Ring-closing metathesis in the, synthesis of large and medium-sized oxacycles. Application to the synthesis of polyoxygenated macrocycles

Journal of Organic Chemistry

Volumn 64, Issue 13, 1999, Pages 4798-4816

  Delgado, Mercedes ^a   Martín, Julio D ^a  

^a CSIC JA USE Centro de Investigaciones Cientificas Isla de la Cartuja CICIC   (Spain)

Author keywords

[No Author keywords available]

Indexed keywords

ALKADIENE; ALKENE; BENZYLIDENE DERIVATIVE; MACROCYCLIC COMPOUND; POLYETHER;

ARTICLE; CATALYSIS; CHEMICAL BINDING; CHEMICAL REACTION; CHEMICAL STRUCTURE; CYCLIZATION; NONHUMAN; SYNTHESIS;

EID: 0033603457     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo9901438     Document Type: Article

References (66)

1. Recent reviews about olefin metathesis and its application to organic synthesis: (a) Ivin, K. J.; Mol, J. C. Olefin Metathesis and Metathesis Polymerization; Academic Press: San Diego, 1997. (b) Schmalz, H.-G. Angew. Chem., Int. Ed. Engl. 1985, 34, 1833-1836. (c) Schuster, M.; Blechert, S. Angew. Chem., Int. Ed. Engl. 1997, 36, 2036-2056. (d) Armstrong, S. K. J. Chem. Soc., Perkin Trans, 1 1998, 371-388. (e) Grubbs, H. H.; Chang, S. Tetrahedron 1998, 54, 4413- 4450.
2. Recent reviews about olefin metathesis and its application to organic synthesis: (a) Ivin, K. J.; Mol, J. C. Olefin Metathesis and Metathesis Polymerization; Academic Press: San Diego, 1997. (b) Schmalz, H.-G. Angew. Chem., Int. Ed. Engl. 1985, 34, 1833-1836. (c) Schuster, M.; Blechert, S. Angew. Chem., Int. Ed. Engl. 1997, 36, 2036-2056. (d) Armstrong, S. K. J. Chem. Soc., Perkin Trans, 1 1998, 371-388. (e) Grubbs, H. H.; Chang, S. Tetrahedron 1998, 54, 4413- 4450.
3. Recent reviews about olefin metathesis and its application to organic synthesis: (a) Ivin, K. J.; Mol, J. C. Olefin Metathesis and Metathesis Polymerization; Academic Press: San Diego, 1997. (b) Schmalz, H.-G. Angew. Chem., Int. Ed. Engl. 1985, 34, 1833-1836. (c) Schuster, M.; Blechert, S. Angew. Chem., Int. Ed. Engl. 1997, 36, 2036-2056. (d) Armstrong, S. K. J. Chem. Soc., Perkin Trans, 1 1998, 371-388. (e) Grubbs, H. H.; Chang, S. Tetrahedron 1998, 54, 4413- 4450.
4. Recent reviews about olefin metathesis and its application to organic synthesis: (a) Ivin, K. J.; Mol, J. C. Olefin Metathesis and Metathesis Polymerization; Academic Press: San Diego, 1997. (b) Schmalz, H.-G. Angew. Chem., Int. Ed. Engl. 1985, 34, 1833-1836. (c) Schuster, M.; Blechert, S. Angew. Chem., Int. Ed. Engl. 1997, 36, 2036-2056. (d) Armstrong, S. K. J. Chem. Soc., Perkin Trans, 1 1998, 371-388. (e) Grubbs, H. H.; Chang, S. Tetrahedron 1998, 54, 4413- 4450.
5. Recent reviews about olefin metathesis and its application to organic synthesis: (a) Ivin, K. J.; Mol, J. C. Olefin Metathesis and Metathesis Polymerization; Academic Press: San Diego, 1997. (b) Schmalz, H.-G. Angew. Chem., Int. Ed. Engl. 1985, 34, 1833-1836. (c) Schuster, M.; Blechert, S. Angew. Chem., Int. Ed. Engl. 1997, 36, 2036-2056. (d) Armstrong, S. K. J. Chem. Soc., Perkin Trans, 1 1998, 371-388. (e) Grubbs, H. H.; Chang, S. Tetrahedron 1998, 54, 4413-4450.
6. Molybdenum-based catalyst: (a) Schrock, R. R.; Murdzek, J. S.; Bazan, G. C.; Robbins, J.; DiMare, M.; O'Regan, M. J. Am. Chem. Soc. 1990, 112, 3875-3886. (b) Bazan, G. C.; Khosravi, E.; Schrock, R. R.; Feast, W. J.; Gibson, V. C.; O'Regan, M. B.; Thomas, J. K.; Davis, W. M. J. Am. Chem. Soc. 1990, 112, 8378-8387. (c) Bazan, G. C.; Oskam, J. H.; Cho, H.-N.; Park, L.; Schrock, R. R. J. Am. Chem. Soc. 1991, 113, 6899-6907. Ruthenium-based catalysts: (d) Nguyen, S. T.; Johnson, L. K.; Grubbs, R. H. J. Am. Chem. Soc. 1992, 114, 3974- 3975. (e) Nguyen, S. T.; Grubbs, R. H. J. Am. Chem. Soc. 1993, 115, 9858-9859. (f) Wu, Z.; Nguyen, S. T.; Grubbs, R. H.; Ziller, J. W. J. Am. Chem. Soc. 1995, 117, 5503-5511. (g) Schwab, P.; France, M. B.; Ziller, J. W.; Grubbs, R. H. Angew. Chem., Int. Ed. Engl. 1995, 34, 2039-2041. (h) Schwab, P.; Grubbs, R. H.; Ziller, J. W. J. Am. Chem. Soc. 1996, 118, 100-110.
7. Molybdenum-based catalyst: (a) Schrock, R. R.; Murdzek, J. S.; Bazan, G. C.; Robbins, J.; DiMare, M.; O'Regan, M. J. Am. Chem. Soc. 1990, 112, 3875-3886. (b) Bazan, G. C.; Khosravi, E.; Schrock, R. R.; Feast, W. J.; Gibson, V. C.; O'Regan, M. B.; Thomas, J. K.; Davis, W. M. J. Am. Chem. Soc. 1990, 112, 8378-8387. (c) Bazan, G. C.; Oskam, J. H.; Cho, H.-N.; Park, L.; Schrock, R. R. J. Am. Chem. Soc. 1991, 113, 6899-6907. Ruthenium-based catalysts: (d) Nguyen, S. T.; Johnson, L. K.; Grubbs, R. H. J. Am. Chem. Soc. 1992, 114, 3974- 3975. (e) Nguyen, S. T.; Grubbs, R. H. J. Am. Chem. Soc. 1993, 115, 9858-9859. (f) Wu, Z.; Nguyen, S. T.; Grubbs, R. H.; Ziller, J. W. J. Am. Chem. Soc. 1995, 117, 5503-5511. (g) Schwab, P.; France, M. B.; Ziller, J. W.; Grubbs, R. H. Angew. Chem., Int. Ed. Engl. 1995, 34, 2039-2041. (h) Schwab, P.; Grubbs, R. H.; Ziller, J. W. J. Am. Chem. Soc. 1996, 118, 100-110.
8. Molybdenum-based catalyst: (a) Schrock, R. R.; Murdzek, J. S.; Bazan, G. C.; Robbins, J.; DiMare, M.; O'Regan, M. J. Am. Chem. Soc. 1990, 112, 3875-3886. (b) Bazan, G. C.; Khosravi, E.; Schrock, R. R.; Feast, W. J.; Gibson, V. C.; O'Regan, M. B.; Thomas, J. K.; Davis, W. M. J. Am. Chem. Soc. 1990, 112, 8378-8387. (c) Bazan, G. C.; Oskam, J. H.; Cho, H.-N.; Park, L.; Schrock, R. R. J. Am. Chem. Soc. 1991, 113, 6899-6907. Ruthenium-based catalysts: (d) Nguyen, S. T.; Johnson, L. K.; Grubbs, R. H. J. Am. Chem. Soc. 1992, 114, 3974- 3975. (e) Nguyen, S. T.; Grubbs, R. H. J. Am. Chem. Soc. 1993, 115, 9858-9859. (f) Wu, Z.; Nguyen, S. T.; Grubbs, R. H.; Ziller, J. W. J. Am. Chem. Soc. 1995, 117, 5503-5511. (g) Schwab, P.; France, M. B.; Ziller, J. W.; Grubbs, R. H. Angew. Chem., Int. Ed. Engl. 1995, 34, 2039-2041. (h) Schwab, P.; Grubbs, R. H.; Ziller, J. W. J. Am. Chem. Soc. 1996, 118, 100-110.
9. Molybdenum-based catalyst: (a) Schrock, R. R.; Murdzek, J. S.; Bazan, G. C.; Robbins, J.; DiMare, M.; O'Regan, M. J. Am. Chem. Soc. 1990, 112, 3875-3886. (b) Bazan, G. C.; Khosravi, E.; Schrock, R. R.; Feast, W. J.; Gibson, V. C.; O'Regan, M. B.; Thomas, J. K.; Davis, W. M. J. Am. Chem. Soc. 1990, 112, 8378-8387. (c) Bazan, G. C.; Oskam, J. H.; Cho, H.-N.; Park, L.; Schrock, R. R. J. Am. Chem. Soc. 1991, 113, 6899-6907. Ruthenium-based catalysts: (d) Nguyen, S. T.; Johnson, L. K.; Grubbs, R. H. J. Am. Chem. Soc. 1992, 114, 3974-3975. (e) Nguyen, S. T.; Grubbs, R. H. J. Am. Chem. Soc. 1993, 115, 9858-9859. (f) Wu, Z.; Nguyen, S. T.; Grubbs, R. H.; Ziller, J. W. J. Am. Chem. Soc. 1995, 117, 5503-5511. (g) Schwab, P.; France, M. B.; Ziller, J. W.; Grubbs, R. H. Angew. Chem., Int. Ed. Engl. 1995, 34, 2039-2041. (h) Schwab, P.; Grubbs, R. H.; Ziller, J. W. J. Am. Chem. Soc. 1996, 118, 100-110.
