J. Org. Chem. 1967, 32, 3934-3937 (m) McDonald, R. N.; Tabor, T. E. J. Am. Chem. Soc. 1967, 89, 6573-6578. (n) Smith, S. C.; Heathcock, C. H. J. Org. Chem. 1992, 57, 6379-6380.
14. For examples of acid-catalyzed and thermal rearrangements of enol ester epoxides, see: (a) Soloway, A. H.; Considine, W. J.; Fukushima, D. K.; Gallagher, T. F. J. Am. Chem. Soc. 1954, 76, 2941-2943. (b) Leeds, N. S.; Fukushima, D. K.; Gallagher, T. F. J. Am. Chem. Soc. 1954, 76, 2943-2948. (c) Gardner, P. D. J. Am. Chem. Soc. 1956, 78, 3421-3424. (d) Johnson, W. S.; Gastambide, B.; Pappo, R. J. Am. Chem. Soc. 1957, 79, 1991-1994. (e) Shine, H. J.; Hunt, G. E. J. Am. Chem. Soc. 1958, 80, 2434-2435. (f) House, H. O.; Thompson, H. W. J. Org. Chem. 1961, 26, 3729-3734. (g) Williamson, K. L.; Johnson, W. S. J. Org. Chem. 1961, 26, 4563-4569. (h) Nambara, T.; Fishman, J. J. Org. Chem. 1962, 27, 2131-2135. (i) Draper, A. L.; Heilman, W. J.; Schaeffer, W. E.; Shine, H. J.; Shoolery, J. N. J. Org. Chem. 1962, 27, 2727-2729. (j) Riehl, J.-J.; Lehn, J.-M.; Hemmert, F. Bull Soc. Chim. Fr. 1963, 224-227. (k) Rhone, J. R.; Huffman, M. N. Tetrahedron Lett. 1965, 1395-1398. (l) Williamson, K. L.; Coburn, J. I.; Herr, M. F. J. Org. Chem. 1967, 32, 3934-3937 (m) McDonald, R. N.; Tabor, T. E. J. Am. Chem. Soc. 1967, 89, 6573-6578. (n) Smith, S. C.; Heathcock, C. H. J. Org. Chem. 1992, 57, 6379-6380.
15. For examples of acid-catalyzed and thermal rearrangements of enol ester epoxides, see: (a) Soloway, A. H.; Considine, W. J.; Fukushima, D. K.; Gallagher, T. F. J. Am. Chem. Soc. 1954, 76, 2941-2943. (b) Leeds, N. S.; Fukushima, D. K.; Gallagher, T. F. J. Am. Chem. Soc. 1954, 76, 2943-2948. (c) Gardner, P. D. J. Am. Chem. Soc. 1956, 78, 3421-3424. (d) Johnson, W. S.; Gastambide, B.; Pappo, R. J. Am. Chem. Soc. 1957, 79, 1991-1994. (e) Shine, H. J.; Hunt, G. E. J. Am. Chem. Soc. 1958, 80, 2434-2435. (f) House, H. O.; Thompson, H. W. J. Org. Chem. 1961, 26, 3729-3734. (g) Williamson, K. L.; Johnson, W. S. J. Org. Chem. 1961, 26, 4563-4569. (h) Nambara, T.; Fishman, J. J. Org. Chem. 1962, 27, 2131-2135. (i) Draper, A. L.; Heilman, W. J.; Schaeffer, W. E.; Shine, H. J.; Shoolery, J. N. J. Org. Chem. 1962, 27, 2727-2729. (j) Riehl, J.-J.; Lehn, J.-M.; Hemmert, F. Bull Soc. Chim. Fr. 1963, 224-227. (k) Rhone, J. R.; Huffman, M. N. Tetrahedron Lett. 1965, 1395-1398. (l) Williamson, K. L.; Coburn, J. I.; Herr, M. F. J. Org. Chem. 1967, 32, 3934-3937 (m) McDonald, R. N.; Tabor, T. E. J. Am. Chem. Soc. 1967, 89, 6573-6578. (n) Smith, S. C.; Heathcock, C. H. J. Org. Chem. 1992, 57, 6379-6380.
