Stereospecific synthesis of chiral tertiary alkyl-aryl ethers via Mitsunobu reaction with complete inversion of configuration

Tetrahedron Letters

Volumn 44, Issue 18, 2003, Pages 3609-3611

  Shi, Yao Jun ^a   Hughes, David L ^a   McNamara, James M ^a  

^a MERCK RESEARCH LABORATORIES   (United States)

Author keywords

Alkyl aryl ether; Inversion; Mitsunobu reaction; SN2 displacement; Tertiary alcohols

Indexed keywords

ALCOHOL DERIVATIVE; ALKYL ARYL ETHER; PHENOL;

ARTICLE; CHIRALITY; MITSUNOBU REACTION; REACTION ANALYSIS; STEREOSPECIFICITY; SYNTHESIS; TEMPERATURE;

EID: 0037471454     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(03)00728-7     Document Type: Article

References (20)

1. Mitsunobu O., Yamada M. Bull. Chem. Soc. Jpn. 40:1967;2380.
2. Reviews of the Mitsunobu reaction: (a) Mitsunobu, O. Synthesis 1981, 1; (b) Hughes, D. L. Org. Reactions 1992, 42, 335; (c) Hughes, D. L. Org. Prep. Proc. Int. 1996, 28, 127.
3. Reviews of the Mitsunobu reaction: (a) Mitsunobu, O. Synthesis 1981, 1; (b) Hughes, D. L. Org. Reactions 1992, 42, 335; (c) Hughes, D. L. Org. Prep. Proc. Int. 1996, 28, 127.
4. Reviews of the Mitsunobu reaction: (a) Mitsunobu, O. Synthesis 1981, 1; (b) Hughes, D. L. Org. Reactions 1992, 42, 335; (c) Hughes, D. L. Org. Prep. Proc. Int. 1996, 28, 127.
5. Dirlam N.L., Moore B.S., Urban F.J. J. Org. Chem. 52:1987;3587.
6. For intermolecular reactions: (a) Bittner, S.; Assaf, Y. Chem. Ind. (London) 1975, 281; (b) Subramanian, R. S.; Balasubramanian, K. K. Synth. Commun. 1989, 19, 1255; (c) Subramanian, R. S.; Balasubramanian, K. K. Tetrahedron Lett. 1989, 30, 2297; (d) Brunner, H.; Hankofer, P.; Treittinger, B. Chem. Ber. 1990, 1029. For intramolecular reactions: (d) Reisch, J.; Voerste, A. A. W. J. Chem. Soc., Perkin Trans. 1 1994, 3251.
7. For intermolecular reactions: (a) Bittner, S.; Assaf, Y. Chem. Ind. (London) 1975, 281; (b) Subramanian, R. S.; Balasubramanian, K. K. Synth. Commun. 1989, 19, 1255; (c) Subramanian, R. S.; Balasubramanian, K. K. Tetrahedron Lett. 1989, 30, 2297; (d) Brunner, H.; Hankofer, P.; Treittinger, B. Chem. Ber. 1990, 1029. For intramolecular reactions: (d) Reisch, J.; Voerste, A. A. W. J. Chem. Soc., Perkin Trans. 1 1994, 3251.
8. For intermolecular reactions: (a) Bittner, S.; Assaf, Y. Chem. Ind. (London) 1975, 281; (b) Subramanian, R. S.; Balasubramanian, K. K. Synth. Commun. 1989, 19, 1255; (c) Subramanian, R. S.; Balasubramanian, K. K. Tetrahedron Lett. 1989, 30, 2297; (d) Brunner, H.; Hankofer, P.; Treittinger, B. Chem. Ber. 1990, 1029. For intramolecular reactions: (d) Reisch, J.; Voerste, A. A. W. J. Chem. Soc., Perkin Trans. 1 1994, 3251.
9. For intermolecular reactions: (a) Bittner, S.; Assaf, Y. Chem. Ind. (London) 1975, 281; (b) Subramanian, R. S.; Balasubramanian, K. K. Synth. Commun. 1989, 19, 1255; (c) Subramanian, R. S.; Balasubramanian, K. K. Tetrahedron Lett. 1989, 30, 2297; (d) Brunner, H.; Hankofer, P.; Treittinger, B. Chem. Ber. 1990, 1029. For intramolecular reactions: (d) Reisch, J.; Voerste, A. A. W. J. Chem. Soc., Perkin Trans. 1 1994, 3251.
10. For intermolecular reactions: (a) Bittner, S.; Assaf, Y. Chem. Ind. (London) 1975, 281; (b) Subramanian, R. S.; Balasubramanian, K. K. Synth. Commun. 1989, 19, 1255; (c) Subramanian, R. S.; Balasubramanian, K. K. Tetrahedron Lett. 1989, 30, 2297; (d) Brunner, H.; Hankofer, P.; Treittinger, B. Chem. Ber. 1990, 1029. For intramolecular reactions: (d) Reisch, J.; Voerste, A. A. W. J. Chem. Soc., Perkin Trans. 1 1994, 3251.
11. 2/pyridine, Müller, P.; Rossier, J.-C. J. Chem. Soc., Perkin Trans. 2 2000, 2232 and references cited therein; (b) DAST, Wachtmeister, J.; Mühlman, A.; Classon, B.; Samuelsson, B. Tetrahedron 1999, 55, 10761 and references cited therein.
12. 2/pyridine, Müller, P.; Rossier, J.-C. J. Chem. Soc., Perkin Trans. 2 2000, 2232 and references cited therein; (b) DAST, Wachtmeister, J.; Mühlman, A.; Classon, B.; Samuelsson, B. Tetrahedron 1999, 55, 10761 and references cited therein.
13. Racemic ether (±)-1 was made from alkylation of 4-(benzyloxy)phenol with methyl 2-bromobutyrate followed by α-methylation with methyl iodide and subsequent chiral HPLC separation afforded enantiomerically pure (R)-1 and (S)-1 (communication with Dr. R. Desai in our laboratories).
14. Attempts to synthesis chiral ether (S)-1 using the Pd-catalyzed cross-coupling of chiral alcohol (S)-2 and 4-(benzyloxy)phenyl bromide were unsuccessful. However, the copper-promoted cross-coupling of (S)-2 with 4-(benzyloxy)phenylboronic acid has afforded a low yield of (S)-1 with compete retention of configuration that was confirmed by chiral HPLC assay (unpublished results of Conlon, D. A.; Drahus, A. L. and Shi, Y.-J. in our laboratories). For the copper-promoted arylation of phenols with arylboronic acid, see: Evans, D. A.; Katz, J. L.; West, T. R. Tetrahedron Lett. 1998, 39, 2937.
15. The chiral alcohol (S)-2 is activated by the α-ester moiety, see: Bordwell F.G., Brannen W.T. Jr. J. Am. Chem. Soc. 5:1964;4645. and references cited therein.
16. For synthesis of chiral alcohol (S)-2, see: Tan L., Chen C.-y., Frey L., King A.O., Tillyer R.D., Xu F., Zhao D., Grabowski E.J.J., Reider P.J., O'Shea P., Dagneau P., Wang X. Tetrahedron. 58:2002;7403.
17. For temperature effects on the Mitsunobu reaction, see Ref. 2b.
18. The order of addition of reagents was critical, see Ref. 2b.
19. 4), eluent (B): MeCN, gradient (25°C): A/B from 40/60 to 20/80 over 20 min, 1.0 ml/min, 210 nm, retention time: 9.84 min for (R)-1 and 13.38 min for (S)-1 ].
20. 13C) and LCMS.