Diastereoselective Formation of Trisubstituted Pyrrolidine-3-carboxylates

Fabrice Denes; Fabrice Chemla; Jean F. Normant

doi:10.1055/s-2002-31898

Subscribe to RSS

Please copy the URL and add it into your RSS Feed Reader.

https://www.thieme-connect.de/rss/thieme/en/10.1055-s-00000083.xml

Share / Bookmark

Facebook X Linkedin Weibo

Download PDF

Synlett 2002(6): 0919-0922
DOI: 10.1055/s-2002-31898

LETTER

Diastereoselective Formation of Trisubstituted Pyrrolidine-3-carboxylates

Fabrice Denes, Fabrice Chemla*, Jean F. Normant
Laboratoire de Chimie des OrganoEléments, Tour 44-45 2è étage, Bte 183 - Université Pierre et Marie Curie - 4 place Jussieu 75252 Paris Cedex 05
Fax: +33(1)44277567; e-Mail: fchemla@ccr.jussieu.fr;

Further Information

Publication History

Received 17 April 2002
Publication Date:
07 February 2007 (online)

Abstract
Full Text
References

Permissions and Reprints All articles of this category

Abstract

Zinc enolates derived from the deprotonation of substituted β-(N-allyl)-aminoesters undergo smooth carbocyclization reaction to give, after reaction with electrophiles, 3,4-disubstituted-3-carbomethoxypyrrolidines with excellent stereochemical control.

Key words

amino acids - cyclizations - pyrrolidines - stereoselectivity - zinc enolates

References

1a Knochel P. In Comprehensive Organic Synthesis Vol. 4: Trost B. Fleming I. Pergamon Press; New York: 1991. p.865

Search in Google Scholar
1b Marek I. Normant J.-F. In Cross Coupling Reactions Diederich D. Stang P. VCH; Weinheim: 1997. p.271
2 Kitagawa O. Suzuki T. Fujiwara H. Fujita M. Taguchi T. Tetrahedron Lett. 1999, 40: 4585

Crossref Search in Google Scholar
3 Rodriguez AL. Bunlakananusorn T. Knochel P. Org. Lett. 2000, 2: 3285

Crossref PubMed Search in Google Scholar
4 For a review, see: Poli G. Giambastiani G. Heumann A. Tetrahedron 2000, 56: 5959

Crossref Search in Google Scholar
5a Kitagawa O. Suzuki T. Fujiwara H. Taguchi T. Tetrahedron Lett. 1999, 40: 2549

Crossref Search in Google Scholar
5b Kitagawa O. Fujiwara H. Suzuki T. Taguchi T. Shiro M. J. Org. Chem. 2000, 65: 6819

Crossref Search in Google Scholar
6a Rosenblum M. Rosan A. Tancrede J. J. Am. Chem. Soc. 1973, 95: 3062

Crossref Search in Google Scholar
6b Lennon P. Rosan AM. Rosenblum M. J. Am. Chem. Soc. 1977, 99: 8426

Crossref Search in Google Scholar
6c Rosenblum M. Acc. Chem. Res. 1974, 122

Crossref
7 Roberts B. Wong J. J. Chem. Soc., Chem. Commun. 1977, 20

Crossref
8a Chuang L.-W. Fu HW. Sheu BA. Tau SI. Yeh M.-C. J. Am. Chem. Soc. 1993, 115: 5941

Search in Google Scholar
8b Lai M.-L. Chang S.-C. Hwu C.-C. Yeh M.-C. Tetrahedron Lett. 1996, 37: 6149

Search in Google Scholar
8c Yeh M.-CP. Chuang L.-W. Ueng C.-H. J. Org. Chem. 1996, 61: 3874

Search in Google Scholar
9a Khan MdNI. Pearson AJ. J. Am. Chem. Soc. 1984, 106: 1872

Crossref Search in Google Scholar
9b Clardy JC. Cun-heng H. Khan MdNI. Pearson AJ. J. Am. Chem. Soc. 1985, 107: 2748

Crossref Search in Google Scholar
9c Khan MdNI. Pearson AJ. Tetrahedron Lett. 1985, 26: 1407

Crossref Search in Google Scholar
10a Nakamura E. Kubota K. Tetrahedron Lett. 1997, 38: 7099