10. Molybdenum-based catalyst: (a) Schrock, R. R.; Murdzek, J. S.; Bazan, G. C.; Robbins, J.; DiMare, M.; O'Regan, M. J. Am. Chem. Soc. 1990, 112, 3875-3886. (b) Bazan, G. C.; Khosravi, E.; Schrock, R. R.; Feast, W. J.; Gibson, V. C.; O'Regan, M. B.; Thomas, J. K.; Davis, W. M. J. Am. Chem. Soc. 1990, 112, 8378-8387. (c) Bazan, G. C.; Oskam, J. H.; Cho, H.-N.; Park, L.; Schrock, R. R. J. Am. Chem. Soc. 1991, 113, 6899-6907. Ruthenium-based catalysts: (d) Nguyen, S. T.; Johnson, L. K.; Grubbs, R. H. J. Am. Chem. Soc. 1992, 114, 3974- 3975. (e) Nguyen, S. T.; Grubbs, R. H. J. Am. Chem. Soc. 1993, 115, 9858-9859. (f) Wu, Z.; Nguyen, S. T.; Grubbs, R. H.; Ziller, J. W. J. Am. Chem. Soc. 1995, 117, 5503-5511. (g) Schwab, P.; France, M. B.; Ziller, J. W.; Grubbs, R. H. Angew. Chem., Int. Ed. Engl. 1995, 34, 2039-2041. (h) Schwab, P.; Grubbs, R. H.; Ziller, J. W. J. Am. Chem. Soc. 1996, 118, 100-110.
11. Molybdenum-based catalyst: (a) Schrock, R. R.; Murdzek, J. S.; Bazan, G. C.; Robbins, J.; DiMare, M.; O'Regan, M. J. Am. Chem. Soc. 1990, 112, 3875-3886. (b) Bazan, G. C.; Khosravi, E.; Schrock, R. R.; Feast, W. J.; Gibson, V. C.; O'Regan, M. B.; Thomas, J. K.; Davis, W. M. J. Am. Chem. Soc. 1990, 112, 8378-8387. (c) Bazan, G. C.; Oskam, J. H.; Cho, H.-N.; Park, L.; Schrock, R. R. J. Am. Chem. Soc. 1991, 113, 6899-6907. Ruthenium-based catalysts: (d) Nguyen, S. T.; Johnson, L. K.; Grubbs, R. H. J. Am. Chem. Soc. 1992, 114, 3974- 3975. (e) Nguyen, S. T.; Grubbs, R. H. J. Am. Chem. Soc. 1993, 115, 9858-9859. (f) Wu, Z.; Nguyen, S. T.; Grubbs, R. H.; Ziller, J. W. J. Am. Chem. Soc. 1995, 117, 5503-5511. (g) Schwab, P.; France, M. B.; Ziller, J. W.; Grubbs, R. H. Angew. Chem., Int. Ed. Engl. 1995, 34, 2039-2041. (h) Schwab, P.; Grubbs, R. H.; Ziller, J. W. J. Am. Chem. Soc. 1996, 118, 100-110.
12. Molybdenum-based catalyst: (a) Schrock, R. R.; Murdzek, J. S.; Bazan, G. C.; Robbins, J.; DiMare, M.; O'Regan, M. J. Am. Chem. Soc. 1990, 112, 3875-3886. (b) Bazan, G. C.; Khosravi, E.; Schrock, R. R.; Feast, W. J.; Gibson, V. C.; O'Regan, M. B.; Thomas, J. K.; Davis, W. M. J. Am. Chem. Soc. 1990, 112, 8378-8387. (c) Bazan, G. C.; Oskam, J. H.; Cho, H.-N.; Park, L.; Schrock, R. R. J. Am. Chem. Soc. 1991, 113, 6899-6907. Ruthenium-based catalysts: (d) Nguyen, S. T.; Johnson, L. K.; Grubbs, R. H. J. Am. Chem. Soc. 1992, 114, 3974- 3975. (e) Nguyen, S. T.; Grubbs, R. H. J. Am. Chem. Soc. 1993, 115, 9858-9859. (f) Wu, Z.; Nguyen, S. T.; Grubbs, R. H.; Ziller, J. W. J. Am. Chem. Soc. 1995, 117, 5503-5511. (g) Schwab, P.; France, M. B.; Ziller, J. W.; Grubbs, R. H. Angew. Chem., Int. Ed. Engl. 1995, 34, 2039-2041. (h) Schwab, P.; Grubbs, R. H.; Ziller, J. W. J. Am. Chem. Soc. 1996, 118, 100-110.
13. Molybdenum-based catalyst: (a) Schrock, R. R.; Murdzek, J. S.; Bazan, G. C.; Robbins, J.; DiMare, M.; O'Regan, M. J. Am. Chem. Soc. 1990, 112, 3875-3886. (b) Bazan, G. C.; Khosravi, E.; Schrock, R. R.; Feast, W. J.; Gibson, V. C.; O'Regan, M. B.; Thomas, J. K.; Davis, W. M. J. Am. Chem. Soc. 1990, 112, 8378-8387. (c) Bazan, G. C.; Oskam, J. H.; Cho, H.-N.; Park, L.; Schrock, R. R. J. Am. Chem. Soc. 1991, 113, 6899-6907. Ruthenium-based catalysts: (d) Nguyen, S. T.; Johnson, L. K.; Grubbs, R. H. J. Am. Chem. Soc. 1992, 114, 3974- 3975. (e) Nguyen, S. T.; Grubbs, R. H. J. Am. Chem. Soc. 1993, 115, 9858-9859. (f) Wu, Z.; Nguyen, S. T.; Grubbs, R. H.; Ziller, J. W. J. Am. Chem. Soc. 1995, 117, 5503-5511. (g) Schwab, P.; France, M. B.; Ziller, J. W.; Grubbs, R. H. Angew. Chem., Int. Ed. Engl. 1995, 34, 2039-2041. (h) Schwab, P.; Grubbs, R. H.; Ziller, J. W. J. Am. Chem. Soc. 1996, 118, 100-110.
14. Recent reviews about RCM: (a) Grubbs, R. H.; Miller, S. J.; Fu, G. C. Acc. Chem. Res. 1995, 28, 446-452. (b) Hashimi, A. S. K. J. Prakt. Chem. 1997, 339, 195-199.
15. Recent reviews about RCM: (a) Grubbs, R. H.; Miller, S. J.; Fu, G. C. Acc. Chem. Res. 1995, 28, 446-452. (b) Hashimi, A. S. K. J. Prakt. Chem. 1997, 339, 195-199.
16. Examples of the use of RCM in the synthesis of trans-fused polyethers: (a) Nicolaou, K. C.; Postema, M. H. D.; Claiborne, C. F. J. Am. Chem. Soc. 1996, 118, 1565-1566. (b) Nicolaou, K. C.; Postema, M. H. D.; Yue, E. W.; Nadin, A. J. Am. Chem. Soc. 1996, 118, 10335- 10336. (c) Clark, J. S.; Kettle, J. G. Tetrahedron Lett. 1987, 38, 123- 126. (d) Clark, J. S.; Kettle, J. G. Tetrahedron Lett. 1997, 38, 127- 130. (e) Oishi, T.; Nagumo, Y.; Hirama, M. Synlett 1997, 980-982. (f) Oishi, T.; Nagumo, Y.; Hirama, M. J. Chem. Soc., Chem. Commun. 1998, 1041-1042. (g) Rainier, J. D.; Allwein, S. P. J. Org. Chem. 1998, 63, 5310-5311. (h) Clark, J. S.; Hamelin, O.; Hufton, R. Tetrahedron Lett. 1998, 39, 8321-8324.
17. Examples of the use of RCM in the synthesis of trans-fused polyethers: (a) Nicolaou, K. C.; Postema, M. H. D.; Claiborne, C. F. J. Am. Chem. Soc. 1996, 118, 1565-1566. (b) Nicolaou, K. C.; Postema, M. H. D.; Yue, E. W.; Nadin, A. J. Am. Chem. Soc. 1996, 118, 10335-10336. (c) Clark, J. S.; Kettle, J. G. Tetrahedron Lett. 1987, 38, 123- 126. (d) Clark, J. S.; Kettle, J. G. Tetrahedron Lett. 1997, 38, 127- 130. (e) Oishi, T.; Nagumo, Y.; Hirama, M. Synlett 1997, 980-982. (f) Oishi, T.; Nagumo, Y.; Hirama, M. J. Chem. Soc., Chem. Commun. 1998, 1041-1042. (g) Rainier, J. D.; Allwein, S. P. J. Org. Chem. 1998, 63, 5310-5311. (h) Clark, J. S.; Hamelin, O.; Hufton, R. Tetrahedron Lett. 1998, 39, 8321-8324.
