Expeditious syntheses of sugar-modified nucleosides and collections thereof exploiting furan-, pyrrole-, and thiophene-based siloxy dienes

Journal of Medicinal Chemistry

Volumn 40, Issue 2, 1997, Pages 168-180

  Rassu, Gloria ^a   Zanardi, Franca ^b   Battistini, Lucia ^b   Gaetani, Enrico ^b   Casiraghi, Giovanni ^b  

^a Ist l'Applic Tecniche Chimiche A   (Italy)

^b UNIVERSITY OF PARMA   (Italy)

Author keywords

[No Author keywords available]

Indexed keywords

2 (TERT BUTYLDIMETHYLSILOXY)FURAN; 2 (TERT BUTYLDIMETHYLSILOXY)THIOPHENE; N (TERT BUTOXYCARBONYL) 2 (TERT BUTYLDIMETHYLSILOXY)PYRROLE; NUCLEOSIDE DERIVATIVE; UNCLASSIFIED DRUG;

ARTICLE; CHEMICAL REACTION KINETICS; CHIRALITY; ENANTIOMER; NUCLEOSIDE TRANSPORT; NUCLEOTIDE METABOLISM; RACEMIC MIXTURE; STEREOCHEMISTRY;

FURANS; NUCLEOSIDES; PYRROLES; SILICON COMPOUNDS; STEREOISOMERISM; THIOPHENES;

EID: 0031012830     PISSN: 00222623     EISSN: None     Source Type: Journal    
DOI: 10.1021/jm960400q     Document Type: Article

References (66)

1. (1) For recent reviews and general articles on the use of combinatorial technology for drug discovery, see: Madden, D.; Krchnák, V.; Lebl, M. Synthetic Combinatorial Libraries: Views on Techniques and their Application. Perspect. Drug Disc. Des. 1995, 2, 269-285. Ellman, J. A. Combinatorial Organic Libraries Chemtracts - Org. Chem. 1995, 8, 1-4. Pirrung, M. C. Combinatorial Libraries: Chemistry Meets Darwin. Ibid. 1995, 8, 5-12. Czarnik, A. W. Why Combinatorial Chemistry, Why Now (and Why You Should Care). Ibid. 1995, 8, 13-18. Mitscher, L. A. Some Ruminations on the Present and Future Roles of Combinatorial and Multiplex Syntheses in Medicinal Chemistry. Ibid. 1995, 8, 19-25. Cabri, W. Combinatorial Chemistry: Status and Perspectives. Chim. Ind. (Milan) 1995, 77, 406-410. Gallop, M. A.; Barrett, R. W.; Dower, W. J.; Fodor, S. P. A.; Gordon, E. M. Applications of Combinatorial Technologies to Drug Discovery. 1. Background and Peptide Combinatorial Libraries. J. Med. Chem. 1994, 37, 1233-1251. Gordon, E. M.; Barrett, R. W.; Dower, W. J.; Fodor, S. P. A.; Gallop, M. A. Applications of Combinatorial Technologies to Drug Discovery. 2. Combinatorial Organic Synthesis, Library Screening Strategies, and Future Directions. J. Med. Chem. 1994, 37, 1385-1401. Moos, W. H.; Green, G. D.; Pavia, M. R. Recent Advances in the Generation of Molecular Diversity. Annu. Rep. Med. Chem. 1993, 28, 315-324.
2. For recent reviews and general articles on the use of combinatorial technology for drug discovery, see: Madden, D.; Krchnák, V.; Lebl, M. Synthetic Combinatorial Libraries: Views on Techniques and their Application. Perspect. Drug Disc. Des. 1995, 2, 269-285. Ellman, J. A. Combinatorial Organic Libraries Chemtracts - Org. Chem. 1995, 8, 1-4. Pirrung, M. C. Combinatorial Libraries: Chemistry Meets Darwin. Ibid. 1995, 8, 5-12. Czarnik, A. W. Why Combinatorial Chemistry, Why Now (and Why You Should Care). Ibid. 1995, 8, 13-18. Mitscher, L. A. Some Ruminations on the Present and Future Roles of Combinatorial and Multiplex Syntheses in Medicinal Chemistry. Ibid. 1995, 8, 19-25. Cabri, W. Combinatorial Chemistry: Status and Perspectives. Chim. Ind. (Milan) 1995, 77, 406-410. Gallop, M. A.; Barrett, R. W.; Dower, W. J.; Fodor, S. P. A.; Gordon, E. M. Applications of Combinatorial Technologies to Drug Discovery. 1. Background and Peptide Combinatorial Libraries. J. Med. Chem. 1994, 37, 1233-1251. Gordon, E. M.; Barrett, R. W.; Dower, W. J.; Fodor, S. P. A.; Gallop, M. A. Applications of Combinatorial Technologies to Drug Discovery. 2. Combinatorial Organic Synthesis, Library Screening Strategies, and Future Directions. J. Med. Chem. 1994, 37, 1385-1401. Moos, W. H.; Green, G. D.; Pavia, M. R. Recent Advances in the Generation of Molecular Diversity. Annu. Rep. Med. Chem. 1993, 28, 315-324.