Crossref Search in Google Scholar
10b Kubota K. Nakamura E. Angew. Chem. Int., Ed. Engl. 1997, 36: 2491

Crossref Search in Google Scholar
10c Kubota K. Nakamura E. J. Org. Chem. 1997, 62: 792

Crossref Search in Google Scholar
10d Nakamura E. Sakata G. Kubota K. Tetrahedron Lett. 1998, 39: 2157

Crossref Search in Google Scholar
11a Lorthiois E. Marek I. Normant J.-F. J. Org. Chem. 1998, 63: 566

Crossref Search in Google Scholar
11b Lorthiois E. Marek I. Normant J.-F. J. Org. Chem. 1998, 63: 2442

Crossref Search in Google Scholar
12a Karoyan P. Chassaing G. Tetrahedron Lett. 1997, 38: 85

Crossref Search in Google Scholar
12b Karoyan P. Triolo A. Nannicini R. Giannotti D. Altamura M. Chassaing G. Perotta E. Tetrahedron Lett. 1999, 40: 71

Crossref Search in Google Scholar
12c Chassaing G. Karoyan P. Tetrahedron: Asymmetry 1997, 8: 2025

Crossref Search in Google Scholar
12d Karoyan P. Chassaing G. Tetrahedron Lett. 2002, 43: 253

Crossref Search in Google Scholar
13 Ling R. Ekhato IV. Rubin JR. Wustrow DJ. Tetrahedron 2001, 57: 6579

Crossref Search in Google Scholar
23 Chemla F. Synlett 1998, 894

Thieme Connect
26 For a review, see: Fürstner A. Synthesis 1989, 571 ; and references cited therein.

Thieme Connect

14

Compound 3a. Major diastereomer: IR (neat): 3028, 2958, 2872, 2794, 1737, 1495, 1454, 1435, 1366, 1265, 1202, 1170, 1028, 742, 700 cm^-1; ¹H NMR (400 MHz, CDCl₃): δ = 1.16 (3 H, d, J = 6.6 Hz), 2.24 (1 H, dd, J = 9.2, 6.6 Hz), 2.47-2.57 (1 H, m), 2.56-2.62 (1 H, m), 2.78-2.82 (1 H, m), 2.83 (1 H, dd, J = 8.6, 7.6 Hz), 2.89 (1 H, dd, J = 9.7, 6.6 Hz), 3.59 (1 H, d, J = 12.7 Hz), 3.67 (1 H, d, J = 12.7 Hz), 3.70 (3 H, s), 7.25-7.36 (5 H, m); ¹³C NMR (100 MHz, CDCl₃): δ = 19.86, 36.89, 50.60, 51.87, 56.76, 60.20, 61.70, 127.01, 128.31, 128.81, 139.00, 175. 24; Anal. Calcd for C₁₄H₁₉NO₂: C, 72.07; H, 8.21; N, 6.00. Found: C, 72.10; H, 8.25; N, 5.98.

15

Crystal structure deposited at the Cambridge Crystallographic Data Centre (deposition numbers 178455).

16

A similar enhanced reactivity of substituted zincated hydrazones compared to unsubstituted ones has been already noticed: see ref. [10c] .

17

Compound 3c. IR (neat): 3062, 3027, 2963, 2876, 2792, 1732, 1495, 1453, 1435, 1377, 1263, 1198, 1123, 1072, 1029, 984, 910, 736, 700 cm^-1; ¹H NMR (500 MHz, CDCl₃): δ = 0.99 (3 H, d, J = 7.3 Hz), 1.21 (3 H, s), 2.17-2.22 (1 H, m), 2.30 (1 H, d, J = 9.5 Hz), 2.64-2.71 (1 H, m), 2.91-2.96 (1 H, m), 3.32 (1 H, d, J = 9.5 Hz), 3.57 (1 H, d, J = 13.2 Hz), 3.65 (1 H, J = 13.2 Hz), 3.67 (3 H, s), 7.21-7.37 (5 H, m); ¹³C NMR (125 MHz, CDCl₃): δ = 13.88, 19.27, 38.90, 50.40, 52.03, 60.32, 61.07, 64.68, 126.98, 128.31, 128.68, 139.25, 177.84; Anal. Calcd for C₁₅H₂₁NO₂: C, 72.84; H, 8.56; N, 5.66. Found: C, 72.79; H, 8.64; N, 5.74.