18. Examples of the use of RCM in the synthesis of trans-fused polyethers: (a) Nicolaou, K. C.; Postema, M. H. D.; Claiborne, C. F. J. Am. Chem. Soc. 1996, 118, 1565-1566. (b) Nicolaou, K. C.; Postema, M. H. D.; Yue, E. W.; Nadin, A. J. Am. Chem. Soc. 1996, 118, 10335- 10336. (c) Clark, J. S.; Kettle, J. G. Tetrahedron Lett. 1987, 38, 123-126. (d) Clark, J. S.; Kettle, J. G. Tetrahedron Lett. 1997, 38, 127- 130. (e) Oishi, T.; Nagumo, Y.; Hirama, M. Synlett 1997, 980-982. (f) Oishi, T.; Nagumo, Y.; Hirama, M. J. Chem. Soc., Chem. Commun. 1998, 1041-1042. (g) Rainier, J. D.; Allwein, S. P. J. Org. Chem. 1998, 63, 5310-5311. (h) Clark, J. S.; Hamelin, O.; Hufton, R. Tetrahedron Lett. 1998, 39, 8321-8324.
19. Examples of the use of RCM in the synthesis of trans-fused polyethers: (a) Nicolaou, K. C.; Postema, M. H. D.; Claiborne, C. F. J. Am. Chem. Soc. 1996, 118, 1565-1566. (b) Nicolaou, K. C.; Postema, M. H. D.; Yue, E. W.; Nadin, A. J. Am. Chem. Soc. 1996, 118, 10335- 10336. (c) Clark, J. S.; Kettle, J. G. Tetrahedron Lett. 1987, 38, 123- 126. (d) Clark, J. S.; Kettle, J. G. Tetrahedron Lett. 1997, 38, 127-130. (e) Oishi, T.; Nagumo, Y.; Hirama, M. Synlett 1997, 980-982. (f) Oishi, T.; Nagumo, Y.; Hirama, M. J. Chem. Soc., Chem. Commun. 1998, 1041-1042. (g) Rainier, J. D.; Allwein, S. P. J. Org. Chem. 1998, 63, 5310-5311. (h) Clark, J. S.; Hamelin, O.; Hufton, R. Tetrahedron Lett. 1998, 39, 8321-8324.
20. Examples of the use of RCM in the synthesis of trans-fused polyethers: (a) Nicolaou, K. C.; Postema, M. H. D.; Claiborne, C. F. J. Am. Chem. Soc. 1996, 118, 1565-1566. (b) Nicolaou, K. C.; Postema, M. H. D.; Yue, E. W.; Nadin, A. J. Am. Chem. Soc. 1996, 118, 10335- 10336. (c) Clark, J. S.; Kettle, J. G. Tetrahedron Lett. 1987, 38, 123- 126. (d) Clark, J. S.; Kettle, J. G. Tetrahedron Lett. 1997, 38, 127- 130. (e) Oishi, T.; Nagumo, Y.; Hirama, M. Synlett 1997, 980-982. (f) Oishi, T.; Nagumo, Y.; Hirama, M. J. Chem. Soc., Chem. Commun. 1998, 1041-1042. (g) Rainier, J. D.; Allwein, S. P. J. Org. Chem. 1998, 63, 5310-5311. (h) Clark, J. S.; Hamelin, O.; Hufton, R. Tetrahedron Lett. 1998, 39, 8321-8324.
21. Examples of the use of RCM in the synthesis of trans-fused polyethers: (a) Nicolaou, K. C.; Postema, M. H. D.; Claiborne, C. F. J. Am. Chem. Soc. 1996, 118, 1565-1566. (b) Nicolaou, K. C.; Postema, M. H. D.; Yue, E. W.; Nadin, A. J. Am. Chem. Soc. 1996, 118, 10335- 10336. (c) Clark, J. S.; Kettle, J. G. Tetrahedron Lett. 1987, 38, 123- 126. (d) Clark, J. S.; Kettle, J. G. Tetrahedron Lett. 1997, 38, 127- 130. (e) Oishi, T.; Nagumo, Y.; Hirama, M. Synlett 1997, 980-982. (f) Oishi, T.; Nagumo, Y.; Hirama, M. J. Chem. Soc., Chem. Commun. 1998, 1041-1042. (g) Rainier, J. D.; Allwein, S. P. J. Org. Chem. 1998, 63, 5310-5311. (h) Clark, J. S.; Hamelin, O.; Hufton, R. Tetrahedron Lett. 1998, 39, 8321-8324.
22. Examples of the use of RCM in the synthesis of trans-fused polyethers: (a) Nicolaou, K. C.; Postema, M. H. D.; Claiborne, C. F. J. Am. Chem. Soc. 1996, 118, 1565-1566. (b) Nicolaou, K. C.; Postema, M. H. D.; Yue, E. W.; Nadin, A. J. Am. Chem. Soc. 1996, 118, 10335- 10336. (c) Clark, J. S.; Kettle, J. G. Tetrahedron Lett. 1987, 38, 123- 126. (d) Clark, J. S.; Kettle, J. G. Tetrahedron Lett. 1997, 38, 127- 130. (e) Oishi, T.; Nagumo, Y.; Hirama, M. Synlett 1997, 980-982. (f) Oishi, T.; Nagumo, Y.; Hirama, M. J. Chem. Soc., Chem. Commun. 1998, 1041-1042. (g) Rainier, J. D.; Allwein, S. P. J. Org. Chem. 1998, 63, 5310-5311. (h) Clark, J. S.; Hamelin, O.; Hufton, R. Tetrahedron Lett. 1998, 39, 8321-8324.
23. Examples of the use of RCM in the synthesis of trans-fused polyethers: (a) Nicolaou, K. C.; Postema, M. H. D.; Claiborne, C. F. J. Am. Chem. Soc. 1996, 118, 1565-1566. (b) Nicolaou, K. C.; Postema, M. H. D.; Yue, E. W.; Nadin, A. J. Am. Chem. Soc. 1996, 118, 10335- 10336. (c) Clark, J. S.; Kettle, J. G. Tetrahedron Lett. 1987, 38, 123- 126. (d) Clark, J. S.; Kettle, J. G. Tetrahedron Lett. 1997, 38, 127- 130. (e) Oishi, T.; Nagumo, Y.; Hirama, M. Synlett 1997, 980-982. (f) Oishi, T.; Nagumo, Y.; Hirama, M. J. Chem. Soc., Chem. Commun. 1998, 1041-1042. (g) Rainier, J. D.; Allwein, S. P. J. Org. Chem. 1998, 63, 5310-5311. (h) Clark, J. S.; Hamelin, O.; Hufton, R. Tetrahedron Lett. 1998, 39, 8321-8324.
24. Delgado, M.; Martín, J. D. Tetrahedron Lett. 1997, 38, 6299-6300.
25. Nicolaou, K. C.; Hwang, C.-K.; Marron, B. E.; DeFrees, S. A.; Couladourus, E. A.; Abe, Y.; Carroll, O. J.; Snyder, J. P. J. Am. Chem. Soc. 1990, 112, 3040-3054.
26. For the preparation of these aldehydes, see Supporting Information.
27. The configuration of the new asymmetric center was unequivocally assigned by NOESY experiments.
28. Garegg, P. J.; Samuelson, D. J. Chem. Soc., Perkin Trans. 1 1980, 2866-2869.
29. Adam, G.; Seebach, D. Synthesis 1988, 373-375.
30. Low yields obtained in the case of the smaller dienes are due to the volatility of the products.
31. Marshall, J. A.; Andersen, N. H.; Schlicher, J. W. J. Org. Chem. 1970, 35, 858-861.
32. Keck, G. E.; Enholm, E. J.; Yates, J. B.; Wiley: M. R. Tetrahedron 1985, 41, 4079-4094.
33. Eliel, E. L.; Wilen, S. H. Stereochemistry of Organic Compounds; John Wiley and Sons: New York, 1994.
34. Examples of formation of eight-membered rings by olefin metathesis of acyclic precursors containing some conformational restriction: (a) Linderman, R. J.; Siedlecki, J.; O'Neill, S. A.; Sun, H. J. Am. Chem. Soc. 1997, 119, 6919-6920. (b) Crimmins, M. T.; Choy, A. L. J. Org. Chem. 1997, 62, 7548-7549. (c) Visser, M. S.; Heron, N. M.; Didiuk, M. T.; Sagal, J. F.; Hoveyda, A. H. J. Am. Chem. Soc. 1996, 118, 4291-4298.
35. Examples of formation of eight-membered rings by olefin metathesis of acyclic precursors containing some conformational restriction: (a) Linderman, R. J.; Siedlecki, J.; O'Neill, S. A.; Sun, H. J. Am. Chem. Soc. 1997, 119, 6919-6920. (b) Crimmins, M. T.; Choy, A. L. J. Org. Chem. 1997, 62, 7548-7549. (c) Visser, M. S.; Heron, N. M.; Didiuk, M. T.; Sagal, J. F.; Hoveyda, A. H. J. Am. Chem. Soc. 1996, 118, 4291-4298.
36. Examples of formation of eight-membered rings by olefin metathesis of acyclic precursors containing some conformational restriction: (a) Linderman, R. J.; Siedlecki, J.; O'Neill, S. A.; Sun, H. J. Am. Chem. Soc. 1997, 119, 6919-6920. (b) Crimmins, M. T.; Choy, A. L. J. Org. Chem. 1997, 62, 7548-7549. (c) Visser, M. S.; Heron, N. M.; Didiuk, M. T.; Sagal, J. F.; Hoveyda, A. H. J. Am. Chem. Soc. 1996, 118, 4291-4298.
