Scaleable syntheses of isomeric limonene aziridines from the commercially available mixture of cis- and trans-limonene oxides

Organic Process Research and Development

Volumn 9, Issue 2, 2005, Pages 221-224

  Voronkov, Michael V ^a   Gontcharov, Alexander V ^a   Kanamarlapudi, Ramanaiah C ^a   Richardson, Paul F ^a   Wang, Zhi Min ^a  

^a LEXICON PHARMACEUTICALS INC   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

LIMONENE;

ARTICLE; CHEMICAL PROCEDURES; CHIRALITY; CIS ISOMER; ISOMERISM; SCALE UP; SYNTHESIS; TRANS ISOMER;

EID: 17444400112     PISSN: 10836160     EISSN: None     Source Type: Journal    
DOI: 10.1021/op0498464     Document Type: Article

References (64)

1. For examples of syntheses utilizing limonene as the chiral template, see: (a) Van Tamelen, E. E.; Anderson, R. J. J. Am. Chem. Soc. 1972, 94, 8225. (b) Pawson, B. A.; Cheung, H.-C.; Gurbaxani, S.; Saucy, G. J. Am. Chem. Soc. 1970, 92, 336. (c) Baudouy, R.; Prince, P. Tetrahedron 1989, 45, 2067. (d) Raquette, L. A.; Kang, H.-J. J. Am. Chem. Soc. 1991, 113, 2610. (e) Mori, K.; Kato, M. Tetrahedron Lett. 1986, 27, 981. (f) Marron, B. E.; Nicolaou, K. C. Synthesis 1989, 537. (g) Tius, M. A.; Kerr, M. A. Synth. Commun. 1988, 18, 1905. (h) Dauphin, G. Synthesis 1979, 799.
2. For examples of syntheses utilizing limonene as the chiral template, see: (a) Van Tamelen, E. E.; Anderson, R. J. J. Am. Chem. Soc. 1972, 94, 8225. (b) Pawson, B. A.; Cheung, H.-C.; Gurbaxani, S.; Saucy, G. J. Am. Chem. Soc. 1970, 92, 336. (c) Baudouy, R.; Prince, P. Tetrahedron 1989, 45, 2067. (d) Raquette, L. A.; Kang, H.-J. J. Am. Chem. Soc. 1991, 113, 2610. (e) Mori, K.; Kato, M. Tetrahedron Lett. 1986, 27, 981. (f) Marron, B. E.; Nicolaou, K. C. Synthesis 1989, 537. (g) Tius, M. A.; Kerr, M. A. Synth. Commun. 1988, 18, 1905. (h) Dauphin, G. Synthesis 1979, 799.
3. For examples of syntheses utilizing limonene as the chiral template, see: (a) Van Tamelen, E. E.; Anderson, R. J. J. Am. Chem. Soc. 1972, 94, 8225. (b) Pawson, B. A.; Cheung, H.-C.; Gurbaxani, S.; Saucy, G. J. Am. Chem. Soc. 1970, 92, 336. (c) Baudouy, R.; Prince, P. Tetrahedron 1989, 45, 2067. (d) Raquette, L. A.; Kang, H.-J. J. Am. Chem. Soc. 1991, 113, 2610. (e) Mori, K.; Kato, M. Tetrahedron Lett. 1986, 27, 981. (f) Marron, B. E.; Nicolaou, K. C. Synthesis 1989, 537. (g) Tius, M. A.; Kerr, M. A. Synth. Commun. 1988, 18, 1905. (h) Dauphin, G. Synthesis 1979, 799.
4. For examples of syntheses utilizing limonene as the chiral template, see: (a) Van Tamelen, E. E.; Anderson, R. J. J. Am. Chem. Soc. 1972, 94, 8225. (b) Pawson, B. A.; Cheung, H.-C.; Gurbaxani, S.; Saucy, G. J. Am. Chem. Soc. 1970, 92, 336. (c) Baudouy, R.; Prince, P. Tetrahedron 1989, 45, 2067. (d) Raquette, L. A.; Kang, H.-J. J. Am. Chem. Soc. 1991, 113, 2610. (e) Mori, K.; Kato, M. Tetrahedron Lett. 1986, 27, 981. (f) Marron, B. E.; Nicolaou, K. C. Synthesis 1989, 537. (g) Tius, M. A.; Kerr, M. A. Synth. Commun. 1988, 18, 1905. (h) Dauphin, G. Synthesis 1979, 799.
5. For examples of syntheses utilizing limonene as the chiral template, see: (a) Van Tamelen, E. E.; Anderson, R. J. J. Am. Chem. Soc. 1972, 94, 8225. (b) Pawson, B. A.; Cheung, H.-C.; Gurbaxani, S.; Saucy, G. J. Am. Chem. Soc. 1970, 92, 336. (c) Baudouy, R.; Prince, P. Tetrahedron 1989, 45, 2067. (d) Raquette, L. A.; Kang, H.-J. J. Am. Chem. Soc. 1991, 113, 2610. (e) Mori, K.; Kato, M. Tetrahedron Lett. 1986, 27, 981. (f) Marron, B. E.; Nicolaou, K. C. Synthesis 1989, 537. (g) Tius, M. A.; Kerr, M. A. Synth. Commun. 1988, 18, 1905. (h) Dauphin, G. Synthesis 1979, 799.
6. For examples of syntheses utilizing limonene as the chiral template, see: (a) Van Tamelen, E. E.; Anderson, R. J. J. Am. Chem. Soc. 1972, 94, 8225. (b) Pawson, B. A.; Cheung, H.-C.; Gurbaxani, S.; Saucy, G. J. Am. Chem. Soc. 1970, 92, 336. (c) Baudouy, R.; Prince, P. Tetrahedron 1989, 45, 2067. (d) Raquette, L. A.; Kang, H.-J. J. Am. Chem. Soc. 1991, 113, 2610. (e) Mori, K.; Kato, M. Tetrahedron Lett. 1986, 27, 981. (f) Marron, B. E.; Nicolaou, K. C. Synthesis 1989, 537. (g) Tius, M. A.; Kerr, M. A. Synth. Commun. 1988, 18, 1905. (h) Dauphin, G. Synthesis 1979, 799.