16. For examples of acid-catalyzed and thermal rearrangements of enol ester epoxides, see: (a) Soloway, A. H.; Considine, W. J.; Fukushima, D. K.; Gallagher, T. F. J. Am. Chem. Soc. 1954, 76, 2941-2943. (b) Leeds, N. S.; Fukushima, D. K.; Gallagher, T. F. J. Am. Chem. Soc. 1954, 76, 2943-2948. (c) Gardner, P. D. J. Am. Chem. Soc. 1956, 78, 3421-3424. (d) Johnson, W. S.; Gastambide, B.; Pappo, R. J. Am. Chem. Soc. 1957, 79, 1991-1994. (e) Shine, H. J.; Hunt, G. E. J. Am. Chem. Soc. 1958, 80, 2434-2435. (f) House, H. O.; Thompson, H. W. J. Org. Chem. 1961, 26, 3729-3734. (g) Williamson, K. L.; Johnson, W. S. J. Org. Chem. 1961, 26, 4563-4569. (h) Nambara, T.; Fishman, J. J. Org. Chem. 1962, 27, 2131-2135. (i) Draper, A. L.; Heilman, W. J.; Schaeffer, W. E.; Shine, H. J.; Shoolery, J. N. J. Org. Chem. 1962, 27, 2727-2729. (j) Riehl, J.-J.; Lehn, J.-M.; Hemmert, F. Bull Soc. Chim. Fr. 1963, 224-227. (k) Rhone, J. R.; Huffman, M. N. Tetrahedron Lett. 1965, 1395-1398. (l) Williamson, K. L.; Coburn, J. I.; Herr, M. F. J. Org. Chem. 1967, 32, 3934-3937 (m) McDonald, R. N.; Tabor, T. E. J. Am. Chem. Soc. 1967, 89, 6573-6578. (n) Smith, S. C.; Heathcock, C. H. J. Org. Chem. 1992, 57, 6379-6380.
17. For example, it was observed that treating an enol ester epoxide of epiandrosterone acetate with silicic acid at 50 °C for 17 h led to the formation of a mixture α and β epimeric 16-acetoxy ketones with a ratio of 1.8:1 in a 16.7% isolated yield (see ref 2d). The a isomer resulted from a rearrangement with retention of configuration, and the β isomer resulted from a rearrangement with inversion. On the basis of the observation that the α and β isomers did not undergo isomerization under the reaction conditions, it was suggested that these two isomers came from two competing reactions. However, it is not clear whether these two reactions were induced by acid alone or both acid and heat since the reaction was carried out at 50 °C.
18. Zhu, Y.; Tu, Y.; Yu, H.; Shi, Y. Tetrahedron Lett. 1998, 39, 7819-7822.
19. For leading references on nonenzymatic synthesis of enantiomerically enriched hydroxyketones and their derivatives, see: (a) Enders, D.; Bhushan, V. Tetrahedron Lett. 1988, 29, 2437-2440. (b) Davis, F. A.; Sheppard, A. C.; Chen, B.-C.; Haque, M. S. J. Am. Chem. Soc. 1990, 112, 6679-6690. (c) Davis, F. A.; Chen, B.-C. Chem. Rev. 1992, 92, 919-934. (d) Hashiyama, T.; Morikawa, K.; Sharpless, K. B. J. Org. Chem. 1992, 57, 5067-5068. (e) Reddy, D. R.; Thornton, E. R. J. Chem. Soc., Chem. Commun. 1992, 172-173. (f) D'Accolti, L.; Detomaso, A.; Fusco, C.; Rosa, A.; Curci, R. J. Org. Chem. 1993, 58, 3600-3601. (g) Chang, S.; Heid, R. M.; Jacobsen, E. N. Tetrahedron Lett. 1994, 35, 669-672. (h) Fududa, T.; Katsuki, T. Tetrahedron Lett. 1996, 37, 4389-4392. (i) Adam, W.; Fell, R. T.; Stegmann, V. R.; Saha-Moller, C. R. J. Am. Chem. Soc. 1998, 120, 708-714.
