Design of a new bifunctional asymmetric catalyst from carbohydrates: Application to catalytic asymmetric cyanosilylation of aldehydes and acetophenone

Tetrahedron Letters

Volumn 41, Issue 14, 2000, Pages 2405-2409

  Kanai, Motomu ^a   Hamashima, Yoshitaka ^a   Shibasaki, Masakatsu ^a  

^a UNIVERSITY OF TOKYO   (Japan)

Author keywords

Bifunctional asymmetric catalyst; Conformation; Cyanosilylation; Lewis acid; Lewis base

Indexed keywords

ACETOPHENONE; ALDEHYDE; CARBOHYDRATE;

ARTICLE; CATALYSIS; CATALYST; REACTION ANALYSIS;

EID: 0034175598     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(00)00174-X     Document Type: Article

References (25)

1. Hamashima, Y.; Sawada, D.; Kanai, M.; Shibasaki, M. J. Am. Chem. Soc. 1999, 121, 2641-2642.
2. Shibasaki, M.; Sasai, H.; Arai, T. Angew. Chem., Int. Ed. Engl. 1997, 36, 1236-1256.
3. To our knowledge, the only example is a Ti catalyst for the phosphonylation of aldehydes. However, these catalysts derived from a carbohydrate were not the most effective ones in this work: Groaning, M. D.; Rowe, B. J.; Spilling, C. D. Tetrahedron Lett. 1998, 39, 5485-5488.
4. For other selected examples of asymmetric catalysts derived from carbohydrates, see: Chiral phosphinites or phosphines: Shin, S.; RajanBabu, T. V. Org. Lett. 1999, 1, 1229-1232; Yonehara, K.; Hashizume, T.; Ohe, K.; Uemura, S. Tetrahedron: Asymmetry 1999, 10, 4029-4035. Chiral crown ethers: van Maarschalkerwaart, D. A. H.; Willard, N. P.; Pandit, U. K. Tetrahedron 1992, 48, 8825-8840. Chiral dioxiranes: Tu, Y.; Wang, Z.-X.; Frohn, M.; He, M.; Yu, H.; Tang, Y.; Shi, Y. J. Org. Chem. 1998, 63, 8475-8485.
5. For other selected examples of asymmetric catalysts derived from carbohydrates, see: Chiral phosphinites or phosphines: Shin, S.; RajanBabu, T. V. Org. Lett. 1999, 1, 1229-1232; Yonehara, K.; Hashizume, T.; Ohe, K.; Uemura, S. Tetrahedron: Asymmetry 1999, 10, 4029-4035. Chiral crown ethers: van Maarschalkerwaart, D. A. H.; Willard, N. P.; Pandit, U. K. Tetrahedron 1992, 48, 8825-8840. Chiral dioxiranes: Tu, Y.; Wang, Z.-X.; Frohn, M.; He, M.; Yu, H.; Tang, Y.; Shi, Y. J. Org. Chem. 1998, 63, 8475-8485.
6. For other selected examples of asymmetric catalysts derived from carbohydrates, see: Chiral phosphinites or phosphines: Shin, S.; RajanBabu, T. V. Org. Lett. 1999, 1, 1229-1232; Yonehara, K.; Hashizume, T.; Ohe, K.; Uemura, S. Tetrahedron: Asymmetry 1999, 10, 4029-4035. Chiral crown ethers: van Maarschalkerwaart, D. A. H.; Willard, N. P.; Pandit, U. K. Tetrahedron 1992, 48, 8825-8840. Chiral dioxiranes: Tu, Y.; Wang, Z.-X.; Frohn, M.; He, M.; Yu, H.; Tang, Y.; Shi, Y. J. Org. Chem. 1998, 63, 8475-8485.
7. For other selected examples of asymmetric catalysts derived from carbohydrates, see: Chiral phosphinites or phosphines: Shin, S.; RajanBabu, T. V. Org. Lett. 1999, 1, 1229-1232; Yonehara, K.; Hashizume, T.; Ohe, K.; Uemura, S. Tetrahedron: Asymmetry 1999, 10, 4029-4035. Chiral crown ethers: van Maarschalkerwaart, D. A. H.; Willard, N. P.; Pandit, U. K. Tetrahedron 1992, 48, 8825-8840. Chiral dioxiranes: Tu, Y.; Wang, Z.-X.; Frohn, M.; He, M.; Yu, H.; Tang, Y.; Shi, Y. J. Org. Chem. 1998, 63, 8475-8485.