7. For examples of syntheses utilizing limonene as the chiral template, see: (a) Van Tamelen, E. E.; Anderson, R. J. J. Am. Chem. Soc. 1972, 94, 8225. (b) Pawson, B. A.; Cheung, H.-C.; Gurbaxani, S.; Saucy, G. J. Am. Chem. Soc. 1970, 92, 336. (c) Baudouy, R.; Prince, P. Tetrahedron 1989, 45, 2067. (d) Raquette, L. A.; Kang, H.-J. J. Am. Chem. Soc. 1991, 113, 2610. (e) Mori, K.; Kato, M. Tetrahedron Lett. 1986, 27, 981. (f) Marron, B. E.; Nicolaou, K. C. Synthesis 1989, 537. (g) Tius, M. A.; Kerr, M. A. Synth. Commun. 1988, 18, 1905. (h) Dauphin, G. Synthesis 1979, 799.
8. For examples of syntheses utilizing limonene as the chiral template, see: (a) Van Tamelen, E. E.; Anderson, R. J. J. Am. Chem. Soc. 1972, 94, 8225. (b) Pawson, B. A.; Cheung, H.-C.; Gurbaxani, S.; Saucy, G. J. Am. Chem. Soc. 1970, 92, 336. (c) Baudouy, R.; Prince, P. Tetrahedron 1989, 45, 2067. (d) Raquette, L. A.; Kang, H.-J. J. Am. Chem. Soc. 1991, 113, 2610. (e) Mori, K.; Kato, M. Tetrahedron Lett. 1986, 27, 981. (f) Marron, B. E.; Nicolaou, K. C. Synthesis 1989, 537. (g) Tius, M. A.; Kerr, M. A. Synth. Commun. 1988, 18, 1905. (h) Dauphin, G. Synthesis 1979, 799.
9. For examples, see: (a) Goralski, C. T.; Chrisman, W.; Hasha, D. L.; Nicholson, L. W.; Rudolf, P. R.; Zakett., D.; Singaram, B. Tetrahedron: Asymmetry 1997, 8, 3863. (b) Masui, M.; Shiori, T. Tetrahedron 1995, 51, 8363. (c) Masui, M.; Shiori, T. Synlett 1995, 49. (d) Kauffman, G. S.; Harris, G. D.; Dorow, R. L.; Stone, B. R. P.; Parsons, R. L., Jr.; Pesti, J. A.; Magnus, N. A.; Fortunak, J. M.; Confalone, P. N.; Nugent, W. A. Org. Lett. 2000, 2, 3119. (e) Noyori, R.; Kitamura, M.; Suga, S.; Kawai, K. J. Am. Chem. Soc. 1986, 108, 6071.
10. For examples, see: (a) Goralski, C. T.; Chrisman, W.; Hasha, D. L.; Nicholson, L. W.; Rudolf, P. R.; Zakett., D.; Singaram, B. Tetrahedron: Asymmetry 1997, 8, 3863. (b) Masui, M.; Shiori, T. Tetrahedron 1995, 51, 8363. (c) Masui, M.; Shiori, T. Synlett 1995, 49. (d) Kauffman, G. S.; Harris, G. D.; Dorow, R. L.; Stone, B. R. P.; Parsons, R. L., Jr.; Pesti, J. A.; Magnus, N. A.; Fortunak, J. M.; Confalone, P. N.; Nugent, W. A. Org. Lett. 2000, 2, 3119. (e) Noyori, R.; Kitamura, M.; Suga, S.; Kawai, K. J. Am. Chem. Soc. 1986, 108, 6071.
11. For examples, see: (a) Goralski, C. T.; Chrisman, W.; Hasha, D. L.; Nicholson, L. W.; Rudolf, P. R.; Zakett., D.; Singaram, B. Tetrahedron: Asymmetry 1997, 8, 3863. (b) Masui, M.; Shiori, T. Tetrahedron 1995, 51, 8363. (c) Masui, M.; Shiori, T. Synlett 1995, 49. (d) Kauffman, G. S.; Harris, G. D.; Dorow, R. L.; Stone, B. R. P.; Parsons, R. L., Jr.; Pesti, J. A.; Magnus, N. A.; Fortunak, J. M.; Confalone, P. N.; Nugent, W. A. Org. Lett. 2000, 2, 3119. (e) Noyori, R.; Kitamura, M.; Suga, S.; Kawai, K. J. Am. Chem. Soc. 1986, 108, 6071.
12. For examples, see: (a) Goralski, C. T.; Chrisman, W.; Hasha, D. L.; Nicholson, L. W.; Rudolf, P. R.; Zakett., D.; Singaram, B. Tetrahedron: Asymmetry 1997, 8, 3863. (b) Masui, M.; Shiori, T. Tetrahedron 1995, 51, 8363. (c) Masui, M.; Shiori, T. Synlett 1995, 49. (d) Kauffman, G. S.; Harris, G. D.; Dorow, R. L.; Stone, B. R. P.; Parsons, R. L., Jr.; Pesti, J. A.; Magnus, N. A.; Fortunak, J. M.; Confalone, P. N.; Nugent, W. A. Org. Lett. 2000, 2, 3119. (e) Noyori, R.; Kitamura, M.; Suga, S.; Kawai, K. J. Am. Chem. Soc. 1986, 108, 6071.
13. For examples, see: (a) Goralski, C. T.; Chrisman, W.; Hasha, D. L.; Nicholson, L. W.; Rudolf, P. R.; Zakett., D.; Singaram, B. Tetrahedron: Asymmetry 1997, 8, 3863. (b) Masui, M.; Shiori, T. Tetrahedron 1995, 51, 8363. (c) Masui, M.; Shiori, T. Synlett 1995, 49. (d) Kauffman, G. S.; Harris, G. D.; Dorow, R. L.; Stone, B. R. P.; Parsons, R. L., Jr.; Pesti, J. A.; Magnus, N. A.; Fortunak, J. M.; Confalone, P. N.; Nugent, W. A. Org. Lett. 2000, 2, 3119. (e) Noyori, R.; Kitamura, M.; Suga, S.; Kawai, K. J. Am. Chem. Soc. 1986, 108, 6071.
