Polymer-supported mukaiyama reagent: A useful coupling reagent for the synthesis of esters and amides

Organic Letters

Volumn 6, Issue 24, 2004, Pages 4579-4582

  Crosignani, Stefano ^a   Gonzalez, Jerome ^a   Swinnen, Dominique ^a  

^a SERONO PHARMACEUTICAL RES INSTITUTE   (Switzerland)

Author keywords

[No Author keywords available]

Indexed keywords

AMIDE; CARBOXYLIC ACID DERIVATIVE; ESTER DERIVATIVE; REAGENT; RESIN;

AMINATION; ARTICLE; CROSS COUPLING REACTION; MUKAIYAMA REACTION; PROCESS DEVELOPMENT; QUANTUM YIELD; RACEMIZATION; REACTION ANALYSIS; SYNTHESIS;

EID: 10044264447     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol0480372     Document Type: Article

References (24)

1. Mukaiyama, T. Angew. Chem., Int. Ed. Engl. 1979, 18, 707-708.
2. Mukaiyama, T.; Usui, M.; Shimada, E.; Saigo, K. Chem. Lett. 1975, 1045-1048.
3. Bald, E.; Saigo, K.; Mukaiyama, T. Chem. Lett. 1975, 1163-1166.
4. Mukaiyama, T.; Usui, M.; Saigo, K. Chem. Lett. 1976, 49-50.
5. (a) Huang, H.; Iwasawa, N.; Mukaiyama, T. Chem. Lett. 1984, 1465-1466.
6. (b) Amin, S. G.; Glazer, R. D.; Manhas, M. S. Synthesis 1979, 210-213.
7. (c) Georg, G. I.; Mashava, P. M.; Guan, X. Tetrahedron Lett. 1991, 32, 581-584.
8. Funk, R. L.; Abelman, M. M.; Jellison, K. M. Synlett 1989, 36-37.
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10. Li, P.; Xu, J. Tetrahedron 2000, 56, 8119-8131.
11. Although sulfonic acid SPE columns could be used to scavenge both the residual Mukaiyama reagent and the byproduct (N-methyl-2-pyridone), this strategy is not compatible with molecules possessing basic sites, which represents a very serious limitation, especially for applications in medicinal chemistry.
12. (a) Ley, S. V.; Baxendale, I. R.; Bream, R. N.; Jackson, P. S.; Leach, A. G.; Longbottom, D. A.; Nesi, M.; Scott, J. S.; Storer, R. I.; Taylor, S. J. J. Chem. Soc., Perkin Trans. 1 2000, 23, 3815-4195.
13. (b) Storer, R. I.; Takemoto, T.; Jackson, P. S.; Ley, S. V. Angew. Chem., Int. Ed. 2003, 42, 2521-2525.
14. (c) For a review covering polymer-supported coupling reagents, see: Katritzky, A. R.; Suzuky, K.; Singh, S. K. ARKIVOC, 2004, 1, 12-35.
15. Convers, E.; Tye, H.; Whittaker, M. Tetrahedron Lett. 2004, 45, 3401-3404.
16. Hydroxymethylphenoxymethyl polystyrene (cross-linked with 1% divinylbenzene) 150-300 μm, loading 1.7 mmol/g, from Polymer Laboratories.
17. Experimental Procedure. Wang resin (5.00 g, 8.5 mmol) was suspended in dry DCM (50 mL). 2-Chloropyridine (4.0 mL, 42.5 mmol, 5 equiv) was added, and the mixture was cooled with an ice bath. Trifluoromethanesulfonic anhydride (2.0 mL, 11.9 mmol, 1.4 equiv) was added dropwise, and after 5 min the ice bath was removed. The mixture was stirred overnight at room temperature. The resin was collected by filtration and washed with DCM, DMF, and DCM and dried under vacuum.
18. Elemental analysis of the resin gave 1.83% N, 4.22% S, and 5.85% Cl, which corresponds to a loading of 1.3 mmol/g (nitrogen and sulfur analyses) or 1.6 mmol/g (chlorine analysis, probably due to ca. 1% w/w DCM still trapped in the resin).
19. (a) Folmer, J. J.; Acero, C.; Thai, D. L.; Rapoport, H. J. Org. Chem. 1998, 63, 8170-8182.
20. (b) Bradlow, H. L.; Vanderwerf, C. A. J. Org. Chem. 1951, 16, 1143-1152.
21. (c) Sutherland, J. K.; Widdowson, D. A. J. Chem. Soc. 1964, 4650-4651.
22. 2 SPE column, 2 g, part no. 470-0200-D.
23. Typical Experimental Procedure. The carboxylic acid (0.16 mmol, 1.05 equiv), the alcohol or amine (0.15 mmol, 1 equiv), and TEA (0.45 mmol, 3 equiv) were dissolved in anhydrous DCM (3 mL). When needed, PS-DMAP was added (20 mg, 0.03 mmol, 0.2 equiv). Resin 1 (240 mg, 0.3 mmol, 2 equiv) was added, and stirring was continued until completion of the reaction (HPLC). The resin was removed by filtration, and the filtrates were passed through an amino-functionalized SPE column (2 g). The resin and SPE column were washed with 10 mL of DCM, and then the combined filtrates were evaporated under vacuum to afford the desired ester or amide.
24. Isolute SCX SPE column, 2 g, part no. 530-0200-D.