8. For selected examples, see: Belokon', Y. N.; Caveda-Cepas, S.; Green, B.; Ikonnikov, N. S.; Khrustalev, V. N.; Larichev, V. S.; Moscalenko, M. A.; North, M.; Orizu, C.; Tararov, V. I.; Tasinazzo, M.; Timofeeva, G. I.; Yashkina, L. V. J. Am. Chem. Soc. 1999, 121, 3968-3973; Hwang, C.-D.; Hwang, D.-R.; Uang, B.-J. J. Org. Chem. 1998, 63, 6762-6763; Abiko, A.; Wang, G.-Q. J. Org. Chem. 1996, 61, 2264-2265; Corey, E. J.; Wang, Z. Tetrahedron Lett. 1993, 34, 4001-4004; Ohno, H.; Nitta, H.; Tanaka, K.; Mori, A.; Inoue, S. J. Org. Chem. 1992, 57, 6778-6783; Kobayashi, S.; Tsuchiya, Y.; Mukaiyama, T. Chem. Lett. 1991, 541-544.
9. For selected examples, see: Belokon', Y. N.; Caveda-Cepas, S.; Green, B.; Ikonnikov, N. S.; Khrustalev, V. N.; Larichev, V. S.; Moscalenko, M. A.; North, M.; Orizu, C.; Tararov, V. I.; Tasinazzo, M.; Timofeeva, G. I.; Yashkina, L. V. J. Am. Chem. Soc. 1999, 121, 3968-3973; Hwang, C.-D.; Hwang, D.-R.; Uang, B.-J. J. Org. Chem. 1998, 63, 6762-6763; Abiko, A.; Wang, G.-Q. J. Org. Chem. 1996, 61, 2264-2265; Corey, E. J.; Wang, Z. Tetrahedron Lett. 1993, 34, 4001-4004; Ohno, H.; Nitta, H.; Tanaka, K.; Mori, A.; Inoue, S. J. Org. Chem. 1992, 57, 6778-6783; Kobayashi, S.; Tsuchiya, Y.; Mukaiyama, T. Chem. Lett. 1991, 541-544.
10. For selected examples, see: Belokon', Y. N.; Caveda-Cepas, S.; Green, B.; Ikonnikov, N. S.; Khrustalev, V. N.; Larichev, V. S.; Moscalenko, M. A.; North, M.; Orizu, C.; Tararov, V. I.; Tasinazzo, M.; Timofeeva, G. I.; Yashkina, L. V. J. Am. Chem. Soc. 1999, 121, 3968-3973; Hwang, C.-D.; Hwang, D.-R.; Uang, B.-J. J. Org. Chem. 1998, 63, 6762-6763; Abiko, A.; Wang, G.-Q. J. Org. Chem. 1996, 61, 2264-2265; Corey, E. J.; Wang, Z. Tetrahedron Lett. 1993, 34, 4001-4004; Ohno, H.; Nitta, H.; Tanaka, K.; Mori, A.; Inoue, S. J. Org. Chem. 1992, 57, 6778-6783; Kobayashi, S.; Tsuchiya, Y.; Mukaiyama, T. Chem. Lett. 1991, 541-544.
11. For selected examples, see: Belokon', Y. N.; Caveda-Cepas, S.; Green, B.; Ikonnikov, N. S.; Khrustalev, V. N.; Larichev, V. S.; Moscalenko, M. A.; North, M.; Orizu, C.; Tararov, V. I.; Tasinazzo, M.; Timofeeva, G. I.; Yashkina, L. V. J. Am. Chem. Soc. 1999, 121, 3968-3973; Hwang, C.-D.; Hwang, D.-R.; Uang, B.-J. J. Org. Chem. 1998, 63, 6762-6763; Abiko, A.; Wang, G.-Q. J. Org. Chem. 1996, 61, 2264-2265; Corey, E. J.; Wang, Z. Tetrahedron Lett. 1993, 34, 4001-4004; Ohno, H.; Nitta, H.; Tanaka, K.; Mori, A.; Inoue, S. J. Org. Chem. 1992, 57, 6778-6783; Kobayashi, S.; Tsuchiya, Y.; Mukaiyama, T. Chem. Lett. 1991, 541-544.
