Convenient preparation of (Z)-α-halo-α,β-unsaturated aldehydes: synthesis of a Laurencia flexilis toxin

Tetrahedron Letters

Volumn 49, Issue 28, 2008, Pages 4359-4361

  Barma, Deb K ^a   Lu, Biao ^a   Baati, Rachid ^b   Mioskowski, Charles ^b   Falck, J R ^a  

^a UNIVERSITY OF TEXAS SOUTHWESTERN MEDICAL CENTER   (United States)

^b UNIVERSITÉ DE STRASBOURG   (France)

Author keywords

Aldehydes; Chromium; Enals; Homologation

Indexed keywords

2 CHLOROPENTADEC 2(Z) ENAL; ALDEHYDE DERIVATIVE; ALKENYL GROUP; ALPHA HALO ALPHA,BETA ALDEHYDE DERIVATIVE; CARBON; CHROMIUM; MARINE TOXIN;

ARTICLE; CHEMICAL REACTION; CHEMICAL STRUCTURE; COLUMN CHROMATOGRAPHY; ISOMERIZATION; LAURENCIA; PURIFICATION; ROOM TEMPERATURE; STEREOCHEMISTRY; SYNTHESIS;

LAURENCIA FLEXILIS; RHODOPHYTA;

EID: 44649095154     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/j.tetlet.2008.05.026     Document Type: Article

References (27)

1. Reviews. Fürstner A. Chem. Rev. 99 (1999) 991-1045
2. Hodgson D.M. J. Organomet. Chem. 476 (1994) 1-5
3. Barma D.K., Kundu A., Bandyopadhyay A., Kundu A., Sangras B., Briot A., Mioskowski C., and Falck J.R. Tetrahedron Lett. 45 (2004) 5917-5920
4. Barma D.K., Kundu A., Zhang H., Mioskowski C., and Falck J.R. J. Am. Chem. Soc. 125 (2003) 3218-3219
5. Falck J.R., Bandyopadhyay A., Barma D.K., Shin D.-S., Kundu A., and Kishore R.V.K. Tetrahedron Lett. 45 (2004) 3039-3042
6. Nagamitsu T., Takano D., Marumoto K., Fukuda T., Furuya K., Otoguro K., Takeda K., Kuwajima I., Harigaya Y., and Omura S. J. Org. Chem. 72 (2007) 2744-2756
7. Simpkins S.M.E., Weller M.D., and Cox L.R. Chem. Commun. (2007) 4035-4037
8. Timmons C., Chen D., Cannon J.F., Headley A.D., and Li G. Org. Lett. 6 (2004) 2075-2078
9. de Nys R., König G.M., Wright A.D., and Stricher O. Phytochem. 34 (1993) 725-728
10. Typical examples:. Chen S., and Wang J. J. Org. Chem. 72 (2007) 4993-4996
11. Nenajdenko V.G., Reznichenko A.L., Lenkova O.N., Shastin A.V., and Balenkova E.S. Synthesis (2005) 605-609
12. Kim K.-M., and Park I.-H. Synthesis (2004) 2641-2644
13. Mitani M., and Kobayashi Y. Bull. Chem. Soc. Jpn. 67 (1994) 284-286
14. Satoh T., Kitoh Y., Onda K.-i., Takano K., and Yamakawa K. Tetrahedron 50 (1994) 4957-4972
15. Ley S., and Whittle A.J. Tetrahedron Lett. 22 (1981) 3301-3304
16. Masure D., Chuit C., Sauvêtre R., and Normant J.F. Synthesis (1978) 458-460
17. Poutsma M.L., and Ibarbia P.A. J. Org. Chem. 35 (1970) 4038-4054
18. Jedlinski Z., and Majnusz J. Tetrahedron 25 (1969) 699-705
19. Märkl G. Chem. Ber. 95 (1962) 3003-3007
20. Adduct 2 was identical in all respects with an authentic sample of (Z)-α-chlorocinnamaldehyde from Aldrich Chem. Co. and the spectral data of 25 corresponded closely with literature values (see Ref. 6). All other products were assigned (Z)-stereochemistry in analogy.
21. 5 under reduced pressure, gave 2 in only 56% yield. The superior yields obtained with chloral ethyl hemiacetal may result from the slow release of free chloral. A low steady state concentration of free chloral would minimize side reactions, thus improving overall halo-homologation yields.
22. Organochromium intermediates of the type described here belong to a small but growing class of organometallics, for example, indium reagents, that are tolerant of water, alcohols and hydroxylic solvents, yet are still capable of reaction with organic electrophiles such as aldehydes.
23. Fürstner A., and Shi N. J. Am. Chem. Soc. 118 (1996) 12349-12357
24. Falck J.R., Bejot R., Barma D.K., Bandyopadhyay A., Joseph S., and Mioskowski C. J. Org. Chem. 71 (2006) 8178-8182
25. 2 was used along with 5 equiv of Mn(0) or 5 equiv of Fe(0), only 10% and 21% of 2 were obtained, respectively, at room temperature after 24 h. Increasing the temperature to 45 °C did not improve the yields. The use of other solvents such as DMF (no formation of 2), EtOAc (5-10% of 2), or DME (less than 10% of 2) was also disappointing.
26. 3, 300 MHz) δ 1.50-1.53 (d, 1H, J = 9.0 Hz), 4.22-4.32 (m, 4H), 6.90-6.93 (d, 1H, J = 9.0 Hz), 7.25-7.35 (m, 5H), 9.35 (s, 1H).
27. 2 was transferred to a tared flask under an argon atmosphere and dried in vacuo with a heat-gun or low flame for 3-5 min, then cooled to room temperature prior to weighing and use.