Asymmetric synthesis of α,β-epoxysulfones under phase-transfer catalyzed Darzens reaction

Tetrahedron Letters

Volumn 39, Issue 45, 1998, Pages 8299-8302

  Arai, Shigeru ^a   Ishida, Toshimasa ^b   Shioiri, Takayuki ^a  

^a NAGOYA CITY UNIVERSITY   (Japan)

^b OSAKA MEDICAL COLLEGE   (Japan)

Author keywords

Asymmetric reactions; Darzens reactions; Phase transfer; Sulfones

Indexed keywords

ALPHA,BETA EPOXYSULFONE; QUATERNARY AMMONIUM DERIVATIVE; SULFONE DERIVATIVE; UNCLASSIFIED DRUG;

ARTICLE; CATALYSIS; CHEMICAL REACTION; CHIRALITY; SYNTHESIS; X RAY CRYSTALLOGRAPHY;

EID: 0032487768     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(98)01811-5     Document Type: Article

References (14)

1. 1. Arai, S.; Shioiri, T. Tetrahedron Lett. 1998, 39, 2145-2148.
2. 2. Recently, the chiral crown ether catalyzed asymmetric Darzens condensation was reported, see (a) Bako, P.; Szollosy, A.; Bombicz, P.; Toke, L. Synlett, 1997, 291-292.
3. Other examples of asymmetric Darzens condensation using stoichiometric amount of chiral source are reported, see (b) Ohkata, K.; Kimura, J.; Shinohara, Y.; Takagi, R.; Hiraga, Y. J. Chem. Soc. Chem. Commun. 1996, 2411-2412.
4. (c) Takahashi, T.; Muraoka, M.; Capo, M.; Koga, K. Chem. Pharm. Bull. 1995, 43, 1821-1823.
5. Other examples of the catalytic asymmetric Darzens condensation using chloromethyl phenylsulfone and its derivatives with quaternary salts as PTC derived from ephedrine have been reported, see (d) Colonna, S.; Fornasier, R.; Pfeiffer, U. J. Chem. Soc. Perkin I 1978, 8-11.
6. 3. Mori, Y.; Yaegashi, K.; Furukawa, H. J. Am. Chem. Soc. 1997, 119, 4557-4558.
7. (b) Mori, Y.; Yaegashi, K.; Furukawa, H. J. Am. Chem. Soc. 1996, 118, 8158-8159.
8. (c) Mori, Y.; Yaegashi, K.; Iwase, K.; Yamamori, Y.; Furukawa, H. Tetrahedron Lett. 1996, 37, 2605-2608.
9. 4. KOH gave the best results on enantioselectivities in comparison with the other metal hydroxides.
10. 24 -153.3° (c 0.18, MeOH). Other quaternary salts were synthethized using the corresponding benzyl bromides under similar reaction conditions.
11. 6. Benzene gave results similar to toluene.
12. 7. Use of a catalytic amount of N-(4-trifluoromethybenzyl)quinidinium bromide (10 mol %) or commercially available N-(4-trifluoromethylbenzyl)cinchoninium bromide gave 3a with 49 and 27% ee in (αR,βR)-configuration under similar reaction conditions, respectively. The absolute configuration was determined by X-ray crystallographical analysis by use of anomalous dispersion of the sulfer atom.
13. 2 (31% yield, 56% ee), 4-H (68% yield, 54% ee), 4-Me (76% yield, 53% ee), 4-t-Bu (81% yield, 66% ee), and 4-halogenated PTCs (59-80% yield, 60-67% ee).
14. 3S: C, 68.33; H, 6.37; Found C, 68.18; H, 6.34.