Regiochemical control of the ring opening of aziridines by means of chelating processes. Part 3: Regioselectivity of the opening reactions with methanol of remote O-substituted regio- and diastereoisomeric activated aziridines under condensed- and gas-phase operating conditions

Tetrahedron

Volumn 58, Issue 35, 2002, Pages 7119-7133

  Crotti, Paolo ^a   Di Bussolo, Valeria ^a   Favero, Lucilla ^a   Macchia, Franco ^a   Renzi, Gabriele ^b   Roselli, Graziella ^b  

^a UNIVERSITY OF PISA   (Italy)

^b UNIVERSITY OF CAMERINO   (Italy)

Author keywords

Aziridines; Chelation; Gas phase reactions; Regioselectivity

Indexed keywords

AZIRIDINE DERIVATIVE; CHELATING AGENT; HYDROGEN; METHANOL;

ARTICLE; CARBON NUCLEAR MAGNETIC RESONANCE; CHELATION; DIASTEREOISOMER; INFRARED SPECTROSCOPY; POLYMERIZATION; PRIORITY JOURNAL; PROTON NUCLEAR MAGNETIC RESONANCE; STEREOCHEMISTRY; THIN LAYER CHROMATOGRAPHY; ULTRAVIOLET RADIATION;

EID: 0037178954     PISSN: 00404020     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4020(02)00726-3     Document Type: Article

References (44)

1. (a) Caron M., Sharpless K.B. J. Org. Chem. 50:1985;1557-1560 (b) Behrens C.H., Sharpless K.B. J. Org. Chem. 50:1985;5696-5704 (c) Caron M., Carlier P.R., Sharpless K.B. J. Org. Chem. 53:1988;5185-5187.
2. (a) Chini M., Crotti P., Flippin L.A., Macchia F. J. Org. Chem. 55:1990;4265-4272 (b) Chini M., Crotti P., Flippin L.A., Macchia F., Pineschi M. J. Org. Chem. 57:1992;1405-1412 (c) Chini M., Crotti P., Flippin L.A., Macchia F., Gardelli C. J. Org. Chem. 57:1992;1713-1718 (d) Calvani F., Crotti P., Gardelli C., Pineschi M. Tetrahedron. 50:1994;12999-13021 (e) Crotti P., Di Bussolo V., Favero L., Macchia F., Pineschi M. Eur. J. Org. Chem. 1998;1675-1686. and references therein. For other results on the influence of nearby heterofunctionality, particularly in the α and β position, see: (f) Azzena F., Crotti P., Favero L., Pineschi M. Tetrahedron. 51:1995;13409-13422. and references therein (g) Righi G., Pescatore G., Bonadies F., Bonini C. Tetrahedron. 57:2001;5649-5656 (h) Honda T., Mizutani H. Heterocycles. 48:1998;1753-1757 (i) Wang S., Howe G.P., Mahal R.S., Procter G. Tetrahedron Lett. 33:1992;3351-3354 (j) Ooi T., Kagoshima N., Ichikawa H., Maruoka K. J. Am. Chem. Soc. 121:1999;3328-3333 (k) Flippin L.A., Brown P.A., Jalali-Araghi. J. Org. Chem. 54:1989;3588-3596 (l) Pfaltz A., Mattemberger A. Angew. Chem. Suppl. 1982;161-168.
3. 4, in the methanolysis).
4. Crotti P., Di Bussolo V., Favero L., Pineschi M., Marianucci F., Renzi G., Amici G., Roselli G. Tetrahedron. 56:2000;7513-7524.
5. +, MeOH) ( Tables 1-4 ), making a direct comparison possible between all these conditions and in particular a direct comparison of the behavior of the proton under different operating conditions
6. . Aziridines 1-4 were previously examined by the authors in opening reactions in the cd-phase with different nucleophiles (including MeOH only in the case of 1 and 2), both under standard and chelating conditions: (a) Crotti P., Favero L., Gardelli C., Macchia F., Pineschi M. J. Org. Chem. 60:1995;2514-2525. (aziridines 1 and 2) (b) Crotti P., Di Bussolo V., Favero L., Pineschi M. Tetrahedron. 53:1997;1417-1438. (aziridines 3 and 4).
7. 2b and on the reasonable assumption that epoxides 13 and 14 should have a similar regiochemical behavior also in a fairly similar reaction like acid azidolysis.
8. The C-1 and C-2 product nomenclature refers to the attacking site of the nucleophile, i.e. at the C(1) or C(2) aziridine carbon of aziridines 1-8, in accordance with the numbering scheme shown in Schemes 5-8.
9. 1H NMR examination of the corresponding crude opening reaction product (see Experimental ).
10. (a) Ausloos P., Lias S.G., Gorden R. Jr. J. Chem. Phys. 39:1963;3341-3348 (b) Ausloos P. Franklin J.L., Ion-Molecule Reactions. 1970;Plenum, New York, (c) Ausloos P., Lias S.G. J. Chem. Phys. 36:1962;3163-3170 (d) Freeman G.R. Radiat. Res. Rev. 1:1968;1-74 (e) Sandoval L.B., Ausloos P. J. Chem. Phys. 38:1963;2454-2460 (f) Speranza M., Pepe N., Cipollini R. J. Chem. Soc., Perkin Trans. 2. 1979;1179-1186.
11. (a) Crotti P., Di Bussolo V., Favero L., Pineschi M., Sergiampietri D., Renzi G., Ricciutelli M., Roselli G. Tetrahedron. 53:1997;5515-5536 (b) Chini M., Crotti P., Minutolo F., Dezi E., Lombardozzi A., Pizzabiocca A., Renzi G. Tetrahedron. 49:1993;5845-5858 (c) Cecchi P., Chini M., Crotti P., Pizzabiocca A., Renzi G., Speranza M. Tetrahedron. 47:1991;4683-4692.
12. 3 to the gaseous mixture causes a strong decrease in the product yield, thus demonstrating the ionic origin of the neutral products.
13. 4 no traces of non-addition products were found in the corresponding reactions of aziridines 1-8.
14. 4 can now reasonably be extended to the corresponding reactions of aziridines. In fact, in the cd-phase, the intermediate protonated aziridine 52 ( Scheme 4 ), as the corresponding protonated epoxide, rapidly undergoes nucleophilic addition by the surrounding nucleophilic solvent (MeOH) to afford the corresponding opening products, a situation which actually corresponds to low ion lifetime conditions in the gas-phase.
15. (b) Fürst, A.; Plattner, P. A. Abstract of Papers, 12th International Congress of Pure and Applied Chemistry, 1951; p 409.
16. 6a.
17. 15 can be nucleophilically attacked only at the C(1) aziridine carbon giving the result observed ( Scheme 5 ).
18. 2d.
19. Hunter E.P., Lias S.G. J. Phys. Chem. Ref. Data. 27:1998;413-656.
20. Jackman L.M., Sternhell S. Applications of Nuclear Magnetic Resonance Spectroscopy in Organic Chemistry. 2nd ed: 1969;Pergamon, London. p 286.
21. b) and, as a consequence, with a C-1 product structure for MU 25 which should exist in the largely more stable triequatorial conformation 25a.
22. 2OBn group equatorial.