2848
G. Reyes-Rangel et al. / Tetrahedron: Asymmetry 19 (2008) 2839–2849
(5:95) as eluent to give the desired product in 41% yield, mp
debted to Conacyt, México, for financial support via grant
60366-Q.
121–123 °C. ½a 2D5
¼ ꢀ23 (c 1.0, MeOH) for 95% ee, Chiralcel OD, i-
ꢃ
PrOH–hexane–TFA; 10:90:0.1, 1 mL/min, 254 nm, t = 108.97 min.
[Lit.22
½
a 2D5
ꢃ
¼ ꢀ12:1 (c 0.97, CHCl3)]. IR (KBr, cmꢀ1): mmax 3342,
References
2964, 1700, 1540, 1266. The 1H and 13C NMR data were identical
1. (a) Juaristi, E.; Quintana, D.; Escalante, J. Aldrichim. Acta 1994, 27, 3–11; (b)
Cole, D. C. Tetrahedron 1994, 50, 9517–9582; (c) Cardillo, G.; Tomasini, C. Chem.
Soc. Rev. 1996, 117–128; (d)Enantioselective Synthesis of b-Amino Acids; Juaristi,
E., Ed.; Wiley-VCH: New York, 1997; (e) Juaristi, E.; López-Ruiz, H. Curr. Med.
Chem. 1999, 6, 983–1004; (f) Abele, S.; Seebach, D. Eur. J. Org. Chem. 2000, 1–15;
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4290–4299; (j) Córdova, A. Acc. Chem. Res. 2004, 37, 102–112;
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to those recorded in enantiomeric (S)-11a.
4.9.3. 2(S)-[{[(9H-Fluoren-9-ylmethoxy)carbonyl]amino}methyl]-
4-methylpentanoic acid, (S)-11b
The general procedure was followed and the crude product was
purified by flash chromatography using methanol–dichlorometh-
ane (5:95) as eluent to give the desired product in 41% yield, mp
138–140 °C. ½a 2D5
¼ þ11:6 (c 0.6, MeOH) for 96% ee, Chiralcel OD,
ꢃ
i-PrOH–hexane–TFA; 10:90:0.1, 1 mL/min, 254 nm, t = 69.75 min.
[Lit.21 mp 134 °C, ½a 2D5
ꢃ
¼ þ10:8 (c 0.6, CHCl3)]. IR (KBr, cmꢀ1): mmax
2. Gellman, S. H. Acc. Chem. Res. 1998, 31, 173–180.
3066, 2956, 1550, 1448, 1370, 1164, 1010. 1H NMR (CDCl3,
400 MHz) d (ppm): 10.6 (br s, 1H), 7.77–7.31 (m, 8H), 5.3 (br s,
1H), 4.51–4.22 (m, 3H), 3.47–3.12 (m, 2H), 2.76–2.65 (m, 1H),
1.74–1.22 (m, 3H), 0.95 (d, 6H, J = 4.4 Hz). 13C NMR (CDCl3,
100.5 MHz) d (ppm): 180.8, 156.6, 144.0, 127.8, 127.2, 125.2,
120.1, 66.9, 47.3, 43.8, 42.3, 38.6, 25.9, 22.6.
3. (a) Seebach, D.; Matthews, J. L. Chem. Commun. 1997, 2015–2022; (b) Seebach,
D.; Beck, A. K.; Bierbaum, D. J. Chem. Biodiversity 2004, 1, 1111–1239; (c)
Seebach, D.; Gardiner, J. Acc. Chem. Res. ASAP.
4. (a) Appella, D. H.; Christianson, L. A.; Karle, I. L.; Powell, D. R.; Gellman, S. H.
J. Am. Chem. Soc. 1996, 118, 13071–13072; (b) Huck, B. R.; Fisk, J. D.; Guzei, I. A.;
Carlson, H. A.; Gellman, S. H. J. Am. Chem. Soc. 2003, 125, 9035–9037; (c) Horne,
W. S.; Price, J. L.; Keck, J. L.; Gellman, S. H. J. Am. Chem. Soc. 2007, 129, 4178–
4180.
5. For recent examples see: Lukaszuk, A.; Demaegdt, H.; Szemenyei, E.; Tóth, G.;
Tymecka, D.; Misicka, A.; Karoyan, Ph.; Vanderheyden, P.; Vauquelin, G.;
Tourwé, D. J. Med. Chem. 2008, 51, 2291–2296; Petersson, E. J.; Schepartz, A.
J. Am. Chem. Soc. 2008, 130, 821–823; Schmitt, M. A.; Weisblum, B.; Gellman, S.
H. J. Am. Chem. Soc. 2007, 129, 417–428; Sadowsky, J. D.; Fairlie, W. D.; Hadley,
E. B.; Lee, H-S.; Umezawa, N.; Nikolovska-Coleska, Z.; Wang, S.; Huang, D. C. S.;
Tomita, Y.; Gellman, S. H. J. Am. Chem. Soc. 2007, 129, 139–154; Kritzer, J. A.;
Stephens, O. M.; Guarracino, D. A.; Reznik, S. K.; Schepartz, A. Bioorg. Med. Chem.
