The 2-(N,N-dimethylamino)phenylsulfinyl group as an efficient chiral auxiliary in intramolecular heck reactions

Organic Letters

Volumn 2, Issue 10, 2000, Pages 1451-1454

  Buezo, Nuria Díaz ^a   Mancheño, Olga García ^a   Carretero, Juan C ^a  

^a UNIVERSIDAD AUTÓNOMA DE MADRID   (Spain)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000199230     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol005779w     Document Type: Article

References (40)

1. (a) Mizoroki, T.; Mori, K.; Ozaki, A. Bull. Chem. Soc. Jpn. 1971, 44, 581.
2. (b) Heck, R. F. J. Am. Chem. Soc. 1968, 90, 5518.
3. Recent reviews: (a) Gibson, S. E.; Middleton, R. J. Contemp. Org. Synth. 1996, 3, 447.
4. (b) de Meijere, A.; Meyer, F. E. Angew. Chem., Int. Ed. Engl. 1994, 36, 2379.
5. (c) Cabri, W.; Candiani., I. Acc. Chem. Res. 1995, 28, 2.
6. Reviews on the asymmetric Heck reaction: (a) Shibasaki, M.; Boden, C. D. J.; Kojima, A. Tetrahedron 1997, 53, 7371.
7. (b) Guiry, P. J.; Hennessy, A. J.; Cahill, J. P. Top. Catal. 1997, 4, 311. For some recent references, see:
8. (a) Tietze, L. F.; Thede, K.; Schimpf, R.; Sannicolo, F. Chem. Commun. 2000, 583.
9. (b) Tietze, L. F.; Thede, K.; Sannicolò, F. Chem. Commun. 1999, 1811.
10. (c) Honzawa, S.; Mizutani, T.; Shibasaki, M. Tetrahedron Lett. 1999, 40, 311.
11. (d) Flubacher, D.; Helmchem, G. Tetrahedron Lett. 1999, 40, 3867.
12. (e) Namyslo, C.; Kaufmann, D. E. Synlett 1999, 804.
13. (f) Tschoerner, M.; Pregosin, P. Organometallics 1999, 18, 670.
14. (g) Matsuura, T.; Overman, L. E.; Poon, D. J. J. Am. Chem. Soc. 1998, 120, 6500.
15. (h) Ashimori, A.; Bachand, B.; Overman, L. E.; Poon, D. J. J. Am. Chem. Soc. 1998, 120, 6488.
16. (i) Miyazaki, F.; Votsu, K.; Shibasaki, M. Tetrahedron 1998, 54, 13073.
17. To the best of our knowledge only a few examples using SAMP (or RAMP) as chiral auxiliaries in Heck reactions have been reported: Grigg, R.; Dorrity, M. J. R.; Malone, J. F.; Mongkolaussavaratana, T.; Norbert, W. D. J. A.; Sridharan, V. Tetrahedron Lett. 1990, 31, 3075. See also: Meyer, F. E.; Henniges, H.; de Meijere, A. Tetrahedron Lett. 1992, 33, 8039.
18. To the best of our knowledge only a few examples using SAMP (or RAMP) as chiral auxiliaries in Heck reactions have been reported: Grigg, R.; Dorrity, M. J. R.; Malone, J. F.; Mongkolaussavaratana, T.; Norbert, W. D. J. A.; Sridharan, V. Tetrahedron Lett. 1990, 31, 3075. See also: Meyer, F. E.; Henniges, H.; de Meijere, A. Tetrahedron Lett. 1992, 33, 8039.
19. (a) Priego, J.; Carretero, J. C. Synlett 1999, 1603.
20. (b) Díaz, N.; Alonso, I.; Carretero, J. C. J. Am. Chem. Soc. 1998, 120, 7129.
21. The use of sulfoxides as chiral auxiliaries in metal-catalyzed reactions has not been extensively explored. Recent references: (a) Adrio, J.; Carretero, J. C. J. Am. Chem. Soc. 1999, 121, 7411.
22. (b) Henrich, M.; Delgado, A.; Molins, E.; Roig, A.; Llebaria, A. Tetrahedron Lett. 1999, 40, 4259.
23. (c) Paley, R. S.; Estroff, L. A.; McCulley, D. J.; Martínez-Cruz, L. A.; Jiménez Sánchez, A.; Cano, F. H. Organometallics 1998, 17, 1841.