3. For recent reviews and general articles on the use of combinatorial technology for drug discovery, see: Madden, D.; Krchnák, V.; Lebl, M. Synthetic Combinatorial Libraries: Views on Techniques and their Application. Perspect. Drug Disc. Des. 1995, 2, 269-285. Ellman, J. A. Combinatorial Organic Libraries Chemtracts - Org. Chem. 1995, 8, 1-4. Pirrung, M. C. Combinatorial Libraries: Chemistry Meets Darwin. Ibid. 1995, 8, 5-12. Czarnik, A. W. Why Combinatorial Chemistry, Why Now (and Why You Should Care). Ibid. 1995, 8, 13-18. Mitscher, L. A. Some Ruminations on the Present and Future Roles of Combinatorial and Multiplex Syntheses in Medicinal Chemistry. Ibid. 1995, 8, 19-25. Cabri, W. Combinatorial Chemistry: Status and Perspectives. Chim. Ind. (Milan) 1995, 77, 406-410. Gallop, M. A.; Barrett, R. W.; Dower, W. J.; Fodor, S. P. A.; Gordon, E. M. Applications of Combinatorial Technologies to Drug Discovery. 1. Background and Peptide Combinatorial Libraries. J. Med. Chem. 1994, 37, 1233-1251. Gordon, E. M.; Barrett, R. W.; Dower, W. J.; Fodor, S. P. A.; Gallop, M. A. Applications of Combinatorial Technologies to Drug Discovery. 2. Combinatorial Organic Synthesis, Library Screening Strategies, and Future Directions. J. Med. Chem. 1994, 37, 1385-1401. Moos, W. H.; Green, G. D.; Pavia, M. R. Recent Advances in the Generation of Molecular Diversity. Annu. Rep. Med. Chem. 1993, 28, 315-324.
4. For recent reviews and general articles on the use of combinatorial technology for drug discovery, see: Madden, D.; Krchnák, V.; Lebl, M. Synthetic Combinatorial Libraries: Views on Techniques and their Application. Perspect. Drug Disc. Des. 1995, 2, 269-285. Ellman, J. A. Combinatorial Organic Libraries Chemtracts - Org. Chem. 1995, 8, 1-4. Pirrung, M. C. Combinatorial Libraries: Chemistry Meets Darwin. Ibid. 1995, 8, 5-12. Czarnik, A. W. Why Combinatorial Chemistry, Why Now (and Why You Should Care). Ibid. 1995, 8, 13-18. Mitscher, L. A. Some Ruminations on the Present and Future Roles of Combinatorial and Multiplex Syntheses in Medicinal Chemistry. Ibid. 1995, 8, 19-25. Cabri, W. Combinatorial Chemistry: Status and Perspectives. Chim. Ind. (Milan) 1995, 77, 406-410. Gallop, M. A.; Barrett, R. W.; Dower, W. J.; Fodor, S. P. A.; Gordon, E. M. Applications of Combinatorial Technologies to Drug Discovery. 1. Background and Peptide Combinatorial Libraries. J. Med. Chem. 1994, 37, 1233-1251. Gordon, E. M.; Barrett, R. W.; Dower, W. J.; Fodor, S. P. A.; Gallop, M. A. Applications of Combinatorial Technologies to Drug Discovery. 2. Combinatorial Organic Synthesis, Library Screening Strategies, and Future Directions. J. Med. Chem. 1994, 37, 1385-1401. Moos, W. H.; Green, G. D.; Pavia, M. R. Recent Advances in the Generation of Molecular Diversity. Annu. Rep. Med. Chem. 1993, 28, 315-324.
