Rh(II)-Catalyzed Intramolecular N-H Insertion of d-Glucose-Derived δ-Amino α-Diazo β-Ketoester: Synthesis of Pyrrolidine Iminosugars

Vinod P. Vyavahare; Subrata Chattopadhyay; Vedavati G. Puranik; Dilip D. Dhavale

doi:10.1055/s-2007-970743

LETTER

Rh(II)-Catalyzed Intramolecular N-H Insertion of d-Glucose-Derived δ-Amino α-Diazo β-Ketoester: Synthesis of Pyrrolidine Iminosugars

Vinod P. Vyavahare^a, Subrata Chattopadhyay^b, Vedavati G. Puranik^c, Dilip D. Dhavale*^a
^a Garware Research Centre, Department of Chemistry, University of Pune, Pune 411007, India
^b Bio-Organic Division, Bhaba Atomic Research Centre, Mumbai 400085, India
^c Center for Materials Characterization, National Chemical Laboratory, Pune 411008, India
Fax: +91(20)25691728; e-Mail: ddd@chem.unipune.ernet.in;

Abstract

All articles of this category

Abstract

The rhodium acetate catalyzed reaction of d-glucose-derived δ-amino α-diazo β-ketoester allows a stereoselective β-facial intramolecular N-H insertion reaction that leads to formation of the bicyclic pyrrolidinone ring skeleton in high yield. The sugar-substituted pyrrolidinone thus obtained was elaborated to allow the synthesis of promising glycosidase inhibitors, namely, 2,5-dideoxy-2,5-imino-l-glycero-α-d-galactoheptitol and 2,5-dideoxy-2,5-imino-d-galactitol.

Key words

alkaloids - azasugars - carbohydrates - pyrrolidines - rhodium carbenoid - N-H insertion

Full Text

References

References and Notes

1a O’Hagan D. Nat. Prod. Rep. 2000, 17: 435 ; and references therein

1b Daly JW. Spande TF. Garraffo HM. J. Nat. Prod. 2005, 68: 1556

2a Whitesell JK. Chem. Rev. 1989, 89: 1581

2b White JD. Xu Q. Lee C.-S. Valeriote FA. Org. Biomol. Chem. 2004, 2: 2092

3a Fache F. Schulz E. Tommasino ML. Lernaire M. Chem. Rev. 2000, 100: 2159

3b Hoang L. Bahmanyar S. Houk KN. List B. J. Am. Chem. Soc. 2003, 125: 16

3c Chiral Reagents for Asymmetric Synthesis Paquette LA. Wiley; Chichester: 2003.

3d Rogers CJ. Dickerson TJ. Brogan AP. Janda KD. J. Org. Chem. 2005, 70: 3705

4a Pichon M. Figadere B. Tetrahedron: Asymmetry 1996, 7: 927 ; and references therein

4b Katritzky AR. Cui X.-L. Yang B. Steel PJ. J. Org. Chem. 1999, 64: 1979

4c Besev M. Engman L. Org. Lett. 2002, 4: 3023

5a Coldham I. Hufton R. Tetrahedron Lett. 1995, 36: 2157

5b Pedrosa R. Andres C. Duque-Soldana JP. Mendiguchia P. Eur. J. Org. Chem. 2000, 3727

5c Bustos F. Gorgojo JM. Suero R. Aurrecoechea JM. Tetrahedron 2002, 58: 6837

5d Bajracharya GB. Huo Z. Yamamoto Y. J. Org. Chem. 2005, 70: 4883

5e Bexrud JA. Beard JD. Leitch DC. Schafer LL. Org. Lett. 2005, 7: 1959

5f Kim JY. Livinghouse T. Org. Lett. 2005, 7: 1737

5g Karanjule NS. Markad SD. Shinde VS. Dhavale DD. J. Org. Chem. 2006, 71: 4667

For rhodium carbenoid N-H insertion reaction, see:

6a Salzmann TN. Ratcliffe RW. Christensen BG. Bouffard FA. J. Am. Chem. Soc. 1980, 102: 6161

6b Moyer MP. Feldman PL. Rapoport H. J. Org. Chem. 1985, 50: 5223

6c Ye T. McKervey MA. Chem. Rev. 1994, 94: 1091

6d Garcia CF. McKervey MA. Ye T. Chem. Commun. 1996, 1465

6e Padwa A. Weingarten MD. Chem. Rev. 1996, 96: 223

6f Doyle MP. McKervey MA. Chem. Commun. 1997, 983

6g Doyle MP. McKervey MA. Ye T. Modern Catalytic Methods for Organic Synthesis with Diazo Compounds Wiley-Interscience; New York: 1998.