20. For leading references on nonenzymatic synthesis of enantiomerically enriched hydroxyketones and their derivatives, see: (a) Enders, D.; Bhushan, V. Tetrahedron Lett. 1988, 29, 2437-2440. (b) Davis, F. A.; Sheppard, A. C.; Chen, B.-C.; Haque, M. S. J. Am. Chem. Soc. 1990, 112, 6679-6690. (c) Davis, F. A.; Chen, B.-C. Chem. Rev. 1992, 92, 919-934. (d) Hashiyama, T.; Morikawa, K.; Sharpless, K. B. J. Org. Chem. 1992, 57, 5067-5068. (e) Reddy, D. R.; Thornton, E. R. J. Chem. Soc., Chem. Commun. 1992, 172-173. (f) D'Accolti, L.; Detomaso, A.; Fusco, C.; Rosa, A.; Curci, R. J. Org. Chem. 1993, 58, 3600-3601. (g) Chang, S.; Heid, R. M.; Jacobsen, E. N. Tetrahedron Lett. 1994, 35, 669-672. (h) Fududa, T.; Katsuki, T. Tetrahedron Lett. 1996, 37, 4389-4392. (i) Adam, W.; Fell, R. T.; Stegmann, V. R.; Saha-Moller, C. R. J. Am. Chem. Soc. 1998, 120, 708-714.
21. For leading references on nonenzymatic synthesis of enantiomerically enriched hydroxyketones and their derivatives, see: (a) Enders, D.; Bhushan, V. Tetrahedron Lett. 1988, 29, 2437-2440. (b) Davis, F. A.; Sheppard, A. C.; Chen, B.-C.; Haque, M. S. J. Am. Chem. Soc. 1990, 112, 6679-6690. (c) Davis, F. A.; Chen, B.-C. Chem. Rev. 1992, 92, 919-934. (d) Hashiyama, T.; Morikawa, K.; Sharpless, K. B. J. Org. Chem. 1992, 57, 5067-5068. (e) Reddy, D. R.; Thornton, E. R. J. Chem. Soc., Chem. Commun. 1992, 172-173. (f) D'Accolti, L.; Detomaso, A.; Fusco, C.; Rosa, A.; Curci, R. J. Org. Chem. 1993, 58, 3600-3601. (g) Chang, S.; Heid, R. M.; Jacobsen, E. N. Tetrahedron Lett. 1994, 35, 669-672. (h) Fududa, T.; Katsuki, T. Tetrahedron Lett. 1996, 37, 4389-4392. (i) Adam, W.; Fell, R. T.; Stegmann, V. R.; Saha-Moller, C. R. J. Am. Chem. Soc. 1998, 120, 708-714.
22. For leading references on nonenzymatic synthesis of enantiomerically enriched hydroxyketones and their derivatives, see: (a) Enders, D.; Bhushan, V. Tetrahedron Lett. 1988, 29, 2437-2440. (b) Davis, F. A.; Sheppard, A. C.; Chen, B.-C.; Haque, M. S. J. Am. Chem. Soc. 1990, 112, 6679-6690. (c) Davis, F. A.; Chen, B.-C. Chem. Rev. 1992, 92, 919-934. (d) Hashiyama, T.; Morikawa, K.; Sharpless, K. B. J. Org. Chem. 1992, 57, 5067-5068. (e) Reddy, D. R.; Thornton, E. R. J. Chem. Soc., Chem. Commun. 1992, 172-173. (f) D'Accolti, L.; Detomaso, A.; Fusco, C.; Rosa, A.; Curci, R. J. Org. Chem. 1993, 58, 3600-3601. (g) Chang, S.; Heid, R. M.; Jacobsen, E. N. Tetrahedron Lett. 1994, 35, 669-672. (h) Fududa, T.; Katsuki, T. Tetrahedron Lett. 1996, 37, 4389-4392. (i) Adam, W.; Fell, R. T.; Stegmann, V. R.; Saha-Moller, C. R. J. Am. Chem. Soc. 1998, 120, 708-714.
