A practical pilot-scale synthesis of 4-vinyl-2,3-dihydrobenzofuran using imidate ester chemistry and phase-transfer catalysis

Organic Process Research and Development

Volumn 7, Issue 4, 2003, Pages 547-550

  Rao, Meena ^a   Yang, Ming ^a   Kuehner, Daniel ^a   Grosso, John ^a   Deshpande, Rajendra P ^a  

^a BRISTOL MYERS SQUIBB   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

2,3 BIS(2 HYDROXYETHYL)PHENOL; 4 (2 CHLOROETHYL) 2,3 DIHYDROBENZOFURAN; 4 VINYL 2,3 DIHYDROBENZOFURAN; CHLORIDE; DIHYDROBENZOFURAN DERIVATIVE; IMIDE; PHENOL DERIVATIVE; REAGENT; UNCLASSIFIED DRUG;

ARTICLE; CATALYSIS; CATALYST; HALOGENATION; PHYSICAL PHASE; RING CLOSING METATHESIS; SYNTHESIS;

EID: 0042745635     PISSN: 10836160     EISSN: None     Source Type: Journal    
DOI: 10.1021/op030201y     Document Type: Article

References (10)

1. Catt, J.; Johnson, G.; Keavy, D.; Mattson, R.; Parker, M.; Takaki, K.; Yevich, J. (Bristol-Myers Squibb) U.S. Patent 5,981,571, November 1999.
2. Ellis, F.; Panchal, T.; North, P.; Cooke, J.; Smith, C. (Glaxo Wellcome) W00743272 A2 19971120.
3. At Bristol-Myers Squibb, the preparation of 4-vinyl-2,3-dihydrobenzofuran via the tosylation approach was developed and optimized by W. Li, J. Thornton, Z. Guo, J. Zhu, W. Yang, T. Vu, A. Singh, V. Rosso, D. Lust, S. Prasad, M. Yang, and D. Kacsur.
4. Zhu, J.; Price, B.; Zhao, S.; Skonezny, P. Tetrahedron Lett. 2000, 41, 4011.
5. Procopiou, P.; Brodie, A.; Deal, M.; Hayman; D. Tetrahedron Lett. 1993, 34, 7483.
6. Procopiou, P.; Brodie, A.; Deal, M.; Hayman; D.; Smith, G. J. Chem. Soc., Perkin Trans 1 1996, 2249.
7. Barrett, A.; Braddock, D.; James, R.; Koike, N.; Procopiou, P. J. Org. Chem. 1998, 63, 6273.
8. In the subsequent chemistry, an asymmetric cyclopropanation was accomplished by treating the vinyl-dihydrobenzofuran with ethyl diazoacetate in the presence of a chiral auxiliary. The author would like to thank Drs. James H. Simpson and Atul Kotnis for evaluating several laboratory-scale batches of the vinyl-dihydrobenzofuran in the cyclopropanation chemistry and helping us in identifying optimized parameters for the preparation of the vinyl-dihydrobenzofuran.
9. Unpublished information, Dr. James H. Simpson of Bristol-Myers Squibb.
10. Authors would like to thank Doris Chen and the New Brunswick Pilot Plant staff for helping the authors in successful scale-up operations.