37. In the precursors of eight-membered rings in which the conformational restriction element is a preexisting cycle, RCM is more effective when the two olefinic chains are in trans disposition on the cycle than when they are cis: Miller, S. J.; Kim, S.-H.; Chen, Z.-R.; Grubbs, R. H. J. Am. Chem. Soc. 1995, 117, 2108-2109.
38. Detailed studies of RCM mechanism: (a) Dias, E. L.; Nguyen, S. T.; Grubbs, R. H. J. Am. Chem. Soc. 1997, 119, 3887-3897. (b) Aagaard, O. M.; Meier, R. J.; Buda, F. J. Am. Chem. Soc. 1898, 120, 7174-7182.
39. Detailed studies of RCM mechanism: (a) Dias, E. L.; Nguyen, S. T.; Grubbs, R. H. J. Am. Chem. Soc. 1997, 119, 3887-3897. (b) Aagaard, O. M.; Meier, R. J.; Buda, F. J. Am. Chem. Soc. 1898, 120, 7174-7182.
40. Examples of formation of chelates in RCM: (a) Kirkland, T. A.; Grubbs, R. H. J. Org. Chem. 1997, 62, 7310-7318. (b) Ghosh, A. K.; Capiello, J.; Shin, D. Tetrahedron Lett. 1998, 39, 4651-4654. (c) Fu, G. C.; Grubbs, R. H. J. Am. Chem. Soc. 1992, 114, 7324-7325. (d) Campagne, J.-M.; Ghosez, L. Tetrahedron Lett. 1998, 39, 6175-6178. (e) Harrity, J. P. A.; La, D. S.; Cefalo, D. R.; Visser, M. S.; Hoveyda, A. H. J. Am. Chem. Soc. 1998, 120, 2343-2351. (f) Feldman, J.; Murdzek, J. S.; Davis, W. M.; Schrock, R. R. Organometallics 1989, 8, 2260- 2265. (g) Fürstner, A.; Langemann, K. J. Am. Chem. Soc. 1997, 119, 9130-9136. (h) Kingsbury, J. S.; Harrity, J. P. A.; Bonitatebus, P. J., Jr.; Hoveyda, A. H. J. Am. Chem. Soc. 1999, 121, 791-799.
41. Examples of formation of chelates in RCM: (a) Kirkland, T. A.; Grubbs, R. H. J. Org. Chem. 1997, 62, 7310-7318. (b) Ghosh, A. K.; Capiello, J.; Shin, D. Tetrahedron Lett. 1998, 39, 4651-4654. (c) Fu, G. C.; Grubbs, R. H. J. Am. Chem. Soc. 1992, 114, 7324-7325. (d) Campagne, J.-M.; Ghosez, L. Tetrahedron Lett. 1998, 39, 6175-6178. (e) Harrity, J. P. A.; La, D. S.; Cefalo, D. R.; Visser, M. S.; Hoveyda, A. H. J. Am. Chem. Soc. 1998, 120, 2343-2351. (f) Feldman, J.; Murdzek, J. S.; Davis, W. M.; Schrock, R. R. Organometallics 1989, 8, 2260- 2265. (g) Fürstner, A.; Langemann, K. J. Am. Chem. Soc. 1997, 119, 9130-9136. (h) Kingsbury, J. S.; Harrity, J. P. A.; Bonitatebus, P. J., Jr.; Hoveyda, A. H. J. Am. Chem. Soc. 1999, 121, 791-799.
42. Examples of formation of chelates in RCM: (a) Kirkland, T. A.; Grubbs, R. H. J. Org. Chem. 1997, 62, 7310-7318. (b) Ghosh, A. K.; Capiello, J.; Shin, D. Tetrahedron Lett. 1998, 39, 4651-4654. (c) Fu, G. C.; Grubbs, R. H. J. Am. Chem. Soc. 1992, 114, 7324-7325. (d) Campagne, J.-M.; Ghosez, L. Tetrahedron Lett. 1998, 39, 6175-6178. (e) Harrity, J. P. A.; La, D. S.; Cefalo, D. R.; Visser, M. S.; Hoveyda, A. H. J. Am. Chem. Soc. 1998, 120, 2343-2351. (f) Feldman, J.; Murdzek, J. S.; Davis, W. M.; Schrock, R. R. Organometallics 1989, 8, 2260- 2265. (g) Fürstner, A.; Langemann, K. J. Am. Chem. Soc. 1997, 119, 9130-9136. (h) Kingsbury, J. S.; Harrity, J. P. A.; Bonitatebus, P. J., Jr.; Hoveyda, A. H. J. Am. Chem. Soc. 1999, 121, 791-799.
43. Examples of formation of chelates in RCM: (a) Kirkland, T. A.; Grubbs, R. H. J. Org. Chem. 1997, 62, 7310-7318. (b) Ghosh, A. K.; Capiello, J.; Shin, D. Tetrahedron Lett. 1998, 39, 4651-4654. (c) Fu, G. C.; Grubbs, R. H. J. Am. Chem. Soc. 1992, 114, 7324-7325. (d) Campagne, J.-M.; Ghosez, L. Tetrahedron Lett. 1998, 39, 6175-6178. (e) Harrity, J. P. A.; La, D. S.; Cefalo, D. R.; Visser, M. S.; Hoveyda, A. H. J. Am. Chem. Soc. 1998, 120, 2343-2351. (f) Feldman, J.; Murdzek, J. S.; Davis, W. M.; Schrock, R. R. Organometallics 1989, 8, 2260- 2265. (g) Fürstner, A.; Langemann, K. J. Am. Chem. Soc. 1997, 119, 9130-9136. (h) Kingsbury, J. S.; Harrity, J. P. A.; Bonitatebus, P. J., Jr.; Hoveyda, A. H. J. Am. Chem. Soc. 1999, 121, 791-799.
44. Examples of formation of chelates in RCM: (a) Kirkland, T. A.; Grubbs, R. H. J. Org. Chem. 1997, 62, 7310-7318. (b) Ghosh, A. K.; Capiello, J.; Shin, D. Tetrahedron Lett. 1998, 39, 4651-4654. (c) Fu, G. C.; Grubbs, R. H. J. Am. Chem. Soc. 1992, 114, 7324-7325. (d) Campagne, J.-M.; Ghosez, L. Tetrahedron Lett. 1998, 39, 6175-6178. (e) Harrity, J. P. A.; La, D. S.; Cefalo, D. R.; Visser, M. S.; Hoveyda, A. H. J. Am. Chem. Soc. 1998, 120, 2343-2351. (f) Feldman, J.; Murdzek, J. S.; Davis, W. M.; Schrock, R. R. Organometallics 1989, 8, 2260- 2265. (g) Fürstner, A.; Langemann, K. J. Am. Chem. Soc. 1997, 119, 9130-9136. (h) Kingsbury, J. S.; Harrity, J. P. A.; Bonitatebus, P. J., Jr.; Hoveyda, A. H. J. Am. Chem. Soc. 1999, 121, 791-799.
45. Examples of formation of chelates in RCM: (a) Kirkland, T. A.; Grubbs, R. H. J. Org. Chem. 1997, 62, 7310-7318. (b) Ghosh, A. K.; Capiello, J.; Shin, D. Tetrahedron Lett. 1998, 39, 4651-4654. (c) Fu, G. C.; Grubbs, R. H. J. Am. Chem. Soc. 1992, 114, 7324-7325. (d) Campagne, J.-M.; Ghosez, L. Tetrahedron Lett. 1998, 39, 6175-6178. (e) Harrity, J. P. A.; La, D. S.; Cefalo, D. R.; Visser, M. S.; Hoveyda, A. H. J. Am. Chem. Soc. 1998, 120, 2343-2351. (f) Feldman, J.; Murdzek, J. S.; Davis, W. M.; Schrock, R. R. Organometallics 1989, 8, 2260-2265. (g) Fürstner, A.; Langemann, K. J. Am. Chem. Soc. 1997, 119, 9130-9136. (h) Kingsbury, J. S.; Harrity, J. P. A.; Bonitatebus, P. J., Jr.; Hoveyda, A. H. J. Am. Chem. Soc. 1999, 121, 791-799.
46. Examples of formation of chelates in RCM: (a) Kirkland, T. A.; Grubbs, R. H. J. Org. Chem. 1997, 62, 7310-7318. (b) Ghosh, A. K.; Capiello, J.; Shin, D. Tetrahedron Lett. 1998, 39, 4651-4654. (c) Fu, G. C.; Grubbs, R. H. J. Am. Chem. Soc. 1992, 114, 7324-7325. (d) Campagne, J.-M.; Ghosez, L. Tetrahedron Lett. 1998, 39, 6175-6178. (e) Harrity, J. P. A.; La, D. S.; Cefalo, D. R.; Visser, M. S.; Hoveyda, A. H. J. Am. Chem. Soc. 1998, 120, 2343-2351. (f) Feldman, J.; Murdzek, J. S.; Davis, W. M.; Schrock, R. R. Organometallics 1989, 8, 2260- 2265. (g) Fürstner, A.; Langemann, K. J. Am. Chem. Soc. 1997, 119, 9130-9136. (h) Kingsbury, J. S.; Harrity, J. P. A.; Bonitatebus, P. J., Jr.; Hoveyda, A. H. J. Am. Chem. Soc. 1999, 121, 791-799.