5. For recent reviews and general articles on the use of combinatorial technology for drug discovery, see: Madden, D.; Krchnák, V.; Lebl, M. Synthetic Combinatorial Libraries: Views on Techniques and their Application. Perspect. Drug Disc. Des. 1995, 2, 269-285. Ellman, J. A. Combinatorial Organic Libraries Chemtracts - Org. Chem. 1995, 8, 1-4. Pirrung, M. C. Combinatorial Libraries: Chemistry Meets Darwin. Ibid. 1995, 8, 5-12. Czarnik, A. W. Why Combinatorial Chemistry, Why Now (and Why You Should Care). Ibid. 1995, 8, 13-18. Mitscher, L. A. Some Ruminations on the Present and Future Roles of Combinatorial and Multiplex Syntheses in Medicinal Chemistry. Ibid. 1995, 8, 19-25. Cabri, W. Combinatorial Chemistry: Status and Perspectives. Chim. Ind. (Milan) 1995, 77, 406-410. Gallop, M. A.; Barrett, R. W.; Dower, W. J.; Fodor, S. P. A.; Gordon, E. M. Applications of Combinatorial Technologies to Drug Discovery. 1. Background and Peptide Combinatorial Libraries. J. Med. Chem. 1994, 37, 1233-1251. Gordon, E. M.; Barrett, R. W.; Dower, W. J.; Fodor, S. P. A.; Gallop, M. A. Applications of Combinatorial Technologies to Drug Discovery. 2. Combinatorial Organic Synthesis, Library Screening Strategies, and Future Directions. J. Med. Chem. 1994, 37, 1385-1401. Moos, W. H.; Green, G. D.; Pavia, M. R. Recent Advances in the Generation of Molecular Diversity. Annu. Rep. Med. Chem. 1993, 28, 315-324.
6. For recent reviews and general articles on the use of combinatorial technology for drug discovery, see: Madden, D.; Krchnák, V.; Lebl, M. Synthetic Combinatorial Libraries: Views on Techniques and their Application. Perspect. Drug Disc. Des. 1995, 2, 269-285. Ellman, J. A. Combinatorial Organic Libraries Chemtracts - Org. Chem. 1995, 8, 1-4. Pirrung, M. C. Combinatorial Libraries: Chemistry Meets Darwin. Ibid. 1995, 8, 5-12. Czarnik, A. W. Why Combinatorial Chemistry, Why Now (and Why You Should Care). Ibid. 1995, 8, 13-18. Mitscher, L. A. Some Ruminations on the Present and Future Roles of Combinatorial and Multiplex Syntheses in Medicinal Chemistry. Ibid. 1995, 8, 19-25. Cabri, W. Combinatorial Chemistry: Status and Perspectives. Chim. Ind. (Milan) 1995, 77, 406-410. Gallop, M. A.; Barrett, R. W.; Dower, W. J.; Fodor, S. P. A.; Gordon, E. M. Applications of Combinatorial Technologies to Drug Discovery. 1. Background and Peptide Combinatorial Libraries. J. Med. Chem. 1994, 37, 1233-1251. Gordon, E. M.; Barrett, R. W.; Dower, W. J.; Fodor, S. P. A.; Gallop, M. A. Applications of Combinatorial Technologies to Drug Discovery. 2. Combinatorial Organic Synthesis, Library Screening Strategies, and Future Directions. J. Med. Chem. 1994, 37, 1385-1401. Moos, W. H.; Green, G. D.; Pavia, M. R. Recent Advances in the Generation of Molecular Diversity. Annu. Rep. Med. Chem. 1993, 28, 315-324.
7. For recent reviews and general articles on the use of combinatorial technology for drug discovery, see: Madden, D.; Krchnák, V.; Lebl, M. Synthetic Combinatorial Libraries: Views on Techniques and their Application. Perspect. Drug Disc. Des. 1995, 2, 269-285. Ellman, J. A. Combinatorial Organic Libraries Chemtracts - Org. Chem. 1995, 8, 1-4. Pirrung, M. C. Combinatorial Libraries: Chemistry Meets Darwin. Ibid. 1995, 8, 5-12. Czarnik, A. W. Why Combinatorial Chemistry, Why Now (and Why You Should Care). Ibid. 1995, 8, 13-18. Mitscher, L. A. Some Ruminations on the Present and Future Roles of Combinatorial and Multiplex Syntheses in Medicinal Chemistry. Ibid. 1995, 8, 19-25. Cabri, W. Combinatorial Chemistry: Status and Perspectives. Chim. Ind. (Milan) 1995, 77, 406-410. Gallop, M. A.; Barrett, R. W.; Dower, W. J.; Fodor, S. P. A.; Gordon, E. M. Applications of Combinatorial Technologies to Drug Discovery. 1. Background and Peptide Combinatorial Libraries. J. Med. Chem. 1994, 37, 1233-1251. Gordon, E. M.; Barrett, R. W.; Dower, W. J.; Fodor, S. P. A.; Gallop, M. A. Applications of Combinatorial Technologies to Drug Discovery. 2. Combinatorial Organic Synthesis, Library Screening Strategies, and Future Directions. J. Med. Chem. 1994, 37, 1385-1401. Moos, W. H.; Green, G. D.; Pavia, M. R. Recent Advances in the Generation of Molecular Diversity. Annu. Rep. Med. Chem. 1993, 28, 315-324.
