Enantiodivergent synthesis of tetra-ortho-substituted biphenyls by enzymatic desymmetrization

Synlett

Volumn , Issue 6, 2009, Pages 941-944

  Okuyama, Kumi ^a   Shingubara, Koji ^a   Tsujiyama, Shin Ichiro ^a   Suzuki, Keisuke ^a   Matsumoto, Takashi ^a  

^a TOKYO INSTITUTE OF TECHNOLOGY   (Japan)

Author keywords

Asymmetric synthesis; Biphenyl; Desymmetrization; Enzyme catalysis; Hydrolysis

Indexed keywords

BIPHENYL DERIVATIVE;

ARTICLE; CATALYST; CHEMICAL REACTION; CHEMICAL STRUCTURE; ENANTIOMER; ENANTIOSELECTIVITY; ENZYMATIC ASSAY; HYDROLYSIS; SYNTHESIS;

EID: 64249151382     PISSN: 09365214     EISSN: 14372096     Source Type: Journal    
DOI: 10.1055/s-0028-1088215     Document Type: Article

References (23)

1. (a) Bringmann, G.; Mortimer, A. J. P.; Keller, P. A.; Gresser, M. J.; Garner, J.; Breuning, M.Angew. Chem. Int. Ed. 2005, 44,5384.
2. (b) Baudoin, O. Eur. J. Org. Chem. 2005, 4223.
3. (c) Cepanec, I. In Synthesis of Biaryls; Elsevier: Oxford, 2004.
4. Recent examples of stereoselective synthesis of tetra-orthosubstituted biaryls: (a) Meyers, A. I.; Nelson, T. D.; Moorlag, H.; Raeson, D. J.; Meier, A. Tetrahedron 2004,60, 4459.
5. (b) Ohmori, K.; Tamiya, M.; Kitamura, M.; Kato, H.; Ohrui, M.; Suzuki, K. Angew. Chem. Int. Ed. 2005, 44, 3871.
6. (c) Nishida, G.; Suzuki, N.; Noguchi, K.; Tanaka, K. Org. Lett. 2006, 8, 3489.
7. (d) Bringmann, G.; Scharl, H.; Maksimenka, K.; Radacki, K.; Braunschweig, H.; Wich, P.; Schmuck, C. Eur. J. Org. Chem. 2006, 4349.
8. (e) Nishida, G.; Noguchi, K.; Hirano, M.; Tanaka, K. Angew. Chem. Int. Ed. 2007, 46, 3951.
9. (f) Shibata, T.; Yoshida, S.; Arai, Y.; Otsuka, M.; Endo, K. Tetrahedron 2008, 64, 821.
10. (g) Ashizawa, T.; Tanaka, S.; Yamada, T. Org. Lett. 2008,2008, 2521.
11. (a) Matsumoto, T.; Konegawa, T.; Nakamura, T.; Suzuki, K. Synlett 2002, 122.
12. (b) For a review on enantioselective enzymatic desymmetrization, see: García-Urdiales, E.; Alfonso, I.; Gotor, V. Chem. Rev. 2005, 105, 313.
13. Other examples of asymmetric desymmetrization of achiral biaryl derivatives: (a) Hayashi, T.; Niizuma, S.; Kamikawa, T.; Suzuki, N.; Uozumi, Y. J. Am. Chem. Soc. 1995, 117, 9101.
14. (b) Harada, T.; Ueda, S.; Yoshida, T.; Inoue, A.; Takeuchi, M.; Ogawa, N.; Oku, A. J. Org. Chem. 1994, 59, 7575.
15. Miyaura, N.; Suzuki, A. Chem. Rev. 1995, 95, 2457.
16. PFL [Pseudomonas fluorescence lipase (Amano, lipase AK)], PLE [pig liver esterase (Sigma)], PCL [Pseudomonas cepacia lipase (Amano, lipase PS)], CRL [Candida rugosa lipase (Amano, lipase AY)], ANL [Aspergillus niger lipase (Amano, lipase A)], PPL [porcine pancreas lipase (Sigma, Type II)], CAL [Candida antarctica lipase (Roche Diagnostics, Chirazyme L-2)], ROL [Rhizopus oryzae lipase (Amano, lipase F-AP15)] were tested.
17. R = 9.2 min for (-)-6a, 14.5 min for (+)-6a; 12.8 min for (-)-6b, 14.8 min for (+)-6b; 9.7 min for (-)-6c, 12.7 min for (+)-6c.
18. The absolute stereostructures of 6a and 6b were determined by X-ray crystallography after derivatization [(-)-camphanic chloride, DMAP, pyridine] to 16a and 16b, respectively (Figure 2). The absolute configuration of (+)-6c was determined by chemical correlation with (+)-6a as shown in Scheme 5.
19. Though less effective, (R)-6b and (R)-6c were also obtained with CAL or PCL, and (S)-6b was also obtained with PLE. It is interesting to note that the enzymes of microorganism origin (ROL, CAL, PCL) showed R preference and the enzymes of mammalian origin (PPL, PLE) showed S preference, whether necessarily or not.
20. 3 (1.5 equiv) in acetone at 50 °C afforded the desired methyl ether in 95% yield but with substantial decrease in ee (91%). Formation of the corresponding diacetate la and diol 7a, albeit in trace amount, suggested involvement of the intermoleculer acyl migration. Nonetheless, other protections, including methoxymethylation and tert- butyldimethylsilylation, proceeded without affecting enantiomeric integrity.
21. Taniguchi, T.; Ogasawara, K. Angew. Chem. Int. Ed. 1998,1998,1136.
22. Nakayama, K.; Uoto, K.; Higashi, K.; Soga, T.; Kusama, T. Chem. Pharm. Bull. 1992, 40, 1718.
23. Quinone 15 proved to racemize gradually after isolation [95% ee after three weeks in a refrigerator (4 °C)].