14. Togni, A.; Venanzi, L. M. Angew. Chem., Int. Ed. Engl. 1994, 33, 497.
15. For recent reviews on aziridines including their synthesis in optically active form and their ring opening reactions, see: (a) Sweeney, J. B. Chem. Soc. Rev. 2002, 31, 247. (b) McCoull, W.; Davis, F. A. Synthesis 2000, 1347. (c) Atkinson, R. S. Tetrahedron 1999, 55, 1519. (d) Jacobsen, E. N. In Comprehensive Asymmetric Catalysis; Jacobsen, E. N., Pfaltz, A., Yamamoto, H., Eds.; Springer-Verlag: Berlin, Heidelberg, New York, 1999; Vol. 2, p 607. (e) Osborn, H. M. I.; Sweeney, J. B. Tetrahedron: Asymmetry 1997, 8, 1693. (f) Tanner, D. Angew. Chem., Int. Ed. Engl. 1994, 33, 599. (g) Tanner, D. Pure Appl. Chem. 1993, 1319.
16. For recent reviews on aziridines including their synthesis in optically active form and their ring opening reactions, see: (a) Sweeney, J. B. Chem. Soc. Rev. 2002, 31, 247. (b) McCoull, W.; Davis, F. A. Synthesis 2000, 1347. (c) Atkinson, R. S. Tetrahedron 1999, 55, 1519. (d) Jacobsen, E. N. In Comprehensive Asymmetric Catalysis; Jacobsen, E. N., Pfaltz, A., Yamamoto, H., Eds.; Springer-Verlag: Berlin, Heidelberg, New York, 1999; Vol. 2, p 607. (e) Osborn, H. M. I.; Sweeney, J. B. Tetrahedron: Asymmetry 1997, 8, 1693. (f) Tanner, D. Angew. Chem., Int. Ed. Engl. 1994, 33, 599. (g) Tanner, D. Pure Appl. Chem. 1993, 1319.
17. For recent reviews on aziridines including their synthesis in optically active form and their ring opening reactions, see: (a) Sweeney, J. B. Chem. Soc. Rev. 2002, 31, 247. (b) McCoull, W.; Davis, F. A. Synthesis 2000, 1347. (c) Atkinson, R. S. Tetrahedron 1999, 55, 1519. (d) Jacobsen, E. N. In Comprehensive Asymmetric Catalysis; Jacobsen, E. N., Pfaltz, A., Yamamoto, H., Eds.; Springer-Verlag: Berlin, Heidelberg, New York, 1999; Vol. 2, p 607. (e) Osborn, H. M. I.; Sweeney, J. B. Tetrahedron: Asymmetry 1997, 8, 1693. (f) Tanner, D. Angew. Chem., Int. Ed. Engl. 1994, 33, 599. (g) Tanner, D. Pure Appl. Chem. 1993, 1319.
18. For recent reviews on aziridines including their synthesis in optically active form and their ring opening reactions, see: (a) Sweeney, J. B. Chem. Soc. Rev. 2002, 31, 247. (b) McCoull, W.; Davis, F. A. Synthesis 2000, 1347. (c) Atkinson, R. S. Tetrahedron 1999, 55, 1519. (d) Jacobsen, E. N. In Comprehensive Asymmetric Catalysis; Jacobsen, E. N., Pfaltz, A., Yamamoto, H., Eds.; Springer-Verlag: Berlin, Heidelberg, New York, 1999; Vol. 2, p 607. (e) Osborn, H. M. I.; Sweeney, J. B. Tetrahedron: Asymmetry 1997, 8, 1693. (f) Tanner, D. Angew. Chem., Int. Ed. Engl. 1994, 33, 599. (g) Tanner, D. Pure Appl. Chem. 1993, 1319.
19. For recent reviews on aziridines including their synthesis in optically active form and their ring opening reactions, see: (a) Sweeney, J. B. Chem. Soc. Rev. 2002, 31, 247. (b) McCoull, W.; Davis, F. A. Synthesis 2000, 1347. (c) Atkinson, R. S. Tetrahedron 1999, 55, 1519. (d) Jacobsen, E. N. In Comprehensive Asymmetric Catalysis; Jacobsen, E. N., Pfaltz, A., Yamamoto, H., Eds.; Springer-Verlag: Berlin, Heidelberg, New York, 1999; Vol. 2, p 607. (e) Osborn, H. M. I.; Sweeney, J. B. Tetrahedron: Asymmetry 1997, 8, 1693. (f) Tanner, D. Angew. Chem., Int. Ed. Engl. 1994, 33, 599. (g) Tanner, D. Pure Appl. Chem. 1993, 1319.
20. For recent reviews on aziridines including their synthesis in optically active form and their ring opening reactions, see: (a) Sweeney, J. B. Chem. Soc. Rev. 2002, 31, 247. (b) McCoull, W.; Davis, F. A. Synthesis 2000, 1347. (c) Atkinson, R. S. Tetrahedron 1999, 55, 1519. (d) Jacobsen, E. N. In Comprehensive Asymmetric Catalysis; Jacobsen, E. N., Pfaltz, A., Yamamoto, H., Eds.; Springer-Verlag: Berlin, Heidelberg, New York, 1999; Vol. 2, p 607. (e) Osborn, H. M. I.; Sweeney, J. B. Tetrahedron: Asymmetry 1997, 8, 1693. (f) Tanner, D. Angew. Chem., Int. Ed. Engl. 1994, 33, 599. (g) Tanner, D. Pure Appl. Chem. 1993, 1319.
