Cr(Salen)-catalyzed addition of 1,3-dichloropropene to aromatic aldehydes. A simple access to optically active vinyl epoxides

Organic Letters

Volumn 3, Issue 8, 2001, Pages 1153-1155

  Bandini, Marco ^a   Cozzi, Pier Giorgio ^a   Melchiorre, Paolo ^a   Morganti, Stefano ^a   Umani Ronchi, Achille ^a  

^a UNIVERSITY OF BOLOGNA   (Italy)

Author keywords

[No Author keywords available]

Indexed keywords

1,3 DICHLORO 1 PROPENE; 1,3-DICHLORO-1-PROPENE; ALDEHYDE; ALLYL COMPOUND; CHLORIDE; CHROMIUM CHLORIDE; CHROMIUM DERIVATIVE; ETHYLENEDIAMINE DERIVATIVE; MANGANESE; N,N' DISALICYLIDENEETHYLENEDIAMINE;

ARTICLE; CHEMICAL MODEL; CHEMISTRY; HIGH PERFORMANCE LIQUID CHROMATOGRAPHY;

ALDEHYDES; ALLYL COMPOUNDS; CHLORIDES; CHROMATOGRAPHY, HIGH PRESSURE LIQUID; CHROMIUM COMPOUNDS; ETHYLENEDIAMINES; MANGANESE; MODELS, CHEMICAL;

EID: 0035912309     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol015597h     Document Type: Article

References (18)

1. (a) Lindström, U. M.; Olofsson, B.; Somfai, P. Tetrahedron Lett. 1999, 40, 9276-9279.
2. (b) Solladié-Cavallo, A.; Bouérat, L.; Roje, M. Tetrahedron Lett. 2000, 41, 7309-7312.
3. Taylor, S. K. Tetrahedron 2000, 56, 1149-1163 and references therein.
4. Lautens, M.; Quellet, S. G.; Raeppel, S. Angew. Chem., Int. Ed. 2000, 39, 4079-4082.
5. α-Halohydrines are easily converted to oxyranes, see: Marshall, J. A. Chem. Rev. 1989, 89, 1503-1511.
6. Hu, S.; Jayaraman, S.; Oehlschlager, A. C. J. Org. Chem. 1996, 61, 7513-7520.
7. Fürstner, A. Chem. Eur. J. 1998, 4, 567-570.
8. (a) Bandini, M.; Cozzi, P. G.; Melchiorre, P.; Umani-Ronchi, A. Angew. Chem., Int. Ed. 1999, 58, 3357-3359.
9. (b) Bandini, M.; Cozzi, P. G.; Umani-Ronchi, A. Angew. Chem., Int. Ed. 2000, 39, 2327-2330.
10. It is worth noting that the addition of crotyl halides to aldehydes promoted by catalytic or stoichiometric amount of Cr salts normally gives the anti diasteroisomer in high yields, see: Fürstner, A.; Shi, N. J. Am. Chem. Soc. 1996, 118, 12349-12357.
11. Wender, P. A.; Wisniewski Grissom J.; Hoffmann, U.; Mah, R. Tetrahedron Lett. 1990, 46, 6605-6609.
12. Commercially available 1,3-dichloropropene is a 55:45 diastereoisomeric mixture (E/Z). However, the simple diastereoselectivity of the reaction is not affected by the diastereoisomeric ratio of the starting halide (see ref 7b). 1,3-Dibromopropene gave only byproducts in the Cr(Salen)-catalyzed reaction.
13. For applications of Cr(Salen) complexes in asymmetric catalysis, see: Jacobsen, E. N. Acc. Chem. Res. 2000, 33, 421-431.
14. 2 by the excess of Mn in the reaction flask.
15. 3 (5 mL) and filtered over Celite. After usual workup the crude O-protected chlorohydrin was desilylated under acid conditions (HCl 2 N, THF, checked by TLC). Finally the product was purified by flash chromatography.
16. 4-CHO (15% yield; symanti 65:35; ee syn = 72%). Aliphatic aldehydes were found to be unreactive. α/β-Unsaturated aldehydes furnished a complex mixture of 1,2 and 1,4 adducts.
17. D = +97.4 (c 2.65, EtOH): see ref 5.
18. An acyclic transition state has been proposed on the basis of detailed mechanistic studies, see: Bandini, M.; Cozzi, P. G.; Umani-Ronchi, A. Tetrahedron 2001, 57, 835-843.