Regioselective and enantiospecific rhodium-catalyzed intermolecular allylic etherification with ortho-substituted phenols [17]

Journal of the American Chemical Society

Volumn 122, Issue 20, 2000, Pages 5012-5013

  Evans, P Andrew ^a   Leahy, David K ^a  

^a UNIVERSITY OF DELAWARE   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

LITHIUM; PHENOL DERIVATIVE; POTASSIUM ION; RHODIUM;

DRUG SELECTIVITY; ENANTIOMER; LETTER; METAL BINDING; ORGANIC CHEMISTRY; STEREOISOMERISM; STRUCTURE ANALYSIS;

EID: 0034709421     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja0003831     Document Type: Letter

References (33)

1. For a recent review on transition metal-catalyzed aryl ether formation, see: Hartwig, J. F. Angew. Chem., Int. Ed. 1998, 37, 2046 and pertinent references therein.
2. For leading references on intra- and intermolecular metal-catalyzed aryl ether formation from aryl halides and alcohols, see: (a) Palucki, M.; Wolfe, J. P.; Buchwald, S. L. J. Am. Chem. Soc. 1996, 118, 10333.
3. (b) Mann, G.; Hartwig, J. F. J. Am. Chem. Soc. 1996, 118, 13109.
4. (c) Palucki, M.; Wolfe, J. P.; Buchwald, S. L. J. Am. Chem. Soc. 1997, 119, 3395.
5. (d) Mann, G.; Hartwig, J. F. J. Org. Chem. 1997, 62, 5413.
6. (e) Widenhoefer, R. A.; Zhong, H. A.; Buchwald, S. L J. Am. Chem. Soc. 1997, 119, 6787.
7. (f) Mann, G.; Incarvito, C.; Rheingold, A. L.; Hartwig, J. F. J. Am. Chem. Soc. 1999, 121, 3224 and pertinent references therein.
8. For recent reviews on the metal-catalyzed allylic substitution reaction, see: (a) Frost, C. G.; Howarth, J.; Williams, J. M. J. Tetrahedron: Asymmetry 1992, 3, 1089.
9. (b) Trost, B. M.; Van Vranken, D. L. Chem. Rev. 1996, 96, 395.
10. (c) Tsuji, J. In Palladium Reagents and Catalysts; John Wiley and Sons: New York, 1996; p 290. For an example of a highly regio- and enantioselective palladium-catalyzed allylic etherification, see: Trost, B. M.; Toste, F. D. J. Am. Chem. Soc. 1998, 120, 9074.
11. (c) Tsuji, J. In Palladium Reagents and Catalysts; John Wiley and Sons: New York, 1996; p 290. For an example of a highly regio- and enantioselective palladium-catalyzed allylic etherification, see: Trost, B. M.; Toste, F. D. J. Am. Chem. Soc. 1998, 120, 9074.
12. For a working model that highlights the challenges of the regio- and enantioselective metal-catalyzed allylic etherification reactions with unsymmetrical substrates, see: Trost, B. M.; Toste, F. D. J. Am. Chem. Soc. 1999, 121, 4545 and pertinent references therein.
13. For an example of the problems associated with obtaining selectivity in the metal-catalyzed allylic etherification reaction, see: Goux, C.; Massacret, M.; Lhoste, P.; Sinou, D. Organometallics 1995, 14, 4585 and pertinent references therein.
14. (a) Evans, P. A.; Nelson, J. D. Tetrahedron Lett. 1998, 38, 1725.
15. (b) Evans, P. A.; Nelson, J. D. J. Am. Chem. Soc. 1998, 120, 5581.
16. (c) Evans, P. A.; Robinson, J. E.; Nelson, J. D. J. Am. Chem. Soc. 1999, 121, 6761.
17. (d) Evans, P. A.; Robinson, J. E. Org. Lett. 1999, 1, 1929.
18. (a) Tsuji, J.; Minami, I.; Shimizu, I. Tetrahedron Lett. 1984, 25, 5157.
19. (b) Minami, I.; Shimizu, I.; Tsuji, J. J. Organomet. Chem. 1985, 296, 269.
20. (c) Takeuchi, R.; Kitamura, N. New J. Chem. 1998, 695.
21. The rhodium-catalyzed allylic alkylation of 1 with phenol at 30°C furnished the aryl allyl ethers 2/3m in only 9% yield, as a 33:1 mixture of regioisomers favoring 2m. Hence, the deprotonated nucleophile appears to be crucial for smooth turnover.
22. 4), filtered, and concentrated in vacuo to afford a crude oil. Purification by flash chromatography (eluting with a 3% ethyl acetate/hexanel furnished the allyl aryl ether (R)-5 (0.108 g, 96%) as a colorless oil, with 93% enantiomeric excess by chiral GLC analysis.
23. 6c
24. The retention of absolute configuration in the rhodium-catalyzed etherification was assigned by the comparison of (R)-5 prepared from (R)-4 (eq 2) with (S)-5 prepared via Mitsunobu inversion of the allylic alcohol (R)-i with 2-phenylphenol. (Matrix Presented)
25. Enyl complexes can be defined as those having a discrete σ- and π-metal carbon component within a single ligand. For definitions and examples, see: (a) Sharp P. R. In Comprehensive Organometallic Chemistry II; Abel, E. W., Stone, F. G. A., Wilkmson, G., Eds.; Pergamon Press: New York, 1995; Chapter 2, p 272.
26. (b) Lawson, D. N.; Osborn, J. A.; Wilkinson, G. J. Chem. Soc. (A) 1966, 1733.
27. (c) Tanaka, I.; Jin-no, N.; Kushida, T.; Tsutsui, N.; Ashida, T.; Suzuki, H.; Sakurai, H.; Moro-oka. Y.; Ikawa, T. Bull. Chem. Soc. Jpn. 1983, 56, 657 and pertinent references therein.
28. For recent examples of approaches to dihydrobenzo[b]furans, see: (a) Bernard, A. M.; Cocco, M. T.; Onnis, V.; Piras, P. P. Synthesis 1997, 41.
29. (b) Snider, B. B.; Han, L.; Xie, C. J. Org. Chem. 1997, 62, 6978.
30. (c) Larock, R. C.; Yang, H.; Pace, P.; Cacchi, S.; Fabrizi, G. Tetrahedron Lett. 1998, 39, 237.
31. (d) Olivero, S.; Rolland, J.-P.; Duñach, E. Organometallics 1998, 17, 3747.
32. (e) Engler, T. A.; Letavic, M. A.; Iyengar, R.; LaTessa, K. O.; Reddy, J. P. J. Org. Chem. 1999, 64, 2391 and pertinent references therein.
33. For a recent review on this reagent, see: Chatgilialoglu, C. Chem. Rev. 1995, 60, 3826.