21. For recent reviews on aziridines including their synthesis in optically active form and their ring opening reactions, see: (a) Sweeney, J. B. Chem. Soc. Rev. 2002, 31, 247. (b) McCoull, W.; Davis, F. A. Synthesis 2000, 1347. (c) Atkinson, R. S. Tetrahedron 1999, 55, 1519. (d) Jacobsen, E. N. In Comprehensive Asymmetric Catalysis; Jacobsen, E. N., Pfaltz, A., Yamamoto, H., Eds.; Springer-Verlag: Berlin, Heidelberg, New York, 1999; Vol. 2, p 607. (e) Osborn, H. M. I.; Sweeney, J. B. Tetrahedron: Asymmetry 1997, 8, 1693. (f) Tanner, D. Angew. Chem., Int. Ed. Engl. 1994, 33, 599. (g) Tanner, D. Pure Appl. Chem. 1993, 1319.
22. For examples of ring closure of amino-alcohols and their derivatives, see: (a) Kelly, J. W.; Eskew, N. L.; Evans, S. A. J. Org. Chem. 1986, 51, 95. (b) Kuyl-Yeheskiely, E.; Lodder, G. A.; van der Marel, G. A.; van Boom, J. H. Tetrahedron Lett. 1987, 28, 1211. (c) Wipf, P.; Miller, C. P. Tetrahedron Lett. 1992, 33, 6267. (d) Pfister, J. R. Synthesis 1994, 969.
23. For examples of ring closure of amino-alcohols and their derivatives, see: (a) Kelly, J. W.; Eskew, N. L.; Evans, S. A. J. Org. Chem. 1986, 51, 95. (b) Kuyl-Yeheskiely, E.; Lodder, G. A.; van der Marel, G. A.; van Boom, J. H. Tetrahedron Lett. 1987, 28, 1211. (c) Wipf, P.; Miller, C. P. Tetrahedron Lett. 1992, 33, 6267. (d) Pfister, J. R. Synthesis 1994, 969.
24. For examples of ring closure of amino-alcohols and their derivatives, see: (a) Kelly, J. W.; Eskew, N. L.; Evans, S. A. J. Org. Chem. 1986, 51, 95. (b) Kuyl-Yeheskiely, E.; Lodder, G. A.; van der Marel, G. A.; van Boom, J. H. Tetrahedron Lett. 1987, 28, 1211. (c) Wipf, P.; Miller, C. P. Tetrahedron Lett. 1992, 33, 6267. (d) Pfister, J. R. Synthesis 1994, 969.
25. For examples of ring closure of amino-alcohols and their derivatives, see: (a) Kelly, J. W.; Eskew, N. L.; Evans, S. A. J. Org. Chem. 1986, 51, 95. (b) Kuyl-Yeheskiely, E.; Lodder, G. A.; van der Marel, G. A.; van Boom, J. H. Tetrahedron Lett. 1987, 28, 1211. (c) Wipf, P.; Miller, C. P. Tetrahedron Lett. 1992, 33, 6267. (d) Pfister, J. R. Synthesis 1994, 969.
26. An exception to this would be to utilize proline as the amino acid, and derivatives of this important synthon have been widely used as chiral auxilaries. For example, see: Soai, K.; Ookawa, A.; Tatsuya, K.; Ogawa, K. J. Am. Chem. Soc. 1987, 109, 7111.
27. For a review on ClickChem, see: Kolb, H. C.; Finn, M. G.; Sharpless, K. B. Angew. Chem., Int. Ed. 2001, 40, 2004.
28. For examples of the epoxidation of the endocyclic double bond of limonene, see: (a) Newhall, W. F. J. Org. Chem. 1959, 24, 1673. (b) Knoll, W.; Tamm, C. Helv. Chim. Acta 1975, 58, 1162. (c) Suemune, H.; Kawahara, T.; Sakai, K. Chem. Pharm. Bull. 1986, 34, 550. (d) Lange, G. L.; Neidert, E. E.; Orrom, W. J.; Wallace, D. J. Can. J. Chem. 1978, 56, 1628. (e) White, J. D.; Ruppert, J. F.; Avery, M. A.; Torri, S.; Nokami, J. J. Am. Chem. Soc. 1981, 103, 1813. (f) Yamasaki, M. J. Chem. Soc., Chem. Commun. 1972, 606.
29. For examples of the epoxidation of the endocyclic double bond of limonene, see: (a) Newhall, W. F. J. Org. Chem. 1959, 24, 1673. (b) Knoll, W.; Tamm, C. Helv. Chim. Acta 1975, 58, 1162. (c) Suemune, H.; Kawahara, T.; Sakai, K. Chem. Pharm. Bull. 1986, 34, 550. (d) Lange, G. L.; Neidert, E. E.; Orrom, W. J.; Wallace, D. J. Can. J. Chem. 1978, 56, 1628. (e) White, J. D.; Ruppert, J. F.; Avery, M. A.; Torri, S.; Nokami, J. J. Am. Chem. Soc. 1981, 103, 1813. (f) Yamasaki, M. J. Chem. Soc., Chem. Commun. 1972, 606.
30. For examples of the epoxidation of the endocyclic double bond of limonene, see: (a) Newhall, W. F. J. Org. Chem. 1959, 24, 1673. (b) Knoll, W.; Tamm, C. Helv. Chim. Acta 1975, 58, 1162. (c) Suemune, H.; Kawahara, T.; Sakai, K. Chem. Pharm. Bull. 1986, 34, 550. (d) Lange, G. L.; Neidert, E. E.; Orrom, W. J.; Wallace, D. J. Can. J. Chem. 1978, 56, 1628. (e) White, J. D.; Ruppert, J. F.; Avery, M. A.; Torri, S.; Nokami, J. J. Am. Chem. Soc. 1981, 103, 1813. (f) Yamasaki, M. J. Chem. Soc., Chem. Commun. 1972, 606.