8. For recent reviews and general articles on the use of combinatorial technology for drug discovery, see: Madden, D.; Krchnák, V.; Lebl, M. Synthetic Combinatorial Libraries: Views on Techniques and their Application. Perspect. Drug Disc. Des. 1995, 2, 269-285. Ellman, J. A. Combinatorial Organic Libraries Chemtracts - Org. Chem. 1995, 8, 1-4. Pirrung, M. C. Combinatorial Libraries: Chemistry Meets Darwin. Ibid. 1995, 8, 5-12. Czarnik, A. W. Why Combinatorial Chemistry, Why Now (and Why You Should Care). Ibid. 1995, 8, 13-18. Mitscher, L. A. Some Ruminations on the Present and Future Roles of Combinatorial and Multiplex Syntheses in Medicinal Chemistry. Ibid. 1995, 8, 19-25. Cabri, W. Combinatorial Chemistry: Status and Perspectives. Chim. Ind. (Milan) 1995, 77, 406-410. Gallop, M. A.; Barrett, R. W.; Dower, W. J.; Fodor, S. P. A.; Gordon, E. M. Applications of Combinatorial Technologies to Drug Discovery. 1. Background and Peptide Combinatorial Libraries. J. Med. Chem. 1994, 37, 1233-1251. Gordon, E. M.; Barrett, R. W.; Dower, W. J.; Fodor, S. P. A.; Gallop, M. A. Applications of Combinatorial Technologies to Drug Discovery. 2. Combinatorial Organic Synthesis, Library Screening Strategies, and Future Directions. J. Med. Chem. 1994, 37, 1385-1401. Moos, W. H.; Green, G. D.; Pavia, M. R. Recent Advances in the Generation of Molecular Diversity. Annu. Rep. Med. Chem. 1993, 28, 315-324.
9. For recent reviews and general articles on the use of combinatorial technology for drug discovery, see: Madden, D.; Krchnák, V.; Lebl, M. Synthetic Combinatorial Libraries: Views on Techniques and their Application. Perspect. Drug Disc. Des. 1995, 2, 269-285. Ellman, J. A. Combinatorial Organic Libraries Chemtracts - Org. Chem. 1995, 8, 1-4. Pirrung, M. C. Combinatorial Libraries: Chemistry Meets Darwin. Ibid. 1995, 8, 5-12. Czarnik, A. W. Why Combinatorial Chemistry, Why Now (and Why You Should Care). Ibid. 1995, 8, 13-18. Mitscher, L. A. Some Ruminations on the Present and Future Roles of Combinatorial and Multiplex Syntheses in Medicinal Chemistry. Ibid. 1995, 8, 19-25. Cabri, W. Combinatorial Chemistry: Status and Perspectives. Chim. Ind. (Milan) 1995, 77, 406-410. Gallop, M. A.; Barrett, R. W.; Dower, W. J.; Fodor, S. P. A.; Gordon, E. M. Applications of Combinatorial Technologies to Drug Discovery. 1. Background and Peptide Combinatorial Libraries. J. Med. Chem. 1994, 37, 1233-1251. Gordon, E. M.; Barrett, R. W.; Dower, W. J.; Fodor, S. P. A.; Gallop, M. A. Applications of Combinatorial Technologies to Drug Discovery. 2. Combinatorial Organic Synthesis, Library Screening Strategies, and Future Directions. J. Med. Chem. 1994, 37, 1385-1401. Moos, W. H.; Green, G. D.; Pavia, M. R. Recent Advances in the Generation of Molecular Diversity. Annu. Rep. Med. Chem. 1993, 28, 315-324.