47. Examples of formation of chelates in RCM: (a) Kirkland, T. A.; Grubbs, R. H. J. Org. Chem. 1997, 62, 7310-7318. (b) Ghosh, A. K.; Capiello, J.; Shin, D. Tetrahedron Lett. 1998, 39, 4651-4654. (c) Fu, G. C.; Grubbs, R. H. J. Am. Chem. Soc. 1992, 114, 7324-7325. (d) Campagne, J.-M.; Ghosez, L. Tetrahedron Lett. 1998, 39, 6175-6178. (e) Harrity, J. P. A.; La, D. S.; Cefalo, D. R.; Visser, M. S.; Hoveyda, A. H. J. Am. Chem. Soc. 1998, 120, 2343-2351. (f) Feldman, J.; Murdzek, J. S.; Davis, W. M.; Schrock, R. R. Organometallics 1989, 8, 2260- 2265. (g) Fürstner, A.; Langemann, K. J. Am. Chem. Soc. 1997, 119, 9130-9136. (h) Kingsbury, J. S.; Harrity, J. P. A.; Bonitatebus, P. J., Jr.; Hoveyda, A. H. J. Am. Chem. Soc. 1999, 121, 791-799.
48. Examples of Z geometry in 9-and 10-membered rings obtained by RCM: (a) Barrett, A. G. M.; Baugh, S. P. D.; Gibson, V. C.; Giles, M. R.; Marshall, E. L.; Procopiou, P. A. Chem. Commun. 1996, 2231-2232. (b) Crimmins, M. T.; Choy, A. L. J. Org. Chem. 1997, 62, 7548- 7549. (c) Sukkari, H. E.; Gesson, J.-P.; Renoux, B. Tetrahedron Lett. 1998, 39, 4043-4046. (d) Oishi, T.; Nagumo, Y.; Hirama. M. Chem. Commun. 1998, 1041-1042. Example of E geometry in a 10-membered ring: (e) Fink, B. E.; Kym, P. R.; Katzenellenbogen, J. A. J. Am. Chem. Soc. 1998, 120, 4334-4344. (f) Sukkari, H. E.; Gesson, J.-P.; Renoux, B. Tetrahedron Lett. 1998, 39, 4043-4046 (9-, 11-, and 15-membered rings). (g) Fürstner, A.; Kindler, N. Tetrahedron Lett. 1996, 37, 7005- 7008 (12-membered ring). (h) Borer, B. C.; Deerenberg, S.; Bieräugel, H.; Pandit, U. K. Tetrahedron Lett. 1994, 35, 3191-3194 (13-membered ring, Z). (i) Kim, S. H.; Figueroa, I.; Fuchs, P. L. Tetrahedron Lett. 1997, 38, 2601-2604 (13-membered ring, E). (j) Houri, A. F.; Xu, Z.; Cogan, D. A.; Hoveyda, A. H. J. Am. Chem. Soc. 1995, 117, 2943- 2944 (14-membered ring, Z). (k) Fürstner, A.; Langemann, K. J. Org. Chem. 1996, 61, 3942-3943 (14-, 16-, and 20-membered rings). (l) Ghosh, A. K.; Hussain, K. A. Tetrahedron Lett. 1998, 39, 1881-1884 (14-membered rings, Z, 15-membered rings, Z and 16-membered rings, mixtures). (m) Ripka, A. S.; Bohacek, R. S.; Rich, D. H. Bioorg. Med. Chem. Lett. 1998, 8, 357-360 (15-membered ring, mixtures). (n) Meng, D.; Su, D.-S.; Balog, A.; Bertinato, P.; Sorensen, E. J.; Danishefsky, S. J.; Zheng, Y.-H.; Chou, T.-C.; He, L.; Horwitz, S. J. Am. Chem. Soc. 1997, 119, 2733-2734.
49. Examples of Z geometry in 9-and 10-membered rings obtained by RCM: (a) Barrett, A. G. M.; Baugh, S. P. D.; Gibson, V. C.; Giles, M. R.; Marshall, E. L.; Procopiou, P. A. Chem. Commun. 1996, 2231- 2232. (b) Crimmins, M. T.; Choy, A. L. J. Org. Chem. 1997, 62, 7548-7549. (c) Sukkari, H. E.; Gesson, J.-P.; Renoux, B. Tetrahedron Lett. 1998, 39, 4043-4046. (d) Oishi, T.; Nagumo, Y.; Hirama. M. Chem. Commun. 1998, 1041-1042. Example of E geometry in a 10-membered ring: (e) Fink, B. E.; Kym, P. R.; Katzenellenbogen, J. A. J. Am. Chem. Soc. 1998, 120, 4334-4344. (f) Sukkari, H. E.; Gesson, J.-P.; Renoux, B. Tetrahedron Lett. 1998, 39, 4043-4046 (9-, 11-, and 15-membered rings). (g) Fürstner, A.; Kindler, N. Tetrahedron Lett. 1996, 37, 7005- 7008 (12-membered ring). (h) Borer, B. C.; Deerenberg, S.; Bieräugel, H.; Pandit, U. K. Tetrahedron Lett. 1994, 35, 3191-3194 (13-membered ring, Z). (i) Kim, S. H.; Figueroa, I.; Fuchs, P. L. Tetrahedron Lett. 1997, 38, 2601-2604 (13-membered ring, E). (j) Houri, A. F.; Xu, Z.; Cogan, D. A.; Hoveyda, A. H. J. Am. Chem. Soc. 1995, 117, 2943- 2944 (14-membered ring, Z). (k) Fürstner, A.; Langemann, K. J. Org. Chem. 1996, 61, 3942-3943 (14-, 16-, and 20-membered rings). (l) Ghosh, A. K.; Hussain, K. A. Tetrahedron Lett. 1998, 39, 1881-1884 (14-membered rings, Z, 15-membered rings, Z and 16-membered rings, mixtures). (m) Ripka, A. S.; Bohacek, R. S.; Rich, D. H. Bioorg. Med. Chem. Lett. 1998, 8, 357-360 (15-membered ring, mixtures). (n) Meng, D.; Su, D.-S.; Balog, A.; Bertinato, P.; Sorensen, E. J.; Danishefsky, S. J.; Zheng, Y.-H.; Chou, T.-C.; He, L.; Horwitz, S. J. Am. Chem. Soc. 1997, 119, 2733-2734.
50. Examples of Z geometry in 9-and 10-membered rings obtained by RCM: (a) Barrett, A. G. M.; Baugh, S. P. D.; Gibson, V. C.; Giles, M. R.; Marshall, E. L.; Procopiou, P. A. Chem. Commun. 1996, 2231- 2232. (b) Crimmins, M. T.; Choy, A. L. J. Org. Chem. 1997, 62, 7548- 7549. (c) Sukkari, H. E.; Gesson, J.-P.; Renoux, B. Tetrahedron Lett. 1998, 39, 4043-4046. (d) Oishi, T.; Nagumo, Y.; Hirama. M. Chem. Commun. 1998, 1041-1042. Example of E geometry in a 10-membered ring: (e) Fink, B. E.; Kym, P. R.; Katzenellenbogen, J. A. J. Am. Chem. Soc. 1998, 120, 4334-4344. (f) Sukkari, H. E.; Gesson, J.-P.; Renoux, B. Tetrahedron Lett. 1998, 39, 4043-4046 (9-, 11-, and 15-membered rings). (g) Fürstner, A.; Kindler, N. Tetrahedron Lett. 1996, 37, 7005- 7008 (12-membered ring). (h) Borer, B. C.; Deerenberg, S.; Bieräugel, H.; Pandit, U. K. Tetrahedron Lett. 1994, 35, 3191-3194 (13-membered ring, Z). (i) Kim, S. H.; Figueroa, I.; Fuchs, P. L. Tetrahedron Lett. 1997, 38, 2601-2604 (13-membered ring, E). (j) Houri, A. F.; Xu, Z.; Cogan, D. A.; Hoveyda, A. H. J. Am. Chem. Soc. 1995, 117, 2943- 2944 (14-membered ring, Z). (k) Fürstner, A.; Langemann, K. J. Org. Chem. 1996, 61, 3942-3943 (14-, 16-, and 20-membered rings). (l) Ghosh, A. K.; Hussain, K. A. Tetrahedron Lett. 1998, 39, 1881-1884 (14-membered rings, Z, 15-membered rings, Z and 16-membered rings, mixtures). (m) Ripka, A. S.; Bohacek, R. S.; Rich, D. H. Bioorg. Med. Chem. Lett. 1998, 8, 357-360 (15-membered ring, mixtures). (n) Meng, D.; Su, D.-S.; Balog, A.; Bertinato, P.; Sorensen, E. J.; Danishefsky, S. J.; Zheng, Y.-H.; Chou, T.-C.; He, L.; Horwitz, S. J. Am. Chem. Soc. 1997, 119, 2733-2734.