31. For examples of the epoxidation of the endocyclic double bond of limonene, see: (a) Newhall, W. F. J. Org. Chem. 1959, 24, 1673. (b) Knoll, W.; Tamm, C. Helv. Chim. Acta 1975, 58, 1162. (c) Suemune, H.; Kawahara, T.; Sakai, K. Chem. Pharm. Bull. 1986, 34, 550. (d) Lange, G. L.; Neidert, E. E.; Orrom, W. J.; Wallace, D. J. Can. J. Chem. 1978, 56, 1628. (e) White, J. D.; Ruppert, J. F.; Avery, M. A.; Torri, S.; Nokami, J. J. Am. Chem. Soc. 1981, 103, 1813. (f) Yamasaki, M. J. Chem. Soc., Chem. Commun. 1972, 606.
32. For examples of the epoxidation of the endocyclic double bond of limonene, see: (a) Newhall, W. F. J. Org. Chem. 1959, 24, 1673. (b) Knoll, W.; Tamm, C. Helv. Chim. Acta 1975, 58, 1162. (c) Suemune, H.; Kawahara, T.; Sakai, K. Chem. Pharm. Bull. 1986, 34, 550. (d) Lange, G. L.; Neidert, E. E.; Orrom, W. J.; Wallace, D. J. Can. J. Chem. 1978, 56, 1628. (e) White, J. D.; Ruppert, J. F.; Avery, M. A.; Torri, S.; Nokami, J. J. Am. Chem. Soc. 1981, 103, 1813. (f) Yamasaki, M. J. Chem. Soc., Chem. Commun. 1972, 606.
33. For examples of the epoxidation of the endocyclic double bond of limonene, see: (a) Newhall, W. F. J. Org. Chem. 1959, 24, 1673. (b) Knoll, W.; Tamm, C. Helv. Chim. Acta 1975, 58, 1162. (c) Suemune, H.; Kawahara, T.; Sakai, K. Chem. Pharm. Bull. 1986, 34, 550. (d) Lange, G. L.; Neidert, E. E.; Orrom, W. J.; Wallace, D. J. Can. J. Chem. 1978, 56, 1628. (e) White, J. D.; Ruppert, J. F.; Avery, M. A.; Torri, S.; Nokami, J. J. Am. Chem. Soc. 1981, 103, 1813. (f) Yamasaki, M. J. Chem. Soc., Chem. Commun. 1972, 606.
34. (a) Steiner, D.; Sethofer, S. G.; Goralski, C. T.; Singaram, B. Tetrahedron: Asymmetry 2002, 13, 1477.
35. (b) Chrisman, W.; Camara, J. N.; Marcellini, K.; Singaram, B.; Goralski, C. T.; Hasha, D. L.; Rudolf, P. R.; Nicholson, L. W.; Borofychuk, K. K. Tetrahedron Lett. 2001, 42, 5805.
36. For examples of other chiral auxiliaries derived from limonene, see: (a) Comins, D. L.; Guerra-Weltzien, L.; Salvador, J. M. Synlett 1994, 972. (b) Comins, D. L.; Guerra-Weltzien, L. Tetrahedron Lett. 1996, 37, 3807. (c) Ho, T.-L.; Lee, K.-Y. Tetrahedron Lett. 1995, 36, 947.
37. For examples of other chiral auxiliaries derived from limonene, see: (a) Comins, D. L.; Guerra-Weltzien, L.; Salvador, J. M. Synlett 1994, 972. (b) Comins, D. L.; Guerra-Weltzien, L. Tetrahedron Lett. 1996, 37, 3807. (c) Ho, T.-L.; Lee, K.-Y. Tetrahedron Lett. 1995, 36, 947.
38. For examples of other chiral auxiliaries derived from limonene, see: (a) Comins, D. L.; Guerra-Weltzien, L.; Salvador, J. M. Synlett 1994, 972. (b) Comins, D. L.; Guerra-Weltzien, L. Tetrahedron Lett. 1996, 37, 3807. (c) Ho, T.-L.; Lee, K.-Y. Tetrahedron Lett. 1995, 36, 947.
39. Fractional distillation is possible but extremely inefficient. Royals, E. E.; Leffingwell, J. C. J. Org. Chem. 1966, 31, 1937.
40. Under harsh conditions, both epoxides can be opened with dimethylamine, and the corresponding amino-alcohols can be separated by salt formation and crystallization. For examples of this and the susbsequent conversion of the amino-alcohols back to the diastereomerically pure epoxides, see: (a) Baker, R.; Borges, M.; Cooke, N. G.; Herbert, R. H. J. Chem. Soc., Chem. Commun. 1987, 414. (b) Newhall, W. F. J. Org. Chem. 1964, 29, 185. (c) Kuczynski, H.; Piatkowski, K. Roczniki Chem. 1959, 33, 299. (d) Patrick, R.; Newhall J. J. Agric. Food Chem. 1960, 8, 397.
41. Under harsh conditions, both epoxides can be opened with dimethylamine, and the corresponding amino-alcohols can be separated by salt formation and crystallization. For examples of this and the susbsequent conversion of the amino-alcohols back to the diastereomerically pure epoxides, see: (a) Baker, R.; Borges, M.; Cooke, N. G.; Herbert, R. H. J. Chem. Soc., Chem. Commun. 1987, 414. (b) Newhall, W. F. J. Org. Chem. 1964, 29, 185. (c) Kuczynski, H.; Piatkowski, K. Roczniki Chem. 1959, 33, 299. (d) Patrick, R.; Newhall J. J. Agric. Food Chem. 1960, 8, 397.
42. Under harsh conditions, both epoxides can be opened with dimethylamine, and the corresponding amino-alcohols can be separated by salt formation and crystallization. For examples of this and the susbsequent conversion of the amino-alcohols back to the diastereomerically pure epoxides, see: (a) Baker, R.; Borges, M.; Cooke, N. G.; Herbert, R. H. J. Chem. Soc., Chem. Commun. 1987, 414. (b) Newhall, W. F. J. Org. Chem. 1964, 29, 185. (c) Kuczynski, H.; Piatkowski, K. Roczniki Chem. 1959, 33, 299. (d) Patrick, R.; Newhall J. J. Agric. Food Chem. 1960, 8, 397.