6h Wang J. Hou Y. Wu P. J. Chem. Soc., Perkin Trans. 1 1999, 2277

6i Yang H. Jurkauskas V. Mackintosh N. Mogren T. Stephenson CRJ. Foster K. Brown W. Roberts E. Can. J. Chem. 2000, 78: 800

6j Davies HML. Beckwith REJ. Chem. Rev. 2003, 103: 2861

6k Davis FA. Fang T. Goswami R. Org. Lett. 2002, 4: 1599

6l Lee S.-H. Clapham B. Koch G. Zimmermann J. Janda KD. J. Comb. Chem. 2003, 5: 188

For rhodium carbenoid N-H insertion of phosphonate, see:

6m Moody CJ. Swann E. Ferris L. Haigh D. Chem. Commun. 1997, 2391

6n Moody CJ. Morfitt CN. Slawin AMZ. Tetrahedron: Asymmetry 2001, 12: 1657

6o Nakamura Y. Ukita T. Org. Lett. 2002, 4: 2317

6p Davis FA. Wu Y. Xu H. Zhang J. Org. Lett. 2004, 6: 4523 ; and references therein

7a Dhavale DD. Bhujbal NN. Joshi P. Desai SG. Carbohydr. Res. 1994, 263: 303

7b Desai VN. Saha NN. Dhavale DD. J. Chem. Soc., Perkin Trans. 1 2000, 147

7c Karche NP. Jachak SM. Dhavale DD. J. Org. Chem. 2001, 66: 6323

8 Karche NP. Jachak SM. Dhavale DD. J. Org. Chem. 2003, 68: 4531

For pyrrolidine alkaloids, see:

9a Chaudhari VD. Ajish Kumar KS. Dhavale DD. Tetrahedron Lett. 2004, 45: 8363

9b Dhavale DD. Ajish Kumar KS. Chaudhari VD. Sharma T. Sabharwal SG. PrakashaReddy J. Org. Biomol. Chem. 2005, 3: 3720

9c Dhavale DD. Matin MM. Sharma T. Sabharwal SG. Bioorg. Med. Chem. 2003, 11: 3295 ; and references therein

For piperidine and azepane alkaloids see:

9d Dhavale DD. Markad SD. Karanjule NS. PrakashaReddy J. J. Org. Chem. 2004, 69: 4760

9e Markad SD. Karanjule NS. Sharma T. Sabharwal SG. Dhavale DD. Bioorg. Med. Chem. 2006, 14: 5535 ; and references therein

10a Evans SV. Fellows LE. Shing TKM. Fleet GWJ. Phytochemistry 1985, 24: 1953

10b Asano N. Kato A. Miyauchi M. Kizu H. Kameda Y. Watson AA. Nash RJ. Fleet GWJ. J. Nat. Prod. 1998, 61: 625

11 Legler G. In Iminosugars as Glycosidase Inhibitors Stütz AE. Wiley-VCH; Weinheim, Germany: 1999. p.31

12 Watson AA. Nash RJ. Wormald MR. Harvey DJ. Dealler S. Lees E. Asano N. Kizu H. Kato A. Griffiths RC. Cairns AJ. Fleet GWJ. Phytochemistry 1997, 46: 255

13 Yamashita T. Yasuda K. Kizu H. Kameda Y. Watson AA. Nash RJ. Fleet GWJ. Asano N. J. Nat. Prod. 2002, 65: 1875

14a Legler G. Adv. Carbohydr. Chem. Biochem. 1990, 48: 319

14b Look GC. Fotsch CH. Wong CH. Acc. Chem. Res. 1993, 26: 182

15a Izquierdo I. Plaza MT. Franco F. Tetrahedron: Asymmetry 2004, 15: 1465

15b Izquierdo I. Plaza MT. Tamayo JA. Tetrahedron 2005, 61: 6527

16a Gouverneur V. Ghosez L. Tetrahedron: Asymmetry 1990, 1: 363

16b Gouverneur V. Ghosez L. Tetrahedron Lett. 1991, 32: 5349

16c Masaki Y. Oda H. Kazuta K. Usai A. Itoh A. Xu F. Tetrahedron Lett. 1992, 33: 5089

16d Shi M. Satoh Y. Makihara T. Masaki Y. Tetrahedron: Asymmetry 1995, 6: 2109

17a Wang Y.-F. Takaoka Y. Wong C.-H. Angew. Chem., Int. Ed. Engl. 1994, 33: 1242

18 Chen H. Guo Z. Liu H.-W. J. Am. Chem. Soc. 1998, 120: 9951

19

The synthesis of α-d-ribopentodialdose is known, however that of α-d-xylopentodialdose is unknown.

20

The formation of 10 as a major product in 94% yield could be explained on the basis of the hydride delivery in LiAlH₄, reducing from the convex face; the concave face attack of hydride afforded the corresponding C-5 epimeric compound in 6% yield as a minor product as evident from the ¹H and ¹³C NMR spectral data.

21

Perbenzylation at room temperature under a variety of reaction conditions for prolonged time afforded a mixture of mono-, di- and tribenzylated products.