51. Examples of Z geometry in 9-and 10-membered rings obtained by RCM: (a) Barrett, A. G. M.; Baugh, S. P. D.; Gibson, V. C.; Giles, M. R.; Marshall, E. L.; Procopiou, P. A. Chem. Commun. 1996, 2231- 2232. (b) Crimmins, M. T.; Choy, A. L. J. Org. Chem. 1997, 62, 7548- 7549. (c) Sukkari, H. E.; Gesson, J.-P.; Renoux, B. Tetrahedron Lett. 1998, 39, 4043-4046. (d) Oishi, T.; Nagumo, Y.; Hirama. M. Chem. Commun. 1998, 1041-1042. Example of E geometry in a 10-membered ring: (e) Fink, B. E.; Kym, P. R.; Katzenellenbogen, J. A. J. Am. Chem. Soc. 1998, 120, 4334-4344. (f) Sukkari, H. E.; Gesson, J.-P.; Renoux, B. Tetrahedron Lett. 1998, 39, 4043-4046 (9-, 11-, and 15-membered rings). (g) Fürstner, A.; Kindler, N. Tetrahedron Lett. 1996, 37, 7005- 7008 (12-membered ring). (h) Borer, B. C.; Deerenberg, S.; Bieräugel, H.; Pandit, U. K. Tetrahedron Lett. 1994, 35, 3191-3194 (13-membered ring, Z). (i) Kim, S. H.; Figueroa, I.; Fuchs, P. L. Tetrahedron Lett. 1997, 38, 2601-2604 (13-membered ring, E). (j) Houri, A. F.; Xu, Z.; Cogan, D. A.; Hoveyda, A. H. J. Am. Chem. Soc. 1995, 117, 2943- 2944 (14-membered ring, Z). (k) Fürstner, A.; Langemann, K. J. Org. Chem. 1996, 61, 3942-3943 (14-, 16-, and 20-membered rings). (l) Ghosh, A. K.; Hussain, K. A. Tetrahedron Lett. 1998, 39, 1881-1884 (14-membered rings, Z, 15-membered rings, Z and 16-membered rings, mixtures). (m) Ripka, A. S.; Bohacek, R. S.; Rich, D. H. Bioorg. Med. Chem. Lett. 1998, 8, 357-360 (15-membered ring, mixtures). (n) Meng, D.; Su, D.-S.; Balog, A.; Bertinato, P.; Sorensen, E. J.; Danishefsky, S. J.; Zheng, Y.-H.; Chou, T.-C.; He, L.; Horwitz, S. J. Am. Chem. Soc. 1997, 119, 2733-2734.
52. Examples of Z geometry in 9-and 10-membered rings obtained by RCM: (a) Barrett, A. G. M.; Baugh, S. P. D.; Gibson, V. C.; Giles, M. R.; Marshall, E. L.; Procopiou, P. A. Chem. Commun. 1996, 2231- 2232. (b) Crimmins, M. T.; Choy, A. L. J. Org. Chem. 1997, 62, 7548- 7549. (c) Sukkari, H. E.; Gesson, J.-P.; Renoux, B. Tetrahedron Lett. 1998, 39, 4043-4046. (d) Oishi, T.; Nagumo, Y.; Hirama. M. Chem. Commun. 1998, 1041-1042. Example of E geometry in a 10-membered ring: (e) Fink, B. E.; Kym, P. R.; Katzenellenbogen, J. A. J. Am. Chem. Soc. 1998, 120, 4334-4344. (f) Sukkari, H. E.; Gesson, J.-P.; Renoux, B. Tetrahedron Lett. 1998, 39, 4043-4046 (9-, 11-, and 15-membered rings). (g) Fürstner, A.; Kindler, N. Tetrahedron Lett. 1996, 37, 7005- 7008 (12-membered ring). (h) Borer, B. C.; Deerenberg, S.; Bieräugel, H.; Pandit, U. K. Tetrahedron Lett. 1994, 35, 3191-3194 (13-membered ring, Z). (i) Kim, S. H.; Figueroa, I.; Fuchs, P. L. Tetrahedron Lett. 1997, 38, 2601-2604 (13-membered ring, E). (j) Houri, A. F.; Xu, Z.; Cogan, D. A.; Hoveyda, A. H. J. Am. Chem. Soc. 1995, 117, 2943- 2944 (14-membered ring, Z). (k) Fürstner, A.; Langemann, K. J. Org. Chem. 1996, 61, 3942-3943 (14-, 16-, and 20-membered rings). (l) Ghosh, A. K.; Hussain, K. A. Tetrahedron Lett. 1998, 39, 1881-1884 (14-membered rings, Z, 15-membered rings, Z and 16-membered rings, mixtures). (m) Ripka, A. S.; Bohacek, R. S.; Rich, D. H. Bioorg. Med. Chem. Lett. 1998, 8, 357-360 (15-membered ring, mixtures). (n) Meng, D.; Su, D.-S.; Balog, A.; Bertinato, P.; Sorensen, E. J.; Danishefsky, S. J.; Zheng, Y.-H.; Chou, T.-C.; He, L.; Horwitz, S. J. Am. Chem. Soc. 1997, 119, 2733-2734.
53. Examples of Z geometry in 9-and 10-membered rings obtained by RCM: (a) Barrett, A. G. M.; Baugh, S. P. D.; Gibson, V. C.; Giles, M. R.; Marshall, E. L.; Procopiou, P. A. Chem. Commun. 1996, 2231- 2232. (b) Crimmins, M. T.; Choy, A. L. J. Org. Chem. 1997, 62, 7548- 7549. (c) Sukkari, H. E.; Gesson, J.-P.; Renoux, B. Tetrahedron Lett. 1998, 39, 4043-4046. (d) Oishi, T.; Nagumo, Y.; Hirama. M. Chem. Commun. 1998, 1041-1042. Example of E geometry in a 10-membered ring: (e) Fink, B. E.; Kym, P. R.; Katzenellenbogen, J. A. J. Am. Chem. Soc. 1998, 120, 4334-4344. (f) Sukkari, H. E.; Gesson, J.-P.; Renoux, B. Tetrahedron Lett. 1998, 39, 4043-4046 (9-, 11-, and 15-membered rings). (g) Fürstner, A.; Kindler, N. Tetrahedron Lett. 1996, 37, 7005- 7008 (12-membered ring). (h) Borer, B. C.; Deerenberg, S.; Bieräugel, H.; Pandit, U. K. Tetrahedron Lett. 1994, 35, 3191-3194 (13-membered ring, Z). (i) Kim, S. H.; Figueroa, I.; Fuchs, P. L. Tetrahedron Lett. 1997, 38, 2601-2604 (13-membered ring, E). (j) Houri, A. F.; Xu, Z.; Cogan, D. A.; Hoveyda, A. H. J. Am. Chem. Soc. 1995, 117, 2943- 2944 (14-membered ring, Z). (k) Fürstner, A.; Langemann, K. J. Org. Chem. 1996, 61, 3942-3943 (14-, 16-, and 20-membered rings). (l) Ghosh, A. K.; Hussain, K. A. Tetrahedron Lett. 1998, 39, 1881-1884 (14-membered rings, Z, 15-membered rings, Z and 16-membered rings, mixtures). (m) Ripka, A. S.; Bohacek, R. S.; Rich, D. H. Bioorg. Med. Chem. Lett. 1998, 8, 357-360 (15-membered ring, mixtures). (n) Meng, D.; Su, D.-S.; Balog, A.; Bertinato, P.; Sorensen, E. J.; Danishefsky, S. J.; Zheng, Y.-H.; Chou, T.-C.; He, L.; Horwitz, S. J. Am. Chem. Soc. 1997, 119, 2733-2734.
54. Examples of Z geometry in 9-and 10-membered rings obtained by RCM: (a) Barrett, A. G. M.; Baugh, S. P. D.; Gibson, V. C.; Giles, M. R.; Marshall, E. L.; Procopiou, P. A. Chem. Commun. 1996, 2231- 2232. (b) Crimmins, M. T.; Choy, A. L. J. Org. Chem. 1997, 62, 7548- 7549. (c) Sukkari, H. E.; Gesson, J.-P.; Renoux, B. Tetrahedron Lett. 1998, 39, 4043-4046. (d) Oishi, T.; Nagumo, Y.; Hirama. M. Chem. Commun. 1998, 1041-1042. Example of E geometry in a 10-membered ring: (e) Fink, B. E.; Kym, P. R.; Katzenellenbogen, J. A. J. Am. Chem. Soc. 1998, 120, 4334-4344. (f) Sukkari, H. E.; Gesson, J.-P.; Renoux, B. Tetrahedron Lett. 1998, 39, 4043-4046 (9-, 11-, and 15-membered rings). (g) Fürstner, A.; Kindler, N. Tetrahedron Lett. 1996, 37, 7005-7008 (12-membered ring). (h) Borer, B. C.; Deerenberg, S.; Bieräugel, H.; Pandit, U. K. Tetrahedron Lett. 1994, 35, 3191-3194 (13-membered ring, Z). (i) Kim, S. H.; Figueroa, I.; Fuchs, P. L. Tetrahedron Lett. 1997, 38, 2601-2604 (13-membered ring, E). (j) Houri, A. F.; Xu, Z.; Cogan, D. A.; Hoveyda, A. H. J. Am. Chem. Soc. 1995, 117, 2943- 2944 (14-membered ring, Z). (k) Fürstner, A.; Langemann, K. J. Org. Chem. 1996, 61, 3942-3943 (14-, 16-, and 20-membered rings). (l) Ghosh, A. K.; Hussain, K. A. Tetrahedron Lett. 1998, 39, 1881-1884 (14-membered rings, Z, 15-membered rings, Z and 16-membered rings, mixtures). (m) Ripka, A. S.; Bohacek, R. S.; Rich, D. H. Bioorg. Med. Chem. Lett. 1998, 8, 357-360 (15-membered ring, mixtures). (n) Meng, D.; Su, D.-S.; Balog, A.; Bertinato, P.; Sorensen, E. J.; Danishefsky, S. J.; Zheng, Y.-H.; Chou, T.-C.; He, L.; Horwitz, S. J. Am. Chem. Soc. 1997, 119, 2733-2734.