10. (2) Casiraghi, G.; Rassu, G. Furan-, Pyrrole-, and Thiophene-Based Siloxydienes for Syntheses of Densely Functionalized Homochiral Compounds. Synthesis 1995, 607-626. Casiraghi, G.; Zanardi, F.; Rassu, G.; Spanu, P. Stereoselective Approaches to Bioactive Carbohydrates and Alkaloids-With a Focus on Recent Syntheses Drawing from the Chiral Pool. Chem. Rev. 1995, 95, 1677-1716. Casiraghi, G.; Colombo, L.; Rassu, G.; Spanu, P. Ascent of the Aldose Series by Four Carbon Atoms: Total Synthesis of D-glygero-D-talo-L-talo-Undecose Pentaacetonide. J. Org. Chem. 1991, 56, 2135-2139. Casiraghi, G.; Colombo, L. Rassu, G.; Spanu, P. Total Synthesis of 6-Deoxy-6-aminohepto-pyranuronic Acid Derivatives. J. Org. Chem. 1991, 56, 6523-6527. Casiraghi, G.; Rassu, G.; Spanu, P.; Pinna, L.; Ulgheri F. Total Syntheses of (+)-2,8,8a-Tri-epi-swainsonine and (-)-1-epi-Swainsonine. J. Org. Chem. 1993, 58, 3397-3400. Casiraghi, G.; Spanu, P.; Rassu, G.; Pinna, L.; Ulgheri, F. Total Syntheses of All Four Isomers of cis-1,2-Dihydroxypyrrolizidine. J. Org. Chem. 1994, 59, 2906-2909. Rassu, G.; Zanardi, F.; Cornia, M.; Casiraghi, G. General Approach to Hydroxylated α-Amino Acids Exploiting N-(tert-Butoxycarbonyl)-2-(terf-butyldimethylsiloxy)-pyrrole. J. Chem. Soc., Perkin Trans. 1 1994, 2431-2437. Zanardi, F.; Battistini, L.; Rassu, G.; Cornia, M.; Casiraghi, G. γ-Substituted Pyrrole-Based Silyl Dienol Ethers as α-Amino Acid Enolate Equivalents: a Versatile Entry to Racemic α-Substituted α-Amino Acids. J. Chem. Soc., Perkin Trans. 1 1995, 2471-2475.
11. Casiraghi, G.; Rassu, G. Furan-, Pyrrole-, and Thiophene-Based Siloxydienes for Syntheses of Densely Functionalized Homochiral Compounds. Synthesis 1995, 607-626. Casiraghi, G.; Zanardi, F.; Rassu, G.; Spanu, P. Stereoselective Approaches to Bioactive Carbohydrates and Alkaloids-With a Focus on Recent Syntheses Drawing from the Chiral Pool. Chem. Rev. 1995, 95, 1677-1716. Casiraghi, G.; Colombo, L.; Rassu, G.; Spanu, P. Ascent of the Aldose Series by Four Carbon Atoms: Total Synthesis of D-glygero-D-talo-L-talo-Undecose Pentaacetonide. J. Org. Chem. 1991, 56, 2135-2139. Casiraghi, G.; Colombo, L. Rassu, G.; Spanu, P. Total Synthesis of 6-Deoxy-6-aminohepto-pyranuronic Acid Derivatives. J. Org. Chem. 1991, 56, 6523-6527. Casiraghi, G.; Rassu, G.; Spanu, P.; Pinna, L.; Ulgheri F. Total Syntheses of (+)-2,8,8a-Tri-epi-swainsonine and (-)-1-epi-Swainsonine. J. Org. Chem. 1993, 58, 3397-3400. Casiraghi, G.; Spanu, P.; Rassu, G.; Pinna, L.; Ulgheri, F. Total Syntheses of All Four Isomers of cis-1,2-Dihydroxypyrrolizidine. J. Org. Chem. 1994, 59, 2906-2909. Rassu, G.; Zanardi, F.; Cornia, M.; Casiraghi, G. General Approach to Hydroxylated α-Amino Acids Exploiting N-(tert-Butoxycarbonyl)-2-(terf-butyldimethylsiloxy)-pyrrole. J. Chem. Soc., Perkin Trans. 1 1994, 2431-2437. Zanardi, F.; Battistini, L.; Rassu, G.; Cornia, M.; Casiraghi, G. γ-Substituted Pyrrole-Based Silyl Dienol Ethers as α-Amino Acid Enolate Equivalents: a Versatile Entry to Racemic α-Substituted α-Amino Acids. J. Chem. Soc., Perkin Trans. 1 1995, 2471-2475.
