Asymmetric aziridination by reaction of chiral N-sulfinylimines with sulfur ylides: Stereoselectivity improvement by use of tert-butylsulfinyl group as chiral auxiliary

Tetrahedron Asymmetry

Volumn 7, Issue 12, 1996, Pages 3407-3414

  García Ruano, José L ^a   Fernández, Inmaculada ^b   Del Prado Catalina, Miriam ^a   Alcudia Cruz, Ana ^b  

^a UNIVERSIDAD AUTÓNOMA DE MADRID   (Spain)

^b UNIVERSITY OF SEVILLE   (Spain)

Author keywords

[No Author keywords available]

Indexed keywords

AZIRIDINE DERIVATIVE; SULFUR;

ARTICLE; CHEMICAL REACTION; CHIRALITY; CRYSTALLIZATION; DIASTEREOISOMER; DRUG SYNTHESIS; PRIORITY JOURNAL; STEREOCHEMISTRY;

EID: 0030561371     PISSN: 09574166     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0957-4166(96)00448-X     Document Type: Article

References (16)

1. 1. See D. Tanner, Angew. Chem., Int. Ed. Engl. 1994, 33, 599 and references cited therein.
2. 2. D. Tanner, Pure and Appl Chem. 1993, 65, 1319.
3. 3. J.L. García Ruano, I. Fernández, C. Hamdouchi, Tetrahedron Lett., 1995, 36, 295.
4. 4. The asignation of the absolute configuration of the major aziridine product made in our previous work (ref. 3) was erroneous. This was due to a typographic error on the sign of the specific rotation, associated to the fact that in the original paper (B.B. Lohray, J.R. Ahuja, J. Chem. Soc., Chem. Commun., 1991, 97) the configurational assignment of (+)-2-phenylaziridine was erroneous.
5. 5. F.A. Davis, P. Zhou, C-H. Liang, R.E. Reddy, Tetrahedron:Asymmetry, 1995, 6, 1511.
6. 6. F.A. Davis, R.E. Reddy, J.M. Szewczyk, P.S. Portonovo, Tetrahedron Lett., 1993, 34, 6229.
7. 7. S.G. Payne, A.R. Hajipour, K. Prabakaran, Tetrahedron Lett., 1994, 35, 645.
8. 8. N. Khiar, I. Fernández, F. Alcudia, Tetrahedron Lett., 1994, 35, 5719.
9. 9. In the case of the N-sulfinylimine 5S, dimethyloxosulfonium methylide was generated in THF with n-BuLi as base (reagent C). When the reaction was conducted in toluene with NaH as base (reagent B) only decomposition products were obtained.
10. 10. In contrast with our findings, Davis reported in ref. 4 that in THF both stereoselectivity and yield decrease when the naphthylsulfinyl group instead of the p-tolyl one is used as chiral auxiliary.
11. S,R) (precursor of the (R)-aziridine) in optical pure form.
12. 12. C.R. Johnson, C.W. Schroeck, J.R. Shanklin, J. Am. Chem. Soc, 1973, 95, 7424.
13. 2- (reagent A), together with the steric factors, determine a much easier N-C intramolecular attack (yielding the aziridine) on the sulfonium salt than that on the oxosulfonium salt (in this case, carbon to be attacked is like neopentyl carbon because sulfur is similar to a t-butyl group), and a different kind of control is opperative with each methylide.
14. 1 is large) but the attack of the reagent A on the less hindered face would yield the same diastereoisomer that I.
15. + to become coordinated, the low polarity of the solvent used (toluene) would allow its association.
16. 16. F. Ohno, T. Kawashima and R. Okazaki, J. Am. Chem. Soc., 1996, 118, 697. In this paper it is suggested that this kind of pentacoordinated species could be involved as intermediates in the reactions of dimethylsulphonium methylide with carbonyl compounds.