23. For leading references on nonenzymatic synthesis of enantiomerically enriched hydroxyketones and their derivatives, see: (a) Enders, D.; Bhushan, V. Tetrahedron Lett. 1988, 29, 2437-2440. (b) Davis, F. A.; Sheppard, A. C.; Chen, B.-C.; Haque, M. S. J. Am. Chem. Soc. 1990, 112, 6679-6690. (c) Davis, F. A.; Chen, B.-C. Chem. Rev. 1992, 92, 919-934. (d) Hashiyama, T.; Morikawa, K.; Sharpless, K. B. J. Org. Chem. 1992, 57, 5067-5068. (e) Reddy, D. R.; Thornton, E. R. J. Chem. Soc., Chem. Commun. 1992, 172-173. (f) D'Accolti, L.; Detomaso, A.; Fusco, C.; Rosa, A.; Curci, R. J. Org. Chem. 1993, 58, 3600-3601. (g) Chang, S.; Heid, R. M.; Jacobsen, E. N. Tetrahedron Lett. 1994, 35, 669-672. (h) Fududa, T.; Katsuki, T. Tetrahedron Lett. 1996, 37, 4389-4392. (i) Adam, W.; Fell, R. T.; Stegmann, V. R.; Saha-Moller, C. R. J. Am. Chem. Soc. 1998, 120, 708-714.
24. For leading references on nonenzymatic synthesis of enantiomerically enriched hydroxyketones and their derivatives, see: (a) Enders, D.; Bhushan, V. Tetrahedron Lett. 1988, 29, 2437-2440. (b) Davis, F. A.; Sheppard, A. C.; Chen, B.-C.; Haque, M. S. J. Am. Chem. Soc. 1990, 112, 6679-6690. (c) Davis, F. A.; Chen, B.-C. Chem. Rev. 1992, 92, 919-934. (d) Hashiyama, T.; Morikawa, K.; Sharpless, K. B. J. Org. Chem. 1992, 57, 5067-5068. (e) Reddy, D. R.; Thornton, E. R. J. Chem. Soc., Chem. Commun. 1992, 172-173. (f) D'Accolti, L.; Detomaso, A.; Fusco, C.; Rosa, A.; Curci, R. J. Org. Chem. 1993, 58, 3600-3601. (g) Chang, S.; Heid, R. M.; Jacobsen, E. N. Tetrahedron Lett. 1994, 35, 669-672. (h) Fududa, T.; Katsuki, T. Tetrahedron Lett. 1996, 37, 4389-4392. (i) Adam, W.; Fell, R. T.; Stegmann, V. R.; Saha-Moller, C. R. J. Am. Chem. Soc. 1998, 120, 708-714.
25. For leading references on nonenzymatic synthesis of enantiomerically enriched hydroxyketones and their derivatives, see: (a) Enders, D.; Bhushan, V. Tetrahedron Lett. 1988, 29, 2437-2440. (b) Davis, F. A.; Sheppard, A. C.; Chen, B.-C.; Haque, M. S. J. Am. Chem. Soc. 1990, 112, 6679-6690. (c) Davis, F. A.; Chen, B.-C. Chem. Rev. 1992, 92, 919-934. (d) Hashiyama, T.; Morikawa, K.; Sharpless, K. B. J. Org. Chem. 1992, 57, 5067-5068. (e) Reddy, D. R.; Thornton, E. R. J. Chem. Soc., Chem. Commun. 1992, 172-173. (f) D'Accolti, L.; Detomaso, A.; Fusco, C.; Rosa, A.; Curci, R. J. Org. Chem. 1993, 58, 3600-3601. (g) Chang, S.; Heid, R. M.; Jacobsen, E. N. Tetrahedron Lett. 1994, 35, 669-672. (h) Fududa, T.; Katsuki, T. Tetrahedron Lett. 1996, 37, 4389-4392. (i) Adam, W.; Fell, R. T.; Stegmann, V. R.; Saha-Moller, C. R. J. Am. Chem. Soc. 1998, 120, 708-714.