43. Under harsh conditions, both epoxides can be opened with dimethylamine, and the corresponding amino-alcohols can be separated by salt formation and crystallization. For examples of this and the susbsequent conversion of the amino-alcohols back to the diastereomerically pure epoxides, see: (a) Baker, R.; Borges, M.; Cooke, N. G.; Herbert, R. H. J. Chem. Soc., Chem. Commun. 1987, 414. (b) Newhall, W. F. J. Org. Chem. 1964, 29, 185. (c) Kuczynski, H.; Piatkowski, K. Roczniki Chem. 1959, 33, 299. (d) Patrick, R.; Newhall J. J. Agric. Food Chem. 1960, 8, 397.
44. For examples, see: (a) Steiner, D.; Ivison, L.; Goralski, C. T.; Appell, R. B.; Gojkovic, J. R.; Singaram, B. Tetrahedron: Asymmetry 2002, 13, 2359. (b) Jones, J.; dos Santos, A. G.; de Lima Castro, F. Synth. Commun. 1996, 26, 2651. (c) Cole-Hamilton, D. J.; Salles, L.; Nixon, A. F.; Russell, N. C.; Clarke, R.; Pogorzelec, P. Tetrahedron: Asymmetry 1999, 10, 1471. (d) Van der Warf, M. J.; Jongejan, H.; Franssen, M. C. R. Tetrahedron Lett. 2001, 42, 5521.
45. For examples, see: (a) Steiner, D.; Ivison, L.; Goralski, C. T.; Appell, R. B.; Gojkovic, J. R.; Singaram, B. Tetrahedron: Asymmetry 2002, 13, 2359. (b) Jones, J.; dos Santos, A. G.; de Lima Castro, F. Synth. Commun. 1996, 26, 2651. (c) Cole-Hamilton, D. J.; Salles, L.; Nixon, A. F.; Russell, N. C.; Clarke, R.; Pogorzelec, P. Tetrahedron: Asymmetry 1999, 10, 1471. (d) Van der Warf, M. J.; Jongejan, H.; Franssen, M. C. R. Tetrahedron Lett. 2001, 42, 5521.
46. For examples, see: (a) Steiner, D.; Ivison, L.; Goralski, C. T.; Appell, R. B.; Gojkovic, J. R.; Singaram, B. Tetrahedron: Asymmetry 2002, 13, 2359. (b) Jones, J.; dos Santos, A. G.; de Lima Castro, F. Synth. Commun. 1996, 26, 2651. (c) Cole-Hamilton, D. J.; Salles, L.; Nixon, A. F.; Russell, N. C.; Clarke, R.; Pogorzelec, P. Tetrahedron: Asymmetry 1999, 10, 1471. (d) Van der Warf, M. J.; Jongejan, H.; Franssen, M. C. R. Tetrahedron Lett. 2001, 42, 5521.
47. For examples, see: (a) Steiner, D.; Ivison, L.; Goralski, C. T.; Appell, R. B.; Gojkovic, J. R.; Singaram, B. Tetrahedron: Asymmetry 2002, 13, 2359. (b) Jones, J.; dos Santos, A. G.; de Lima Castro, F. Synth. Commun. 1996, 26, 2651. (c) Cole-Hamilton, D. J.; Salles, L.; Nixon, A. F.; Russell, N. C.; Clarke, R.; Pogorzelec, P. Tetrahedron: Asymmetry 1999, 10, 1471. (d) Van der Warf, M. J.; Jongejan, H.; Franssen, M. C. R. Tetrahedron Lett. 2001, 42, 5521.
48. Enzyme mediated hydrolyses has also been reported. See: (a) Weijers, C. A. G. M. Tetrahedron: Asymmetry 1997, 8, 639. (b) Van der Werf, M. J.; Orru, R. V. A.; Overcamp, K. M.; Swarts, H. J.; Osprian, A.; de Bont, J. A. M.; Faber, K. Appl. Microbiol. Biotechnol. 1999, 52, 38.
49. Enzyme mediated hydrolyses has also been reported. See: (a) Weijers, C. A. G. M. Tetrahedron: Asymmetry 1997, 8, 639. (b) Van der Werf, M. J.; Orru, R. V. A.; Overcamp, K. M.; Swarts, H. J.; Osprian, A.; de Bont, J. A. M.; Faber, K. Appl. Microbiol. Biotechnol. 1999, 52, 38.
50. For examples, see: (a) Davis, C. E.; Bailey, J. L.; Lockner, J. W.; Coates, R. M. J. Org. Chem. 2003, 68, 75. (b) Bochvic, B.; Kapuscinski, J.; Olejniczak, B. Roczniki Chem. 1971, 45, 869. (c) Subbaraj, A.; Rao, O. S.; Lwowski, W. J. Org. Chem. 1989, 54, 3945. (c) Bergmeier, S. C.; Seth, P. P. Tetrahedron Lett. 1999, 40, 6181. (d) Corey, E. J.; Ortiz de Montellano, P. R.; Lin, K.; Dean, P. D. G. J. Am. Chem. Soc. 1967, 89, 2797. (e) Avruch, L.; Oehlschlager, A. C. Synthesis 1973, 622. (f) van Ende, D.; Krief, A. Angew. Chem., Int. Ed. Engl. 1974, 13, 279. (g) Parrish, E. J.; Nes, W. D. Synth. Commun. 1988, 18, 221. (h) Nes, W. D.; Parrish, E. J. Lipids 1988, 23, 375. (i) Corey, E. J.; Riddiford, L. M.; Ajami, A. M.; Yamamoto, H.; Anderson, J. E. J. Am. Chem. Soc. 1971, 93, 1815.