2005, 13, 11–16; Stephens, O. M.; Kim, S.; Welch, B. D.; Hodsdon, M. E.; Kay, M.
S.; Schepartz, A. J. Am. Chem. Soc. 2005, 127, 13126–13127.
4.9.4. 2(R)-[{[(9H-Fluoren-9-ylmethoxy)carbonyl]amino}methyl]-
4-methylpentanoic acid, (R)-11b
The general procedure was followed and the crude product was
purifiedby flashchromatography usingmethanol–dichloromethane
(5:95) to give the desired product in 46% yield, mp 134–135 °C.
½
a 2D5
ꢃ
¼ ꢀ8:3 (c 0.6, MeOH) for 99% ee, Chiralcel OD, i-PrOH–hex-
ane–TFA; 10:90:0.1, 1 mL/min, 254 nm, t = 129.72 min. IR (KBr,
cmꢀ1): mmax 3066, 2956, 1448, 1368, 1164, 1082. The 1H and 13C
NMR data were identical to those recorded in enantiomeric (S)-11b.
6. (a) Hintermann, T.; Seebach, D. Synlett 1997, 437–438; (b) Seebach, D.;
Gademann, K.; Schreiber, J. V.; Matthews, J. L.; Hintermann, T.; Jaun, B.; Oberer,
L.; Hommel, U.; Widmer, H. Helv. Chim. Acta 1997, 80, 2033–2038; (c) Micuch,
P.; Seebach, D. Helv. Chim. Acta 2002, 85, 1567–1577.
4.9.5. (S)-3-({[(Fluoren-9-yl)methoxy]carbonyl}amino)-2-({1-
([tert-butoxy]carbonyl)-1H-indol-3-yl}methyl)propionic acid,
(S)-11c
7. See, for example: (a) Steer, D. L.; Lew, R. A.; Perlmutter, P.; Smith, A. I.; Aguilar,
M.-I. Curr. Med. Chem. 2002, 9, 811–822; See also: (b) Zubrzak, P.; Williams, H.;
Coast, G. M.; Isaac, R. E.; Reyes-Rangel, G.; Juaristi, E.; Zabrockiy, J.; Nachman, R.
J. Biopolymers, Peptide Science 2007, 88, 76–82.
8. See, for example: Ellmerer-Müller, E. P.; Brössner, D.; Maslouh, N.; Tako, A.
Helv. Chim. Acta 1998, 81, 59–65. and references cited therein.
The general procedure was followed and the crude product was
purifiedby flashchromatography usingmethanol–dichloromethane
(5:95) as eluent to give the desired product in 65% yield, mp 128–
9. For examples of the synthesis of b2-amino acids bearing aliphatic side chains
see: Juaristi, E.; Quintana, D.; Lamatsch, B.; Seebach, D. J. Org. Chem. 1991, 56,
2553–2557; Juaristi, E.; Quintana, D.; Balderas, M.; García-Pérez, E.
Tetrahedron: Asymmetry 1996, 7, 2233–2246; Seebach, D.; Boog, A.;
Schweizer, W. B. Eur. J. Org. Chem. 1999, 335–360; Ponsinet, R.; Chassaing, G.;
Vaissemann, J.; Lavielle, S. Eur. J. Org. Chem. 2000, 83–90; Gutiérrez-García, V.
M.; Reyes-Rangel, G.; López-Ruiz, H.; Juaristi, E. Tetrahedron 2001, 57, 6487–
6496; Nagula, G.; Huber, V. J.; Lum, C.; Goodman, B. A. Org. Lett. 2000, 2, 3527–
3529; Bedow, J. E.; Davies, S. G.; Smith, A. D.; Russel, A. J. J. Chem. Soc., Chem.
Commun. 2004, 2778–2779; Rimkus, A.; Sewald, N. Org. Lett. 2003, 5, 79–80;
Eilitz, U.; Lessmann, F.; Seidelmann, O.; Wendisch, V. Tetrahedron: Asymmetry
2003, 14, 189–191; Dursma, A.; Minard, A. J.; Feringa, B. L. J. Am. Chem. Soc.
2003, 125, 3700–3701; Bower, J. F.; Williams, J. M. J. Synlett 1996, 685–686;
Bower, J. F.; Jumnah, R.; Williams, J. M. J. J. Chem. Soc., Perkin Trans. 1 1997,
1411–1420; Davies, H. M. L.; Venkataramani, C. Angew. Chem., Int. Ed. 2002, 41,
2197–2199; Sibi, M. P.; Patil, K. Angew. Chem., Int. Ed. 2004, 43, 1235–1238.
10. See, for example: Gessier, F.; Schaffer, L.; Kimmerlin, T.; Flögel, O.; Seebach, D.
Helv. Chim. Acta 2005, 88, 2235–2249.
