The role of 4-(3-phenylpropyl)pyridine N-oxide (P3NO) in the manganese-salen-catalyzed asymmetric epoxidation of indene

Tetrahedron Letters

Volumn 37, Issue 19, 1996, Pages 3271-3274

  Senanayake, Chris H ^a,b   Smith, George B ^a   Ryan, Kenneth M ^a   Fredenburgh, Laura E ^a   Liu, Ji ^a   Roberts, F Edward ^a   Hughes, David L ^a   Larsen, Robert D ^a   Verhoeven, Thomas R ^a   Reider, Paul J ^a  

^a MERCK RESEARCH LABORATORIES   (United States)

^b SUNOVION PHARMACEUTICALS INC   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

INDENE DERIVATIVE;

ARTICLE; DRUG SYNTHESIS; REACTION ANALYSIS; TECHNIQUE;

EID: 0029878505     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/0040-4039(96)00565-5     Document Type: Article

References (17)

1. (a) Senanayake, C. H.; Roberts, F. E.; DiMichele, L. M.; Ryan, K. M.; Liu, J.; Fredenburgh, L. E.; Foster, B. S.; Douglas, A. W.; Larsen, R. D.; Verhoeven, T. R.; Reider, P. J. Tetrahedron Lett. 1995, 36, 3993.
2. (b) Askin, D.; Eng, K. K.; Rossen, K.; Purick, R. M.; Wells, R. P.; Volante, R. P.; Reider, P. J. Tetrahedron Lett. 1994, 35, 673.
3. (a) Jacobsen, E. N.; Zhang, W.; Muci, A. R.; Ecker, J. R.; Deng, L. J. Am. Chem. Soc. 1991, 113, 7063.
4. (b) Jacobsen, E. N.; Larrow, F. J. J. Am. Chem. Soc. 1994, 116, 12129, and references cited therein.
5. (a) Srinivasan, K.; Michaud, P.; Kochi, J. K. J. Am. Chem. Soc. 1986, 108, 2309.
6. (b) Brandes, B. D.; Jacobsen, E. N. J. Org. Chem. 1994, 59, 4378.
7. (c) "On the Viability of Oxametallacyclic Intermediates in the Mn(salen)-Catalyzed Epoxidations" Jacobsen, E. N.; Finncy, N. S.; Pospisil, P. J.; Palucki, M.; Hansen, K. B. submitted to J. Am. Chem. Soc.
8. In the comparison study of pyridine N-oxides the hydroxide ion concentration in NaOCl was 0.13M.
9. 4)/acetonitrile = 65 /35 over 20 min; 1.5 mL/min. Aliquots of the reaction mixture were removed periodically and analyzed for unreacted indene and the product, indene oxide.
10. For comparison of the reactivity of the N-oxides, 0.75mol % of MnLCl and 3 mol % of N-oxide in PhCl at 0°C were used in the epoxidation.
11. 3) δ 1.81.98(2H, m), 2.3-2.6(4H, m), 7.05(2H, m), 7.12-7.30(5H, m), 8.11(2H, m).
12. 2
13. 3NO (RT=12.5 min).
14. 3NO but was also observed with 4-PPNO. A full disclosure of these findings are planned.
15. 3NO oxidation, will decrease the hydroxide concentration and, as a result, increase the amount of HOCl. This in turn provides a greater amount of HOCl in the organic phase which increases the rate of decomposition of hypochlorite.
16. Indene epoxidation is exothermic. The controlled addition of the indene and hypochlorite to the catalyst system is necessary in order to dissipate the heat generated in the reaction.
17. Large quantities of S,S-Mn(salen) chloride (MnLCl) was purchased from Sepracor.