18

Compound 3d. IR (neat): 3063, 3027, 2959, 2920, 2791, 1732, 1640, 1495, 1454, 1436, 1377, 1357, 1298, 1216, 1136, 1072, 1028, 992, 914, 735, 699 cm^-1; ¹H NMR (400 MHz, CDCl₃): δ = 1.08 (3 H, d, J = 7.1 Hz), 2.15 (1 H, t, J = 7.1 Hz), 2.23 (1 H, dd, J = 9.5 Hz), 2.35 (1 H, d, J = 9.7 Hz), 2.52-2.63 (2 H, m), 2.95-2.99 (1 H, m), 3.38 (1 H, d, J = 9.9 Hz), 3.60 (1 H, d, J = 13.1 Hz), 3.66 (1 H, d, J = 13.1 Hz), 3.69 (3 H, s), 5.01-5.10 (2 H, m), 5.59-5.69 (1 H, m), 7.22-7.36 (5 H, m); ¹³C NMR (100 MHz, CDCl₃): δ = 14.00, 37.47, 39.89, 51.92, 54.35, 60.22, 61.14, 61.31, 117.85, 126.97, 128.33, 128.64, 134.53, 139.30, 176.61; Anal. Calcd for C₁₇H₂₃NO₂: C, 74.69; H, 8.48; N, 5.12. Found: C, 74.68; H, 8.55; N, 5.21.

19

Compound 3e. IR (neat): 3027, 2953, 2932, 2861, 2788, 1732, 1495, 1454, 1378, 1290, 1256, 1196, 1138, 1072, 1029, 738, 699 cm^-1; ¹H NMR (400 MHz, CDCl₃): δ = 0.83 (3 H, t, J = 7.1 Hz), 0.93-1.13 (2 H, m), 0.99 (3 H, d, J = 7.1 Hz), 1.16-1.27 (4 H, m), 1.31-1.39 (1 H, m), 1.62-1.71 (1 H, m), 1.98 (1 H, t, J = 8.6 Hz), 2.08 (1 H, d, J = 9.7 Hz), 2.41-2.51 (1 H, m), 2.91-2.97 (1 H, m), 3.44 (1 H, d, J = 9.7 Hz), 3.51 (1 H, d, J = 13.7 Hz), 3.62 (1 H, d, J = 13.7 Hz), 3.65 (3 H, s), 7.18-7.31 (5 H, m); ¹³C NMR (100 MHz, CDCl₃): δ = 13.91, 14.07, 22.54, 25.28, 32.44, 33.10, 39.80, 51.84, 54.53, 60.28, 61.55, 61.70, 126.87, 128.25, 128.61, 139.31, 177.39; Anal. Calcd for C₁₉H₂₉NO₂: C, 75.21; H, 9.63; N, 4.62. Found: C, 75.04; H, 9.64; N, 4.49.

20

Compound 3f. IR (neat): 3062, 3028, 2959, 2795, 1728, 1604, 1495, 1473, 1454, 1436, 1377, 1357, 1314, 1271, 1196, 1133, 1097, 1070, 1029, 910, 735, 701 cm^-1; ¹H NMR (400 MHz, CDCl₃): δ = 1.28 (3 H, d, J = 7.1 Hz), 2.44 (1 H, t, J = 8.6 Hz), 2.60 (1 H, d, J = 9.9 Hz), 2.68 (1 H, m), 2.86 (1 H, d, J = 13.4 Hz), 3.02 (1 H, t, J = 8.6 Hz), 3.24 (1 H, d, J = 9.9 Hz), 3.28 (1 H, d, J = 13.4 Hz), 3.72 (3 H, s), 3.74 (2 H, s), 7.15-7.46 (10 H, m); ¹³C NMR (100 MHz, CDCl₃): δ = 14.06, 38.09, 40.88, 51.78, 55.58, 59.95, 60.27, 60.86, 126.59, 127.05, 128.35, 128.40, 128.82, 129.66, 138.30, 139.13, 176.42; Anal. Calcd for C₂₁H₂₅NO₂: C, 77.98; H, 7.79; N, 4.33. Found: C, 78.12; H, 7.73; N, 4.26.