55. Examples of Z geometry in 9-and 10-membered rings obtained by RCM: (a) Barrett, A. G. M.; Baugh, S. P. D.; Gibson, V. C.; Giles, M. R.; Marshall, E. L.; Procopiou, P. A. Chem. Commun. 1996, 2231- 2232. (b) Crimmins, M. T.; Choy, A. L. J. Org. Chem. 1997, 62, 7548- 7549. (c) Sukkari, H. E.; Gesson, J.-P.; Renoux, B. Tetrahedron Lett. 1998, 39, 4043-4046. (d) Oishi, T.; Nagumo, Y.; Hirama. M. Chem. Commun. 1998, 1041-1042. Example of E geometry in a 10-membered ring: (e) Fink, B. E.; Kym, P. R.; Katzenellenbogen, J. A. J. Am. Chem. Soc. 1998, 120, 4334-4344. (f) Sukkari, H. E.; Gesson, J.-P.; Renoux, B. Tetrahedron Lett. 1998, 39, 4043-4046 (9-, 11-, and 15-membered rings). (g) Fürstner, A.; Kindler, N. Tetrahedron Lett. 1996, 37, 7005- 7008 (12-membered ring). (h) Borer, B. C.; Deerenberg, S.; Bieräugel, H.; Pandit, U. K. Tetrahedron Lett. 1994, 35, 3191-3194 (13-membered ring, Z). (i) Kim, S. H.; Figueroa, I.; Fuchs, P. L. Tetrahedron Lett. 1997, 38, 2601-2604 (13-membered ring, E). (j) Houri, A. F.; Xu, Z.; Cogan, D. A.; Hoveyda, A. H. J. Am. Chem. Soc. 1995, 117, 2943- 2944 (14-membered ring, Z). (k) Fürstner, A.; Langemann, K. J. Org. Chem. 1996, 61, 3942-3943 (14-, 16-, and 20-membered rings). (l) Ghosh, A. K.; Hussain, K. A. Tetrahedron Lett. 1998, 39, 1881-1884 (14-membered rings, Z, 15-membered rings, Z and 16-membered rings, mixtures). (m) Ripka, A. S.; Bohacek, R. S.; Rich, D. H. Bioorg. Med. Chem. Lett. 1998, 8, 357-360 (15-membered ring, mixtures). (n) Meng, D.; Su, D.-S.; Balog, A.; Bertinato, P.; Sorensen, E. J.; Danishefsky, S. J.; Zheng, Y.-H.; Chou, T.-C.; He, L.; Horwitz, S. J. Am. Chem. Soc. 1997, 119, 2733-2734.
56. Examples of Z geometry in 9-and 10-membered rings obtained by RCM: (a) Barrett, A. G. M.; Baugh, S. P. D.; Gibson, V. C.; Giles, M. R.; Marshall, E. L.; Procopiou, P. A. Chem. Commun. 1996, 2231- 2232. (b) Crimmins, M. T.; Choy, A. L. J. Org. Chem. 1997, 62, 7548- 7549. (c) Sukkari, H. E.; Gesson, J.-P.; Renoux, B. Tetrahedron Lett. 1998, 39, 4043-4046. (d) Oishi, T.; Nagumo, Y.; Hirama. M. Chem. Commun. 1998, 1041-1042. Example of E geometry in a 10-membered ring: (e) Fink, B. E.; Kym, P. R.; Katzenellenbogen, J. A. J. Am. Chem. Soc. 1998, 120, 4334-4344. (f) Sukkari, H. E.; Gesson, J.-P.; Renoux, B. Tetrahedron Lett. 1998, 39, 4043-4046 (9-, 11-, and 15-membered rings). (g) Fürstner, A.; Kindler, N. Tetrahedron Lett. 1996, 37, 7005- 7008 (12-membered ring). (h) Borer, B. C.; Deerenberg, S.; Bieräugel, H.; Pandit, U. K. Tetrahedron Lett. 1994, 35, 3191-3194 (13-membered ring, Z). (i) Kim, S. H.; Figueroa, I.; Fuchs, P. L. Tetrahedron Lett. 1997, 38, 2601-2604 (13-membered ring, E). (j) Houri, A. F.; Xu, Z.; Cogan, D. A.; Hoveyda, A. H. J. Am. Chem. Soc. 1995, 117, 2943- 2944 (14-membered ring, Z). (k) Fürstner, A.; Langemann, K. J. Org. Chem. 1996, 61, 3942-3943 (14-, 16-, and 20-membered rings). (l) Ghosh, A. K.; Hussain, K. A. Tetrahedron Lett. 1998, 39, 1881-1884 (14-membered rings, Z, 15-membered rings, Z and 16-membered rings, mixtures). (m) Ripka, A. S.; Bohacek, R. S.; Rich, D. H. Bioorg. Med. Chem. Lett. 1998, 8, 357-360 (15-membered ring, mixtures). (n) Meng, D.; Su, D.-S.; Balog, A.; Bertinato, P.; Sorensen, E. J.; Danishefsky, S. J.; Zheng, Y.-H.; Chou, T.-C.; He, L.; Horwitz, S. J. Am. Chem. Soc. 1997, 119, 2733-2734.
57. Examples of Z geometry in 9-and 10-membered rings obtained by RCM: (a) Barrett, A. G. M.; Baugh, S. P. D.; Gibson, V. C.; Giles, M. R.; Marshall, E. L.; Procopiou, P. A. Chem. Commun. 1996, 2231- 2232. (b) Crimmins, M. T.; Choy, A. L. J. Org. Chem. 1997, 62, 7548- 7549. (c) Sukkari, H. E.; Gesson, J.-P.; Renoux, B. Tetrahedron Lett. 1998, 39, 4043-4046. (d) Oishi, T.; Nagumo, Y.; Hirama. M. Chem. Commun. 1998, 1041-1042. Example of E geometry in a 10-membered ring: (e) Fink, B. E.; Kym, P. R.; Katzenellenbogen, J. A. J. Am. Chem. Soc. 1998, 120, 4334-4344. (f) Sukkari, H. E.; Gesson, J.-P.; Renoux, B. Tetrahedron Lett. 1998, 39, 4043-4046 (9-, 11-, and 15-membered rings). (g) Fürstner, A.; Kindler, N. Tetrahedron Lett. 1996, 37, 7005- 7008 (12-membered ring). (h) Borer, B. C.; Deerenberg, S.; Bieräugel, H.; Pandit, U. K. Tetrahedron Lett. 1994, 35, 3191-3194 (13-membered ring, Z). (i) Kim, S. H.; Figueroa, I.; Fuchs, P. L. Tetrahedron Lett. 1997, 38, 2601-2604 (13-membered ring, E). (j) Houri, A. F.; Xu, Z.; Cogan, D. A.; Hoveyda, A. H. J. Am. Chem. Soc. 1995, 117, 2943-2944 (14-membered ring, Z). (k) Fürstner, A.; Langemann, K. J. Org. Chem. 1996, 61, 3942-3943 (14-, 16-, and 20-membered rings). (l) Ghosh, A. K.; Hussain, K. A. Tetrahedron Lett. 1998, 39, 1881-1884 (14-membered rings, Z, 15-membered rings, Z and 16-membered rings, mixtures). (m) Ripka, A. S.; Bohacek, R. S.; Rich, D. H. Bioorg. Med. Chem. Lett. 1998, 8, 357-360 (15-membered ring, mixtures). (n) Meng, D.; Su, D.-S.; Balog, A.; Bertinato, P.; Sorensen, E. J.; Danishefsky, S. J.; Zheng, Y.-H.; Chou, T.-C.; He, L.; Horwitz, S. J. Am. Chem. Soc. 1997, 119, 2733-2734.
58. Examples of Z geometry in 9-and 10-membered rings obtained by RCM: (a) Barrett, A. G. M.; Baugh, S. P. D.; Gibson, V. C.; Giles, M. R.; Marshall, E. L.; Procopiou, P. A. Chem. Commun. 1996, 2231- 2232. (b) Crimmins, M. T.; Choy, A. L. J. Org. Chem. 1997, 62, 7548- 7549. (c) Sukkari, H. E.; Gesson, J.-P.; Renoux, B. Tetrahedron Lett. 1998, 39, 4043-4046. (d) Oishi, T.; Nagumo, Y.; Hirama. M. Chem. Commun. 1998, 1041-1042. Example of E geometry in a 10-membered ring: (e) Fink, B. E.; Kym, P. R.; Katzenellenbogen, J. A. J. Am. Chem. Soc. 1998, 120, 4334-4344. (f) Sukkari, H. E.; Gesson, J.-P.; Renoux, B. Tetrahedron Lett. 1998, 39, 4043-4046 (9-, 11-, and 15-membered rings). (g) Fürstner, A.; Kindler, N. Tetrahedron Lett. 1996, 37, 7005- 7008 (12-membered ring). (h) Borer, B. C.; Deerenberg, S.; Bieräugel, H.; Pandit, U. K. Tetrahedron Lett. 1994, 35, 3191-3194 (13-membered ring, Z). (i) Kim, S. H.; Figueroa, I.; Fuchs, P. L. Tetrahedron Lett. 1997, 38, 2601-2604 (13-membered ring, E). (j) Houri, A. F.; Xu, Z.; Cogan, D. A.; Hoveyda, A. H. J. Am. Chem. Soc. 1995, 117, 2943- 2944 (14-membered ring, Z). (k) Fürstner, A.; Langemann, K. J. Org. Chem. 1996, 61, 3942-3943 (14-, 16-, and 20-membered rings). (l) Ghosh, A. K.; Hussain, K. A. Tetrahedron Lett. 1998, 39, 1881-1884 (14-membered rings, Z, 15-membered rings, Z and 16-membered rings, mixtures). (m) Ripka, A. S.; Bohacek, R. S.; Rich, D. H. Bioorg. Med. Chem. Lett. 1998, 8, 357-360 (15-membered ring, mixtures). (n) Meng, D.; Su, D.-S.; Balog, A.; Bertinato, P.; Sorensen, E. J.; Danishefsky, S. J.; Zheng, Y.-H.; Chou, T.-C.; He, L.; Horwitz, S. J. Am. Chem. Soc. 1997, 119, 2733-2734.