12. For selected examples, see: Belokon', Y. N.; Caveda-Cepas, S.; Green, B.; Ikonnikov, N. S.; Khrustalev, V. N.; Larichev, V. S.; Moscalenko, M. A.; North, M.; Orizu, C.; Tararov, V. I.; Tasinazzo, M.; Timofeeva, G. I.; Yashkina, L. V. J. Am. Chem. Soc. 1999, 121, 3968-3973; Hwang, C.-D.; Hwang, D.-R.; Uang, B.-J. J. Org. Chem. 1998, 63, 6762-6763; Abiko, A.; Wang, G.-Q. J. Org. Chem. 1996, 61, 2264-2265; Corey, E. J.; Wang, Z. Tetrahedron Lett. 1993, 34, 4001-4004; Ohno, H.; Nitta, H.; Tanaka, K.; Mori, A.; Inoue, S. J. Org. Chem. 1992, 57, 6778-6783; Kobayashi, S.; Tsuchiya, Y.; Mukaiyama, T. Chem. Lett. 1991, 541-544.
13. For selected examples, see: Belokon', Y. N.; Caveda-Cepas, S.; Green, B.; Ikonnikov, N. S.; Khrustalev, V. N.; Larichev, V. S.; Moscalenko, M. A.; North, M.; Orizu, C.; Tararov, V. I.; Tasinazzo, M.; Timofeeva, G. I.; Yashkina, L. V. J. Am. Chem. Soc. 1999, 121, 3968-3973; Hwang, C.-D.; Hwang, D.-R.; Uang, B.-J. J. Org. Chem. 1998, 63, 6762-6763; Abiko, A.; Wang, G.-Q. J. Org. Chem. 1996, 61, 2264-2265; Corey, E. J.; Wang, Z. Tetrahedron Lett. 1993, 34, 4001-4004; Ohno, H.; Nitta, H.; Tanaka, K.; Mori, A.; Inoue, S. J. Org. Chem. 1992, 57, 6778-6783; Kobayashi, S.; Tsuchiya, Y.; Mukaiyama, T. Chem. Lett. 1991, 541-544.
14. Developing a practical asymmetric cyanosilylation of ketones is an unsolved problem: Belokon', Y. N.; Green, B.; Ikonnikov, N. S.; North, M.; Tararov, V. I. Tetrahedron Lett. 1999, 40, 8147-8150 and references cited therein; Choi, M. C. K.; Chan, S. S.; Matsumoto, K. Tetrahedron Lett. 1997, 38, 6669-6672.
15. 31P; δ 34.23.
16. The importance of a phosphine oxide as the Lewis base was also confirmed from the fact that the catalysts containing a phosphine or an amine as the Lewis base gave rather low selectivities.
17. 3).
18. 1H NMR as shown below.
19. iPr (32% ee (R)).
20. 2, AcOEt/hexane 1/4). Acid hydrolysis and usual workup followed by purification by silica gel column chromatography gave the corresponding cyanohydrin.
21. These calculations were done with the universal force field of Cerius 2_3.8.
22. From the Curtin-Hammet principle, the distribution of the ground state species may not be reflected on the actual reaction pathway. However, the difference between transition state energies by the dual activation pathway and the mono activation pathway by the Lewis acid seems to be not large enough to overcome the ground state distribution, since the activation of TMSCN by the phosphine oxide is not strong. For the activation ability of the phosphine oxide toward TMSCN, see Ref. 1.
23. The same consideration may explain the lower enantioselectivities by α-substituted catalysts (see Ref. 11). In these cases, the optimum conformer A is destabilized by the α-substituent.
24. However, the cyanosilylation of acetophenone with catalyst 1 did not proceed.
25. iPrOH/hexane 2/98, flow rate 0.5 mL/min, retention time 15 min for the R isomer and 16 min for the S isomer). The absolute configuration of the product was determined by the optical rotation of the cyanohydrin: Kilijunen, E.; Kanerva, L. T. Tetrahedron: Asymmetry 1997, 8, 1551-1557. Compound 7 gave the almost the same ee.