51. For examples, see: (a) Davis, C. E.; Bailey, J. L.; Lockner, J. W.; Coates, R. M. J. Org. Chem. 2003, 68, 75. (b) Bochvic, B.; Kapuscinski, J.; Olejniczak, B. Roczniki Chem. 1971, 45, 869. (c) Subbaraj, A.; Rao, O. S.; Lwowski, W. J. Org. Chem. 1989, 54, 3945. (c) Bergmeier, S. C.; Seth, P. P. Tetrahedron Lett. 1999, 40, 6181. (d) Corey, E. J.; Ortiz de Montellano, P. R.; Lin, K.; Dean, P. D. G. J. Am. Chem. Soc. 1967, 89, 2797. (e) Avruch, L.; Oehlschlager, A. C. Synthesis 1973, 622. (f) van Ende, D.; Krief, A. Angew. Chem., Int. Ed. Engl. 1974, 13, 279. (g) Parrish, E. J.; Nes, W. D. Synth. Commun. 1988, 18, 221. (h) Nes, W. D.; Parrish, E. J. Lipids 1988, 23, 375. (i) Corey, E. J.; Riddiford, L. M.; Ajami, A. M.; Yamamoto, H.; Anderson, J. E. J. Am. Chem. Soc. 1971, 93, 1815.
52. For examples, see: (a) Davis, C. E.; Bailey, J. L.; Lockner, J. W.; Coates, R. M. J. Org. Chem. 2003, 68, 75. (b) Bochvic, B.; Kapuscinski, J.; Olejniczak, B. Roczniki Chem. 1971, 45, 869. (c) Subbaraj, A.; Rao, O. S.; Lwowski, W. J. Org. Chem. 1989, 54, 3945. (c) Bergmeier, S. C.; Seth, P. P. Tetrahedron Lett. 1999, 40, 6181. (d) Corey, E. J.; Ortiz de Montellano, P. R.; Lin, K.; Dean, P. D. G. J. Am. Chem. Soc. 1967, 89, 2797. (e) Avruch, L.; Oehlschlager, A. C. Synthesis 1973, 622. (f) van Ende, D.; Krief, A. Angew. Chem., Int. Ed. Engl. 1974, 13, 279. (g) Parrish, E. J.; Nes, W. D. Synth. Commun. 1988, 18, 221. (h) Nes, W. D.; Parrish, E. J. Lipids 1988, 23, 375. (i) Corey, E. J.; Riddiford, L. M.; Ajami, A. M.; Yamamoto, H.; Anderson, J. E. J. Am. Chem. Soc. 1971, 93, 1815.
53. For examples, see: (a) Davis, C. E.; Bailey, J. L.; Lockner, J. W.; Coates, R. M. J. Org. Chem. 2003, 68, 75. (b) Bochvic, B.; Kapuscinski, J.; Olejniczak, B. Roczniki Chem. 1971, 45, 869. (c) Subbaraj, A.; Rao, O. S.; Lwowski, W. J. Org. Chem. 1989, 54, 3945. (c) Bergmeier, S. C.; Seth, P. P. Tetrahedron Lett. 1999, 40, 6181. (d) Corey, E. J.; Ortiz de Montellano, P. R.; Lin, K.; Dean, P. D. G. J. Am. Chem. Soc. 1967, 89, 2797. (e) Avruch, L.; Oehlschlager, A. C. Synthesis 1973, 622. (f) van Ende, D.; Krief, A. Angew. Chem., Int. Ed. Engl. 1974, 13, 279. (g) Parrish, E. J.; Nes, W. D. Synth. Commun. 1988, 18, 221. (h) Nes, W. D.; Parrish, E. J. Lipids 1988, 23, 375. (i) Corey, E. J.; Riddiford, L. M.; Ajami, A. M.; Yamamoto, H.; Anderson, J. E. J. Am. Chem. Soc. 1971, 93, 1815.
54. For examples, see: (a) Davis, C. E.; Bailey, J. L.; Lockner, J. W.; Coates, R. M. J. Org. Chem. 2003, 68, 75. (b) Bochvic, B.; Kapuscinski, J.; Olejniczak, B. Roczniki Chem. 1971, 45, 869. (c) Subbaraj, A.; Rao, O. S.; Lwowski, W. J. Org. Chem. 1989, 54, 3945. (c) Bergmeier, S. C.; Seth, P. P. Tetrahedron Lett. 1999, 40, 6181. (d) Corey, E. J.; Ortiz de Montellano, P. R.; Lin, K.; Dean, P. D. G. J. Am. Chem. Soc. 1967, 89, 2797. (e) Avruch, L.; Oehlschlager, A. C. Synthesis 1973, 622. (f) van Ende, D.; Krief, A. Angew. Chem., Int. Ed. Engl. 1974, 13, 279. (g) Parrish, E. J.; Nes, W. D. Synth. Commun. 1988, 18, 221. (h) Nes, W. D.; Parrish, E. J. Lipids 1988, 23, 375. (i) Corey, E. J.; Riddiford, L. M.; Ajami, A. M.; Yamamoto, H.; Anderson, J. E. J. Am. Chem. Soc. 1971, 93, 1815.
55. For examples, see: (a) Davis, C. E.; Bailey, J. L.; Lockner, J. W.; Coates, R. M. J. Org. Chem. 2003, 68, 75. (b) Bochvic, B.; Kapuscinski, J.; Olejniczak, B. Roczniki Chem. 1971, 45, 869. (c) Subbaraj, A.; Rao, O. S.; Lwowski, W. J. Org. Chem. 1989, 54, 3945. (c) Bergmeier, S. C.; Seth, P. P. Tetrahedron Lett. 1999, 40, 6181. (d) Corey, E. J.; Ortiz de Montellano, P. R.; Lin, K.; Dean, P. D. G. J. Am. Chem. Soc. 1967, 89, 2797. (e) Avruch, L.; Oehlschlager, A. C. Synthesis 1973, 622. (f) van Ende, D.; Krief, A. Angew. Chem., Int. Ed. Engl. 1974, 13, 279. (g) Parrish, E. J.; Nes, W. D. Synth. Commun. 1988, 18, 221. (h) Nes, W. D.; Parrish, E. J. Lipids 1988, 23, 375. (i) Corey, E. J.; Riddiford, L. M.; Ajami, A. M.; Yamamoto, H.; Anderson, J. E. J. Am. Chem. Soc. 1971, 93, 1815.