12. Casiraghi, G.; Rassu, G. Furan-, Pyrrole-, and Thiophene-Based Siloxydienes for Syntheses of Densely Functionalized Homochiral Compounds. Synthesis 1995, 607-626. Casiraghi, G.; Zanardi, F.; Rassu, G.; Spanu, P. Stereoselective Approaches to Bioactive Carbohydrates and Alkaloids-With a Focus on Recent Syntheses Drawing from the Chiral Pool. Chem. Rev. 1995, 95, 1677-1716. Casiraghi, G.; Colombo, L.; Rassu, G.; Spanu, P. Ascent of the Aldose Series by Four Carbon Atoms: Total Synthesis of D-glygero-D-talo-L-talo-Undecose Pentaacetonide. J. Org. Chem. 1991, 56, 2135-2139. Casiraghi, G.; Colombo, L. Rassu, G.; Spanu, P. Total Synthesis of 6-Deoxy-6-aminohepto-pyranuronic Acid Derivatives. J. Org. Chem. 1991, 56, 6523-6527. Casiraghi, G.; Rassu, G.; Spanu, P.; Pinna, L.; Ulgheri F. Total Syntheses of (+)-2,8,8a-Tri-epi-swainsonine and (-)-1-epi-Swainsonine. J. Org. Chem. 1993, 58, 3397-3400. Casiraghi, G.; Spanu, P.; Rassu, G.; Pinna, L.; Ulgheri, F. Total Syntheses of All Four Isomers of cis-1,2-Dihydroxypyrrolizidine. J. Org. Chem. 1994, 59, 2906-2909. Rassu, G.; Zanardi, F.; Cornia, M.; Casiraghi, G. General Approach to Hydroxylated α-Amino Acids Exploiting N-(tert-Butoxycarbonyl)-2-(terf-butyldimethylsiloxy)-pyrrole. J. Chem. Soc., Perkin Trans. 1 1994, 2431-2437. Zanardi, F.; Battistini, L.; Rassu, G.; Cornia, M.; Casiraghi, G. γ-Substituted Pyrrole-Based Silyl Dienol Ethers as α-Amino Acid Enolate Equivalents: a Versatile Entry to Racemic α-Substituted α-Amino Acids. J. Chem. Soc., Perkin Trans. 1 1995, 2471-2475.
13. Casiraghi, G.; Rassu, G. Furan-, Pyrrole-, and Thiophene-Based Siloxydienes for Syntheses of Densely Functionalized Homochiral Compounds. Synthesis 1995, 607-626. Casiraghi, G.; Zanardi, F.; Rassu, G.; Spanu, P. Stereoselective Approaches to Bioactive Carbohydrates and Alkaloids-With a Focus on Recent Syntheses Drawing from the Chiral Pool. Chem. Rev. 1995, 95, 1677-1716. Casiraghi, G.; Colombo, L.; Rassu, G.; Spanu, P. Ascent of the Aldose Series by Four Carbon Atoms: Total Synthesis of D-glygero-D-talo-L-talo-Undecose Pentaacetonide. J. Org. Chem. 1991, 56, 2135-2139. Casiraghi, G.; Colombo, L. Rassu, G.; Spanu, P. Total Synthesis of 6-Deoxy-6-aminohepto-pyranuronic Acid Derivatives. J. Org. Chem. 1991, 56, 6523-6527. Casiraghi, G.; Rassu, G.; Spanu, P.; Pinna, L.; Ulgheri F. Total Syntheses of (+)-2,8,8a-Tri-epi-swainsonine and (-)-1-epi-Swainsonine. J. Org. Chem. 1993, 58, 3397-3400. Casiraghi, G.; Spanu, P.; Rassu, G.; Pinna, L.; Ulgheri, F. Total Syntheses of All Four Isomers of cis-1,2-Dihydroxypyrrolizidine. J. Org. Chem. 1994, 59, 2906-2909. Rassu, G.; Zanardi, F.; Cornia, M.; Casiraghi, G. General Approach to Hydroxylated α-Amino Acids Exploiting N-(tert-Butoxycarbonyl)-2-(terf-butyldimethylsiloxy)-pyrrole. J. Chem. Soc., Perkin Trans. 1 1994, 2431-2437. Zanardi, F.; Battistini, L.; Rassu, G.; Cornia, M.; Casiraghi, G. γ-Substituted Pyrrole-Based Silyl Dienol Ethers as α-Amino Acid Enolate Equivalents: a Versatile Entry to Racemic α-Substituted α-Amino Acids. J. Chem. Soc., Perkin Trans. 1 1995, 2471-2475.