130 °C. ½a 2D5
¼ þ12:5 (c 1, CHCl3) for 90% ee, Chiralcel OD-H,
ꢃ
i-PrOH–hexane–TFA; 20:80:0.1, 1 mL/min, 210 nm, t = 24.8 min.
[Lit.6c mp 125–128 °C. ½a 2D5
¼ ꢀ5:0 (c 1.04, CHCl3) for the enantio-
ꢃ
mer]. IR (KBr, cmꢀ1): mmax 3340, 3062, 2978, 2928, 2360, 1550,
1728, 1606, 1452, 1372, 1256, 1158, 1090, 856. 1H NMR (CDCl3,
300 MHz) d (ppm): 8.07 (d, 1H, J = 7.9 Hz), 7.71 (d, 2H, J = 7.3 Hz),
7.59–7.43 (m, 4H), 7.34–7.14 (m, 6H), 4.9 (s, 2H), 4.28 (d, 2H,
J = 6.8 Hz), 4.12 (t, 1H, J = 6.7 Hz), 3.47–3.25 (m, 2H), 3.05–2.74 (m,
3H), 1.61 (s, 9H). 13C NMR (CDCl3, 75.5 MHz) d (ppm): 157.9, 150.1,
144.2, 141.5, 135.8, 130.8, 127.7, 127.1, 125.2, 124.4, 123.5, 122.6,
119.9, 119.1, 118.5, 115.1, 83.6, 66.8, 47.4, 42.7, 27.4, 26.9, 25.2.
4.9.6. (R)-3-({[(Fluoren-9-yl)methoxy]carbonyl}amino)-2-({1-
([tert-butoxy]carbonyl)-1H-indol-3-yl}methyl)propionic acid,
(R)-11c
11. (a) Anaya de Parrodi, C.; Juaristi, E.; Quintero, L.; Clara-Sosa, A. Tetrahedron:
Asymmetry 1997, 8, 1075–1082; For reviews on the use of (R) and (S)-
a-
phenylethylamine in the preparation of enantiopure compounds, see: (b)
Juaristi, E.; Escalante, J.; León-Romo, J. L.; Reyes, A. Tetrahedron: Asymmetry
1998, 9, 715–740; (c) Juaristi, E.; León-Romo, J. L.; Reyes, A.; Escalante, J.
Tetrahedron: Asymmetry 1999, 10, 2441–2495.
The general procedure was followed and the crude product was
purified by flash chromatography using methanol–dichlorometh-
ane (5:95) as eluent to give the desired product in 58% yield, mp
12. Anaya de Parrodi, C.; Clara-Sosa, A.; Quintero, L.; Pérez, L.; Marañón, V.;
Toscano, R. A.; Aviña, J. A.; Rojas-Lima, S.; Juaristi, E. Tetrahedron: Asymmetry
2001, 12, 69–79.
13. Clara-Sosa, A.; Pérez, L.; Sánchez, M.; Melgar-Fernández, R.; Juaristi, E.;
Quintero, L.; Anaya de Parrodi, C. Tetrahedron 2004, 60, 12147–12152.
14. Reyes-Rangel, G.; Marañón, V.; Avila-Ortiz, C. G.; Anaya de Parrodi, C.;
Quintero, L.; Juaristi, E. Tetrahedron 2006, 62, 8404–8409.
15. Gage, J. R.; Evans, D. A. Org. Synth. Collective Vol. 1993, 8, 339–343. 528–531.
16. Evans, D. A.; Britton, T. C.; Ellman, J. A.; Dorow, R. L. J. Am. Chem. Soc. 1990, 112,
4011–4030.
17. (a) Evans, D. A.; Bartroli, J.; Shih, T. L. J. Am. Chem. Soc. 1981, 103, 2127–2129;
(b) Evans, D. A.; Takacs, J. M.; McGee, L. R.; Ennis, M.; Mathre, D. J. B. Pure Appl.
Chem. 1981, 53, 1109–1127; (c) Evans, D. A. Aldrichim. Acta 1982, 15, 23–32; (d)
Evans, D. A.; Nelson, J. V.; Taber, T. R. Top. Stereochem. 1982, 13, 1–115.
128–130 °C. ½a 2D5
¼ ꢀ18:5 (c 1, CHCl3) for 88% ee, Chiralcel OD-H,
ꢃ
i-PrOH–hexane–TFA; 20:80:0.1, 1 mL/min, 210 nm, t = 40.38 min.
IR (KBr, cmꢀ1): mmax 3410, 2974, 2934, 2360, 1724, 1574, 1450,
1374, 1258, 1158, 1090, 856. The 1H and 13C NMR data were iden-
tical to those recorded in enantiomeric (S)-11c.
Acknowledgments
The authors are grateful to Rodrigo González-Olvera and Jorge
Vargas-Caporali for technical assistance. The authors are also in-