Allylindium and allylboronic acid pinacolate: Mild reagents for the allylation of resin-bound aldehydes. Application to the solid-phase synthesis of hydroxypropylamines

Tetrahedron Letters

Volumn 40, Issue 14, 1999, Pages 2711-2714

  Cavallaro, Cullen L ^a   Herpin, Timothy ^a   McGuinness, Brian F ^a   Shimshock, Yvonne Class ^a   Dolle, Roland E ^a  

^a PHARMACOPEIA INC   (United States)

Author keywords

Allylation; Homoallylic alcohol; Indium; Solid phase synthesis, hydroxypropylamine

Indexed keywords

ALDEHYDE; ALLYL COMPOUND; BORONIC ACID DERIVATIVE; INDIUM; RESIN;

ACYLATION; ARTICLE; CHEMICAL REACTION; CHEMICAL STRUCTURE; OXIDATION; PHOTOLYSIS; REACTION ANALYSIS; STRUCTURE ACTIVITY RELATION; STRUCTURE ANALYSIS; SYNTHESIS;

EID: 0033515857     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(99)00346-9     Document Type: Article

References (17)

1. (a) Present address: Coelacanth Corp., New Brunswick, NJ 08901.
2. (b) Pharmacopeia postdoctoral fellow, 1996. Present address: Phone-Poulenc Rhorer, Collegeville, PA 19426.
3. (a) Carroll, C. D.; Patel, H.; Johnson, T. O.; Guo, T.; Orlowski, M.; He, Z.-M.; Cavallaro, C. L.; Guo, J.; Oksman, A.; Gluzman, I. Y.; Connelly, J.; Chelsky, D.; Goldberg, D. E.; Dolle, R. E. Bioorg. Med. Chem. Lett. 1998, 8, 2315.
4. (b) Baldwin, J. J.; Burbaum, J. J.; Henderson, I; Ohlmeyer, M. H. J. J. Am. Chem. Soc. 1995, 117, 5588.
5. Wallace, O. B. Tetrahedron Lett. 1997, 38, 4939.
6. (a) Li, C. J.; Chan, T. H. Tetrahedron Lett. 1991, 48, 7017.
7. (b) Li, C. J.; Chan, T. H. J. Chem. Soc., Chem. Commun. 1992, 747.
8. 2. (Microscopic examination of the resin revealed no bead breakage.) The resin was suspended in MeOH (5 mL) and irradiated (365 nm) for 3 h at 40-50 °C. The product was isolated after filtration, evaporation of solvent, and purification via silica gel column chromatography.
9. (d) The success of the solid-phase reaction suggests that the allylation reaction does not take place on the metal surface.
10. (e) It is of interest to note that the nitro group is known to be unstable to the indium condition (Chan, T. H.; Isaac, M. B. Pure Appl. Chem. 1996, 68, 919). The survival of this functional group here may be due to the heterogenous nature of the reaction mixture.
11. (f) The regioselectivity and stereoselectivity of the crotylindium reaction is known (Chan, T. H.; Isaac, M. B. Tetrahedron Lett. 1995, 36, 8957), but was not determined in this study.
12. (a) Hoffmann, R. W.; Kemper, B.; Metternich, R.; Lehmeier, T. Liebigs Ann. Chem. 1985, 2246.
13. 2 and MeOH. Photolytic cleavage and product isolation were carried out as in reference 4c.
14. (a) Overall isolated yields based on resin loading were 60-70% for 5a,b and 30-40% for 11a-f.
15. (b) All new compounds gave satisfactory physical and spectroscopic properties consistent with their structure.
16. 4 reduction) and authentic diol 18 prepared from stereochemically defined N-Boc-phenylalanine statine 19 (NovaBiochem) via borane reduction, Boc-deprotection, and selective N- benzoylation. The syn/anti ratio obtained with resin-bound amino acid aldehyde substrates is consistent with the indium-mediated allylation of amino aldehydes in solution (Paquette, L. A.; Mitzel, T. M.; Isaac, M. B.; Crasto, C. F.; Schomer, W. W. J. Org. Chem. 1997, 62, 4293). (FORMULA PRESENTED)
17. 2. (FORMULA PRESENTED)