14. Casiraghi, G.; Rassu, G. Furan-, Pyrrole-, and Thiophene-Based Siloxydienes for Syntheses of Densely Functionalized Homochiral Compounds. Synthesis 1995, 607-626. Casiraghi, G.; Zanardi, F.; Rassu, G.; Spanu, P. Stereoselective Approaches to Bioactive Carbohydrates and Alkaloids-With a Focus on Recent Syntheses Drawing from the Chiral Pool. Chem. Rev. 1995, 95, 1677-1716. Casiraghi, G.; Colombo, L.; Rassu, G.; Spanu, P. Ascent of the Aldose Series by Four Carbon Atoms: Total Synthesis of D-glygero-D-talo-L-talo-Undecose Pentaacetonide. J. Org. Chem. 1991, 56, 2135-2139. Casiraghi, G.; Colombo, L. Rassu, G.; Spanu, P. Total Synthesis of 6-Deoxy-6-aminohepto-pyranuronic Acid Derivatives. J. Org. Chem. 1991, 56, 6523-6527. Casiraghi, G.; Rassu, G.; Spanu, P.; Pinna, L.; Ulgheri F. Total Syntheses of (+)-2,8,8a-Tri-epi-swainsonine and (-)-1-epi-Swainsonine. J. Org. Chem. 1993, 58, 3397-3400. Casiraghi, G.; Spanu, P.; Rassu, G.; Pinna, L.; Ulgheri, F. Total Syntheses of All Four Isomers of cis-1,2-Dihydroxypyrrolizidine. J. Org. Chem. 1994, 59, 2906-2909. Rassu, G.; Zanardi, F.; Cornia, M.; Casiraghi, G. General Approach to Hydroxylated α-Amino Acids Exploiting N-(tert-Butoxycarbonyl)-2-(terf-butyldimethylsiloxy)-pyrrole. J. Chem. Soc., Perkin Trans. 1 1994, 2431-2437. Zanardi, F.; Battistini, L.; Rassu, G.; Cornia, M.; Casiraghi, G. γ-Substituted Pyrrole-Based Silyl Dienol Ethers as α-Amino Acid Enolate Equivalents: a Versatile Entry to Racemic α-Substituted α-Amino Acids. J. Chem. Soc., Perkin Trans. 1 1995, 2471-2475.
15. Casiraghi, G.; Rassu, G. Furan-, Pyrrole-, and Thiophene-Based Siloxydienes for Syntheses of Densely Functionalized Homochiral Compounds. Synthesis 1995, 607-626. Casiraghi, G.; Zanardi, F.; Rassu, G.; Spanu, P. Stereoselective Approaches to Bioactive Carbohydrates and Alkaloids-With a Focus on Recent Syntheses Drawing from the Chiral Pool. Chem. Rev. 1995, 95, 1677-1716. Casiraghi, G.; Colombo, L.; Rassu, G.; Spanu, P. Ascent of the Aldose Series by Four Carbon Atoms: Total Synthesis of D-glygero-D-talo-L-talo-Undecose Pentaacetonide. J. Org. Chem. 1991, 56, 2135-2139. Casiraghi, G.; Colombo, L. Rassu, G.; Spanu, P. Total Synthesis of 6-Deoxy-6-aminohepto-pyranuronic Acid Derivatives. J. Org. Chem. 1991, 56, 6523-6527. Casiraghi, G.; Rassu, G.; Spanu, P.; Pinna, L.; Ulgheri F. Total Syntheses of (+)-2,8,8a-Tri-epi-swainsonine and (-)-1-epi-Swainsonine. J. Org. Chem. 1993, 58, 3397-3400. Casiraghi, G.; Spanu, P.; Rassu, G.; Pinna, L.; Ulgheri, F. Total Syntheses of All Four Isomers of cis-1,2-Dihydroxypyrrolizidine. J. Org. Chem. 1994, 59, 2906-2909. Rassu, G.; Zanardi, F.; Cornia, M.; Casiraghi, G. General Approach to Hydroxylated α-Amino Acids Exploiting N-(tert-Butoxycarbonyl)-2-(terf-butyldimethylsiloxy)-pyrrole. J. Chem. Soc., Perkin Trans. 1 1994, 2431-2437. Zanardi, F.; Battistini, L.; Rassu, G.; Cornia, M.; Casiraghi, G. γ-Substituted Pyrrole-Based Silyl Dienol Ethers as α-Amino Acid Enolate Equivalents: a Versatile Entry to Racemic α-Substituted α-Amino Acids. J. Chem. Soc., Perkin Trans. 1 1995, 2471-2475.