26. For leading references on nonenzymatic synthesis of enantiomerically enriched hydroxyketones and their derivatives, see: (a) Enders, D.; Bhushan, V. Tetrahedron Lett. 1988, 29, 2437-2440. (b) Davis, F. A.; Sheppard, A. C.; Chen, B.-C.; Haque, M. S. J. Am. Chem. Soc. 1990, 112, 6679-6690. (c) Davis, F. A.; Chen, B.-C. Chem. Rev. 1992, 92, 919-934. (d) Hashiyama, T.; Morikawa, K.; Sharpless, K. B. J. Org. Chem. 1992, 57, 5067-5068. (e) Reddy, D. R.; Thornton, E. R. J. Chem. Soc., Chem. Commun. 1992, 172-173. (f) D'Accolti, L.; Detomaso, A.; Fusco, C.; Rosa, A.; Curci, R. J. Org. Chem. 1993, 58, 3600-3601. (g) Chang, S.; Heid, R. M.; Jacobsen, E. N. Tetrahedron Lett. 1994, 35, 669-672. (h) Fududa, T.; Katsuki, T. Tetrahedron Lett. 1996, 37, 4389-4392. (i) Adam, W.; Fell, R. T.; Stegmann, V. R.; Saha-Moller, C. R. J. Am. Chem. Soc. 1998, 120, 708-714.
27. For leading references on nonenzymatic synthesis of enantiomerically enriched hydroxyketones and their derivatives, see: (a) Enders, D.; Bhushan, V. Tetrahedron Lett. 1988, 29, 2437-2440. (b) Davis, F. A.; Sheppard, A. C.; Chen, B.-C.; Haque, M. S. J. Am. Chem. Soc. 1990, 112, 6679-6690. (c) Davis, F. A.; Chen, B.-C. Chem. Rev. 1992, 92, 919-934. (d) Hashiyama, T.; Morikawa, K.; Sharpless, K. B. J. Org. Chem. 1992, 57, 5067-5068. (e) Reddy, D. R.; Thornton, E. R. J. Chem. Soc., Chem. Commun. 1992, 172-173. (f) D'Accolti, L.; Detomaso, A.; Fusco, C.; Rosa, A.; Curci, R. J. Org. Chem. 1993, 58, 3600-3601. (g) Chang, S.; Heid, R. M.; Jacobsen, E. N. Tetrahedron Lett. 1994, 35, 669-672. (h) Fududa, T.; Katsuki, T. Tetrahedron Lett. 1996, 37, 4389-4392. (i) Adam, W.; Fell, R. T.; Stegmann, V. R.; Saha-Moller, C. R. J. Am. Chem. Soc. 1998, 120, 708-714.
28. For examples of silica gel catalyzed rearrangements, see refs 2a, b, and d. Both inversion and retention of configuration were reported.
29. While the acidity of the catalyst is an important factor affecting the competition of the two pathways, the size and the coordination number of the Lewis acid could also be important. Full elucidation of these factors awaits further studies.
30. 3, and Silica gel, the crossover products were found to be minimal (less than 0.5% at substrate concentration of 0.64 M and less than 0.2% at substrate concentration of 0.018 M) (for details see Supporting Information). All of these results suggest that the acid-catalyzed rearrangements proceed predominantly in an intramolecular fashion, particularly for pathway b. Further experiments with enantiomerically enriched enol ester epoxides showed that the enantioselectivities of the rearranged products were not affected by the substrate concentrations.
31. We found that the thermal rearrangement of these epoxides could also lead to the formation of the inverted product with high stereospecificity when the rearrangements were carried out in sealed tubes at high temperature (160-190 °C) in vacuo. Since the Lewis acid-catalyzed rearrangement can be conveniently carried out at room temperature, it provides a mild method to obtain the inverted product, particularly for systems which are thermally sensitive.
32. Nicolosi, G.; Patti, A.; Piattelli, M.; Sanfilippo, C. Tetrahedron: Asymmetry 1995, 6, 519-524.
33. Naemura, K. Wakebe, T.; Hirose, K.; Tobe, Y. Tetrahedron: Asymmetry 1997, 8, 2585-2595.