59. Examples of Z geometry in 9-and 10-membered rings obtained by RCM: (a) Barrett, A. G. M.; Baugh, S. P. D.; Gibson, V. C.; Giles, M. R.; Marshall, E. L.; Procopiou, P. A. Chem. Commun. 1996, 2231- 2232. (b) Crimmins, M. T.; Choy, A. L. J. Org. Chem. 1997, 62, 7548- 7549. (c) Sukkari, H. E.; Gesson, J.-P.; Renoux, B. Tetrahedron Lett. 1998, 39, 4043-4046. (d) Oishi, T.; Nagumo, Y.; Hirama. M. Chem. Commun. 1998, 1041-1042. Example of E geometry in a 10-membered ring: (e) Fink, B. E.; Kym, P. R.; Katzenellenbogen, J. A. J. Am. Chem. Soc. 1998, 120, 4334-4344. (f) Sukkari, H. E.; Gesson, J.-P.; Renoux, B. Tetrahedron Lett. 1998, 39, 4043-4046 (9-, 11-, and 15-membered rings). (g) Fürstner, A.; Kindler, N. Tetrahedron Lett. 1996, 37, 7005- 7008 (12-membered ring). (h) Borer, B. C.; Deerenberg, S.; Bieräugel, H.; Pandit, U. K. Tetrahedron Lett. 1994, 35, 3191-3194 (13-membered ring, Z). (i) Kim, S. H.; Figueroa, I.; Fuchs, P. L. Tetrahedron Lett. 1997, 38, 2601-2604 (13-membered ring, E). (j) Houri, A. F.; Xu, Z.; Cogan, D. A.; Hoveyda, A. H. J. Am. Chem. Soc. 1995, 117, 2943- 2944 (14-membered ring, Z). (k) Fürstner, A.; Langemann, K. J. Org. Chem. 1996, 61, 3942-3943 (14-, 16-, and 20-membered rings). (l) Ghosh, A. K.; Hussain, K. A. Tetrahedron Lett. 1998, 39, 1881-1884 (14-membered rings, Z, 15-membered rings, Z and 16-membered rings, mixtures). (m) Ripka, A. S.; Bohacek, R. S.; Rich, D. H. Bioorg. Med. Chem. Lett. 1998, 8, 357-360 (15-membered ring, mixtures). (n) Meng, D.; Su, D.-S.; Balog, A.; Bertinato, P.; Sorensen, E. J.; Danishefsky, S. J.; Zheng, Y.-H.; Chou, T.-C.; He, L.; Horwitz, S. J. Am. Chem. Soc. 1997, 119, 2733-2734.
60. Examples of Z geometry in 9-and 10-membered rings obtained by RCM: (a) Barrett, A. G. M.; Baugh, S. P. D.; Gibson, V. C.; Giles, M. R.; Marshall, E. L.; Procopiou, P. A. Chem. Commun. 1996, 2231- 2232. (b) Crimmins, M. T.; Choy, A. L. J. Org. Chem. 1997, 62, 7548- 7549. (c) Sukkari, H. E.; Gesson, J.-P.; Renoux, B. Tetrahedron Lett. 1998, 39, 4043-4046. (d) Oishi, T.; Nagumo, Y.; Hirama. M. Chem. Commun. 1998, 1041-1042. Example of E geometry in a 10-membered ring: (e) Fink, B. E.; Kym, P. R.; Katzenellenbogen, J. A. J. Am. Chem. Soc. 1998, 120, 4334-4344. (f) Sukkari, H. E.; Gesson, J.-P.; Renoux, B. Tetrahedron Lett. 1998, 39, 4043-4046 (9-, 11-, and 15-membered rings). (g) Fürstner, A.; Kindler, N. Tetrahedron Lett. 1996, 37, 7005- 7008 (12-membered ring). (h) Borer, B. C.; Deerenberg, S.; Bieräugel, H.; Pandit, U. K. Tetrahedron Lett. 1994, 35, 3191-3194 (13-membered ring, Z). (i) Kim, S. H.; Figueroa, I.; Fuchs, P. L. Tetrahedron Lett. 1997, 38, 2601-2604 (13-membered ring, E). (j) Houri, A. F.; Xu, Z.; Cogan, D. A.; Hoveyda, A. H. J. Am. Chem. Soc. 1995, 117, 2943- 2944 (14-membered ring, Z). (k) Fürstner, A.; Langemann, K. J. Org. Chem. 1996, 61, 3942-3943 (14-, 16-, and 20-membered rings). (l) Ghosh, A. K.; Hussain, K. A. Tetrahedron Lett. 1998, 39, 1881-1884 (14-membered rings, Z, 15-membered rings, Z and 16-membered rings, mixtures). (m) Ripka, A. S.; Bohacek, R. S.; Rich, D. H. Bioorg. Med. Chem. Lett. 1998, 8, 357-360 (15-membered ring, mixtures). (n) Meng, D.; Su, D.-S.; Balog, A.; Bertinato, P.; Sorensen, E. J.; Danishefsky, S. J.; Zheng, Y.-H.; Chou, T.-C.; He, L.; Horwitz, S. J. Am. Chem. Soc. 1997, 119, 2733-2734.
61. Examples of Z geometry in 9-and 10-membered rings obtained by RCM: (a) Barrett, A. G. M.; Baugh, S. P. D.; Gibson, V. C.; Giles, M. R.; Marshall, E. L.; Procopiou, P. A. Chem. Commun. 1996, 2231- 2232. (b) Crimmins, M. T.; Choy, A. L. J. Org. Chem. 1997, 62, 7548- 7549. (c) Sukkari, H. E.; Gesson, J.-P.; Renoux, B. Tetrahedron Lett. 1998, 39, 4043-4046. (d) Oishi, T.; Nagumo, Y.; Hirama. M. Chem. Commun. 1998, 1041-1042. Example of E geometry in a 10-membered ring: (e) Fink, B. E.; Kym, P. R.; Katzenellenbogen, J. A. J. Am. Chem. Soc. 1998, 120, 4334-4344. (f) Sukkari, H. E.; Gesson, J.-P.; Renoux, B. Tetrahedron Lett. 1998, 39, 4043-4046 (9-, 11-, and 15-membered rings). (g) Fürstner, A.; Kindler, N. Tetrahedron Lett. 1996, 37, 7005- 7008 (12-membered ring). (h) Borer, B. C.; Deerenberg, S.; Bieräugel, H.; Pandit, U. K. Tetrahedron Lett. 1994, 35, 3191-3194 (13-membered ring, Z). (i) Kim, S. H.; Figueroa, I.; Fuchs, P. L. Tetrahedron Lett. 1997, 38, 2601-2604 (13-membered ring, E). (j) Houri, A. F.; Xu, Z.; Cogan, D. A.; Hoveyda, A. H. J. Am. Chem. Soc. 1995, 117, 2943- 2944 (14-membered ring, Z). (k) Fürstner, A.; Langemann, K. J. Org. Chem. 1996, 61, 3942-3943 (14-, 16-, and 20-membered rings). (l) Ghosh, A. K.; Hussain, K. A. Tetrahedron Lett. 1998, 39, 1881-1884 (14-membered rings, Z, 15-membered rings, Z and 16-membered rings, mixtures). (m) Ripka, A. S.; Bohacek, R. S.; Rich, D. H. Bioorg. Med. Chem. Lett. 1998, 8, 357-360 (15-membered ring, mixtures). (n) Meng, D.; Su, D.-S.; Balog, A.; Bertinato, P.; Sorensen, E. J.; Danishefsky, S. J.; Zheng, Y.-H.; Chou, T.-C.; He, L.; Horwitz, S. J. Am. Chem. Soc. 1997, 119, 2733-2734.
62. Precedents in the application of RCM to the synthesis of crown ethers: (a) König, B.; Horn, C. Synlett 1996, 1013-1014. (b) Marsella, M. J.; Maynard, H. D.; Grubbs, R. H. Angew. Chem., Int. Ed. Engl. 1997, 36, 1101-1103.
63. Precedents in the application of RCM to the synthesis of crown ethers: (a) König, B.; Horn, C. Synlett 1996, 1013-1014. (b) Marsella, M. J.; Maynard, H. D.; Grubbs, R. H. Angew. Chem., Int. Ed. Engl. 1997, 36, 1101-1103.
64. Czech, B. P.; Huh, H.; Bartsch, R. A. J. Org. Chem. 1992, 57, 725-728.
65. For the preparation of allyl toluene p-sulfonates 47, 48a-d, and 49, see Supporting Information.
66. Delgado, M.; Martín, J. D. Tetrahedron Lett. 1997, 38, 8387-8390.