24. (d) Paley, R. S.; Rubio, M. B.; Fernández de la Pradilla, R.; Dorado, R.; Hundal, G.; Martínez-Ripoll, M. Organometallics 1996, 15, 4672. For the use of sulfoxides as chiral ligands, see: Hiroi, K.; Suzuki, Y.; Abe, I. Tetrahedron: Asymmetry 1999, 10, 1173 and references therein.
25. (d) Paley, R. S.; Rubio, M. B.; Fernández de la Pradilla, R.; Dorado, R.; Hundal, G.; Martínez-Ripoll, M. Organometallics 1996, 15, 4672. For the use of sulfoxides as chiral ligands, see: Hiroi, K.; Suzuki, Y.; Abe, I. Tetrahedron: Asymmetry 1999, 10, 1173 and references therein.
26. Racemic phosphonates 1 (as mixtures of both diastereomers) were readily prepared in two steps: initial phosphorylation of the α-sulfinyl carbanion of the corresponding methyl sulfoxide with diethyl chlorophosphate followed by methylation (LDA, THF, and then MeI).
27. Aldehyde 2 was prepared from diethyl malonate by two sequential alkylations (bromoacetaldehyde diethyl acetal first and 3-bromo-2-iodo-1-propene second) and acid hydrolysis of the acetal moiety.
28. 3) as a consequence of the deshielding cis-effect of the sulfinyl group. This assignment has also been corroborated by NOE experiments.
29. With these preliminary results, it does not appear to be easy to determine unequivocally the origin of the high stereochemical control exerted by the 2-(N,N-dimethylamino)phenylsulfinyl group in the Heck reactions. At present, we are investigating if this effect could be mainly due to steric reasons, conformational preferences around the C-S bond in the reactants, or a chelation control directed by a previous coordination of the intermediate palladium cationic species with the dimethylamino moiety prior to the insertion step.
30. -3. Crystallographic data of 6 have been deposited in the Cambridge Crystallographic Data Centre as supplementary publication number CCDC 138255.
31. In a manner similar to that described for the preparation of (Z)-3c, (Z)-7, (Z)-S, and (Z)-9 were obtained by a highly (Z)-stereoselective Wadsworth-Emmons olefination of their corresponding aldehydes.
32. The configurations of 10A, 11A, and 12A were assigned by chemical analogy with the case of 4cA. Accordingly, all these compounds show similar NMR parameters for the protons of the 1,4-diene moiety.
33. 3).
34. Determined in the presence of (R)-2,2,2-trifluoro-1-(9-anthryl)-ethanol.
35. 2. Lack of reactiviy or formation of complex mixtures of alkenes and/ or sulfur containing products was observed depending on the reagent used.
36. We were unable to find appropriate conditions to confirm the high enantiomeric composition of the diene (R)-14 [no peak separation of (±)-14 was observed by NMR in the presence of chiral shift reagents or by chiral HPLC or GC].
37. Ochiai, M.; Ukita, T.; Fujita, E. J. Chem. Soc., Chem. Commun. 1983, 619.
38. Both diastereomers 6 + 6′ can be easily separated by flash chromatography.
39. The sign of the specific rotation of 2-ethylcyclopentanone (S)-15 [ref 14] is in agreement with that of related α-alkylated cyclopentanones: (a) Partridge, J. J.; Chadha, N. K.; Uskokovic, M. R. J. Am. Chem. Soc. 1973, 95, 532.
40. (b) Lacote, E.; Delouvrié, B.; Fensterbank, L.; Malacria, M. Angew. Chem., Int. Ed. 1998, 37, 2116.