56. For examples, see: (a) Davis, C. E.; Bailey, J. L.; Lockner, J. W.; Coates, R. M. J. Org. Chem. 2003, 68, 75. (b) Bochvic, B.; Kapuscinski, J.; Olejniczak, B. Roczniki Chem. 1971, 45, 869. (c) Subbaraj, A.; Rao, O. S.; Lwowski, W. J. Org. Chem. 1989, 54, 3945. (c) Bergmeier, S. C.; Seth, P. P. Tetrahedron Lett. 1999, 40, 6181. (d) Corey, E. J.; Ortiz de Montellano, P. R.; Lin, K.; Dean, P. D. G. J. Am. Chem. Soc. 1967, 89, 2797. (e) Avruch, L.; Oehlschlager, A. C. Synthesis 1973, 622. (f) van Ende, D.; Krief, A. Angew. Chem., Int. Ed. Engl. 1974, 13, 279. (g) Parrish, E. J.; Nes, W. D. Synth. Commun. 1988, 18, 221. (h) Nes, W. D.; Parrish, E. J. Lipids 1988, 23, 375. (i) Corey, E. J.; Riddiford, L. M.; Ajami, A. M.; Yamamoto, H.; Anderson, J. E. J. Am. Chem. Soc. 1971, 93, 1815.
57. For examples, see: (a) Davis, C. E.; Bailey, J. L.; Lockner, J. W.; Coates, R. M. J. Org. Chem. 2003, 68, 75. (b) Bochvic, B.; Kapuscinski, J.; Olejniczak, B. Roczniki Chem. 1971, 45, 869. (c) Subbaraj, A.; Rao, O. S.; Lwowski, W. J. Org. Chem. 1989, 54, 3945. (c) Bergmeier, S. C.; Seth, P. P. Tetrahedron Lett. 1999, 40, 6181. (d) Corey, E. J.; Ortiz de Montellano, P. R.; Lin, K.; Dean, P. D. G. J. Am. Chem. Soc. 1967, 89, 2797. (e) Avruch, L.; Oehlschlager, A. C. Synthesis 1973, 622. (f) van Ende, D.; Krief, A. Angew. Chem., Int. Ed. Engl. 1974, 13, 279. (g) Parrish, E. J.; Nes, W. D. Synth. Commun. 1988, 18, 221. (h) Nes, W. D.; Parrish, E. J. Lipids 1988, 23, 375. (i) Corey, E. J.; Riddiford, L. M.; Ajami, A. M.; Yamamoto, H.; Anderson, J. E. J. Am. Chem. Soc. 1971, 93, 1815.
58. For examples, see: (a) Davis, C. E.; Bailey, J. L.; Lockner, J. W.; Coates, R. M. J. Org. Chem. 2003, 68, 75. (b) Bochvic, B.; Kapuscinski, J.; Olejniczak, B. Roczniki Chem. 1971, 45, 869. (c) Subbaraj, A.; Rao, O. S.; Lwowski, W. J. Org. Chem. 1989, 54, 3945. (c) Bergmeier, S. C.; Seth, P. P. Tetrahedron Lett. 1999, 40, 6181. (d) Corey, E. J.; Ortiz de Montellano, P. R.; Lin, K.; Dean, P. D. G. J. Am. Chem. Soc. 1967, 89, 2797. (e) Avruch, L.; Oehlschlager, A. C. Synthesis 1973, 622. (f) van Ende, D.; Krief, A. Angew. Chem., Int. Ed. Engl. 1974, 13, 279. (g) Parrish, E. J.; Nes, W. D. Synth. Commun. 1988, 18, 221. (h) Nes, W. D.; Parrish, E. J. Lipids 1988, 23, 375. (i) Corey, E. J.; Riddiford, L. M.; Ajami, A. M.; Yamamoto, H.; Anderson, J. E. J. Am. Chem. Soc. 1971, 93, 1815.
59. For examples, see: (a) Davis, C. E.; Bailey, J. L.; Lockner, J. W.; Coates, R. M. J. Org. Chem. 2003, 68, 75. (b) Bochvic, B.; Kapuscinski, J.; Olejniczak, B. Roczniki Chem. 1971, 45, 869. (c) Subbaraj, A.; Rao, O. S.; Lwowski, W. J. Org. Chem. 1989, 54, 3945. (c) Bergmeier, S. C.; Seth, P. P. Tetrahedron Lett. 1999, 40, 6181. (d) Corey, E. J.; Ortiz de Montellano, P. R.; Lin, K.; Dean, P. D. G. J. Am. Chem. Soc. 1967, 89, 2797. (e) Avruch, L.; Oehlschlager, A. C. Synthesis 1973, 622. (f) van Ende, D.; Krief, A. Angew. Chem., Int. Ed. Engl. 1974, 13, 279. (g) Parrish, E. J.; Nes, W. D. Synth. Commun. 1988, 18, 221. (h) Nes, W. D.; Parrish, E. J. Lipids 1988, 23, 375. (i) Corey, E. J.; Riddiford, L. M.; Ajami, A. M.; Yamamoto, H.; Anderson, J. E. J. Am. Chem. Soc. 1971, 93, 1815.
60. Deslongchamps, P. Stereoelectronic Effects in Organic Chemistry; Pergamon: New York, 1983; Chapter 5.
61. 15a reports modest selectivity in the ring opening of the mixture of aziridines at low temperature using diethylaluminium azide as the nucleophile.
62. Gololobov, Y G.; Zhmurova, I. N.; Kasukhin, L. F. Tetrahedron 1981, 37, 437.
63. For a similar transformation, see: Sommerdijk, N. A. J. M.; Buynsters, P. J. J. A.; Akdemir, H.; Geurts, D. G.; Nolte, R. J. M.; Zwanenburg, B. J. Org. Chem. 1997, 62, 4955. Interestingly the authors report that the success of the transformation is dependent on the scale on which the reaction is run and that the transformation is not amenable to being run on large scale. This is not the case with our procedure.
64. Ferrero, L.; Geribaldi, S.; Rouillard, M.; Azzaro, M. Can. J. Chem. 1975, 53, 3227.