16. Casiraghi, G.; Rassu, G. Furan-, Pyrrole-, and Thiophene-Based Siloxydienes for Syntheses of Densely Functionalized Homochiral Compounds. Synthesis 1995, 607-626. Casiraghi, G.; Zanardi, F.; Rassu, G.; Spanu, P. Stereoselective Approaches to Bioactive Carbohydrates and Alkaloids-With a Focus on Recent Syntheses Drawing from the Chiral Pool. Chem. Rev. 1995, 95, 1677-1716. Casiraghi, G.; Colombo, L.; Rassu, G.; Spanu, P. Ascent of the Aldose Series by Four Carbon Atoms: Total Synthesis of D-glygero-D-talo-L-talo-Undecose Pentaacetonide. J. Org. Chem. 1991, 56, 2135-2139. Casiraghi, G.; Colombo, L. Rassu, G.; Spanu, P. Total Synthesis of 6-Deoxy-6-aminohepto-pyranuronic Acid Derivatives. J. Org. Chem. 1991, 56, 6523-6527. Casiraghi, G.; Rassu, G.; Spanu, P.; Pinna, L.; Ulgheri F. Total Syntheses of (+)-2,8,8a-Tri-epi-swainsonine and (-)-1-epi-Swainsonine. J. Org. Chem. 1993, 58, 3397-3400. Casiraghi, G.; Spanu, P.; Rassu, G.; Pinna, L.; Ulgheri, F. Total Syntheses of All Four Isomers of cis-1,2-Dihydroxypyrrolizidine. J. Org. Chem. 1994, 59, 2906-2909. Rassu, G.; Zanardi, F.; Cornia, M.; Casiraghi, G. General Approach to Hydroxylated α-Amino Acids Exploiting N-(tert-Butoxycarbonyl)-2-(terf-butyldimethylsiloxy)-pyrrole. J. Chem. Soc., Perkin Trans. 1 1994, 2431-2437. Zanardi, F.; Battistini, L.; Rassu, G.; Cornia, M.; Casiraghi, G. γ-Substituted Pyrrole-Based Silyl Dienol Ethers as α-Amino Acid Enolate Equivalents: a Versatile Entry to Racemic α-Substituted α-Amino Acids. J. Chem. Soc., Perkin Trans. 1 1995, 2471-2475.
17. Casiraghi, G.; Rassu, G. Furan-, Pyrrole-, and Thiophene-Based Siloxydienes for Syntheses of Densely Functionalized Homochiral Compounds. Synthesis 1995, 607-626. Casiraghi, G.; Zanardi, F.; Rassu, G.; Spanu, P. Stereoselective Approaches to Bioactive Carbohydrates and Alkaloids-With a Focus on Recent Syntheses Drawing from the Chiral Pool. Chem. Rev. 1995, 95, 1677-1716. Casiraghi, G.; Colombo, L.; Rassu, G.; Spanu, P. Ascent of the Aldose Series by Four Carbon Atoms: Total Synthesis of D-glygero-D-talo-L-talo-Undecose Pentaacetonide. J. Org. Chem. 1991, 56, 2135-2139. Casiraghi, G.; Colombo, L. Rassu, G.; Spanu, P. Total Synthesis of 6-Deoxy-6-aminohepto-pyranuronic Acid Derivatives. J. Org. Chem. 1991, 56, 6523-6527. Casiraghi, G.; Rassu, G.; Spanu, P.; Pinna, L.; Ulgheri F. Total Syntheses of (+)-2,8,8a-Tri-epi-swainsonine and (-)-1-epi-Swainsonine. J. Org. Chem. 1993, 58, 3397-3400. Casiraghi, G.; Spanu, P.; Rassu, G.; Pinna, L.; Ulgheri, F. Total Syntheses of All Four Isomers of cis-1,2-Dihydroxypyrrolizidine. J. Org. Chem. 1994, 59, 2906-2909. Rassu, G.; Zanardi, F.; Cornia, M.; Casiraghi, G. General Approach to Hydroxylated α-Amino Acids Exploiting N-(tert-Butoxycarbonyl)-2-(terf-butyldimethylsiloxy)-pyrrole. J. Chem. Soc., Perkin Trans. 1 1994, 2431-2437. Zanardi, F.; Battistini, L.; Rassu, G.; Cornia, M.; Casiraghi, G. γ-Substituted Pyrrole-Based Silyl Dienol Ethers as α-Amino Acid Enolate Equivalents: a Versatile Entry to Racemic α-Substituted α-Amino Acids. J. Chem. Soc., Perkin Trans. 1 1995, 2471-2475.
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53. Initial attempts to carry out the coupling reaction on the corresponding O-methyl derivative using a variety of Lewis acid catalysts met with failure.
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62. The absolute configuration of 22 was ascertained by single-crystal X-ray analysis: Rassu, G.; Casiraghi, G.; Spanu, P.; Pinna, L.; Gasparri Fava, G.; Belicchi Ferrari, M.; Pelosi, G. Homochiral α,β-Unsaturated γ-Lactams: Versatile Templates. Tetrahedron Asymmetry 1992, 3, 1035-1048.
63. Thanks are due to Prof. Jean-Claude Depezay (Université de Paris V) for a useful discussion about this topic.
64. To ensure uniform product dispersion within the nucleoside pools by minimizing any kinetic discrepancies, a 4 equiv excess of each silylated base was employed throughout.
65. Cy in this study is under way, and the results should be published in due course.
66. In the oxygen series, the majority of the compounds prepared are known substances. Their preparation should be intended as unavoidable complement of the whole synthetic procedure.