21

Crystal structure deposited at the Cambridge Crystallographic Data Centre (deposition numbers 178454).

22

Compound 5b. IR (neat): 3027, 2950, 2795, 1733, 1494, 1454, 1434, 1374, 1214, 1156, 1112, 1073, 1029, 988, 911, 735, 699 cm^-1; ¹H NMR (400 MHz, CDCl₃): δ = 1.39 (3 H, s), 2.60-2.63 (2 H, m), 3.17-3.30 (3 H, m), 3.41 (1 H, d, J = 9.4 Hz), 3.51-3.52 (1 H, m), 3.74 (1 H, d, J = 13.1 Hz), 3.82 (1 H, d, J = 13.1 Hz), 3.85 (3 H, s), 7.40-7.49 (5 H, m); ¹³C NMR (100 MHz, CDCl₃): δ = 5.22, 18.52, 47.13, 51.14, 52.45, 59.85, 60.66, 65.11, 127.17, 128.42, 128.65, 138.80, 176.61; exact mass (MH⁺): calcd 374.06, exp. 374.062.

24

Compound 5c. IR (neat): 3026, 2949, 2922, 2796, 1731, 1493, 1453, 1434, 1268, 1208, 1158, 1113, 1091, 1028, 1016, 805, 736, 699 cm^-1; ¹H NMR (400 MHz, CDCl₃): δ = 1.30 (3 H, s), 2.32 (3 H, s), 2.40 (1 H, d, J = 9.5 Hz), 2.47 (1 H, t, J = 8.9 Hz), 2.74 (1 H, dd, J = 12.4, 10.9 Hz), 2.85 (1 H, m), 3.04 (1 H, dd, J = 8.9, 7.8 Hz), 3.20 (1 H, d, J = 9.5 Hz), 3.21 (1 H, dd, J = 12.4, 4.5 Hz), 3.58 (1 H, d, J = 13.1 Hz), 3.67 (3 H, s), 3.67 (1 H, d, J = 13.1 Hz), 7.09-7.11 (2 H, d, J = 8.1 Hz), 7.24-7.26 (2 H, d, J = 8.1 Hz), 7.22-7.28 (1 H, m), 7.29-7.31 (4 H, m); ¹³C NMR (100 MHz, CDCl₃): δ = 19.16, 21.05, 34.56, 43.31, 50.37, 52.13, 58.74, 59.97, 64.61, 127.00, 128.28, 128.60, 129.70, 129.75, 132.38, 136.10, 138.74, 176.93; Anal. Calcd for C₂₂H₂₇NO₂S: C, 71.51; H, 7.36; N, 3.79. Found: C, 71.41; H, 7.42; N, 3.75.

25

Compound 5d. IR (neat): 3063, 3026, 2975, 2933, 2857, 2791, 1731, 1640, 1495, 1453, 1434, 1373, 1339, 1263, 1209, 1116, 1073, 1028, 992, 911, 740, 699 cm^-1; ¹H NMR (400 MHz, CDCl₃): δ = 1.23 (3 H, s), 1.31-1.40 (1 H, m), 1.60-1.68 (1 H, m), 1.93-2.08 (2 H, m), 2.25 (1 H, t, J = 9.1 Hz), 2.30 (1 H, d, J = 9.3 Hz), 2.55-2.63 (1 H, m), 2.99 (1 H, t, J = 8.3 Hz), 3.28 (1 H, d, J = 9.3 Hz), 3.58 (1 H, d, J = 13.2 Hz), 3.68 (3 H, s), 3.69 (1 H, d, J = 13.2 Hz), 4.94-5.04 (2 H, m), 5.75 (1 H, m), 7.22-7.34 (5 H, m); ¹³C NMR (100 MHz, CDCl₃): δ = 19.27, 28.91, 32.86, 44.08, 50.43, 52.15, 59.30, 60.40, 65.10, 114.82, 127.03, 128.38, 128.68, 138.61, 139.30, 177.83; Anal. Calcd for C₁₈H₂₅NO₂: C, 75.22; H, 8.77; N, 4.87. Found: C, 74.93; H, 8.80; N, 4.77.