22

The NaBH₄ (2.5 equiv) reduction of an anomeric mixture of hemiacetal was sluggish and led to only 50% conversion into the corresponding alcohol. Use of an excess amount of NaBH₄ did not improve the yield of the product.

23a Fechter MH. Stutz AE. Carbohydr. Res. 1999, 319: 55

23b Singh S. Han H. Tetrahedron Lett. 2004, 45: 6349

23c Izquierdo I. Plaza MT. Rodríguez M. Tamayo JA. Martos A. Tetrahedron 2006, 62: 2693

23d Chikkanna D. Han H. Synlett 2004, 2311

24

All new compounds have been characterized by ¹H NMR, ¹³C NMR, IR, and elemental analysis. Ethyl-3,6-dideoxy-3-benzyloxycarbonylamino-1,2- O -isopropylidene-α- d -xylohept-5-ulofuranuronate ( 7): viscous liquid; R _f 0.65 (n-hexane-EtOAc, 5:1); [α]_D +3.33 (c = 0.60, CHCl₃). IR (neat): 3150-3400(br), 1730, 1650 cm^-1. ¹H NMR (300 MHz, CDCl₃): δ = 1.26 (t, J = 7.4 Hz, 3 H), 1.30 (s, 3 H), 1.50 (s, 3 H), 3.40 (d, J = 16.0 Hz, 1 H), 3.75 (d, J = 16.0 Hz, 1 H), 4.18 (q, J = 7.4 Hz, 2 H), 4.50-4.62 (br m, 2 H), 4.89 (d, J = 3.3 Hz, 1 H), 5.08 (AB quartet, J = 12.0 Hz, 2 H), 5.86 (d, J = 3.6 Hz, 1 H), 5.89 (d, J = 3.3 Hz, 1 H), 7.20-7.40 (br s, 5 H). ¹³C NMR (75 MHz, CDCl₃): δ = 14.0, 26.1, 26.7, 46.8, 58.0, 61.7, 66.9, 83.5, 84.3, 104.7, 112.5, 127.8, 127.9, 128.3, 128.4, 135.9, 155.5, 167.3, 199.4. The ¹H and ¹³C NMR spectrum showed additional signals (<5%) corresponding to the enol form of the β-ketoester. Anal. Calcd for C₂₀H₂₅NO₈ (407.41): C, 58.96; H, 6.18. Found: C, 58.82; H, 6.12.
Ethyl-3,6-dideoxy-6-diazo-3-benzyloxycarbonylamino-1,2- O -isopropylidene-α- d -xylohept-5-ulofuranuronate ( 8): yield: 87%; viscous liquid; R _f 0.60 (n-hexane-EtOAc, 5:1); [α]_D +44.00 (c = 0.5, CHCl₃). IR (neat): 3150-3330, 2146, 1716, 1658 cm^-1. ¹H NMR (300 MHz, CDCl₃): δ = 1.38 (t, J = 6.9 Hz, 3 H), 1.35 (s, 3 H), 1.59 (s, 3 H), 4.32 (q, J = 6.9 Hz, 2 H), 4.57 (d, J = 3.3 Hz, 1 H), 4.67 [(dd, J = 3.6, 8.7 Hz, 1 H); on D₂O exchange became (d, J = 3.6 Hz)], 5.05 (s, 2 H), 5.22 (br d, J = 8.7 Hz, 1 H, exchanges with D₂O), 5.69 (d, J = 3.6 Hz, 1 H), 5.97 (d, J = 3.3 Hz, 1 H), 7.20-7.40 (m, 5 H). ¹³C NMR (75 MHz, CDCl₃): δ = 14.6, 26.6, 27.1, 58.3, 62.4, 67.2, 80.0, 84.8, 104.6, 112.8, 128.1, 128.3, 128.7, 136.2, 155.6, 160.5, 186.1. In the ¹³C NMR the C5 carbon did not appear due to the presence of C=N₂. This is analogous to the earlier observation reported by Davis. [2] Anal. Calcd for C₂₀H₂₃N₃O₈ (433.15): C, 55.42; H, 5.35. Found: C, 55.32; H, 5.32.
Preparation of Ethyl-3,6-dideoxy-3,6-benzyloxy-carbonylamino-1,2- O -isopropylidine-α- d -xylohept-5-ulofuranuronate ( 9): To the solution of the diazo com-pound 8 (1.00 g, 2.30 mmol) in anhyd benzene (5 mL) was added Rh₂(OAc)₄ (0.03g, 0.04 mmol) under nitrogen atmosphere and the solution was refluxed for 20 min. On cooling, the reaction mixture was directly loaded on a silica gel column and eluted (n-hexane-EtOAc, 7:3) to give 9 as a viscous liquid (0.73 g, 78%); R _f 0.50 (n-hexane-EtOAc, 3:2); [α]_D +10.00 (c = 0.8, CHCl₃). IR (neat): 3150-3421 (br), 1750, 1660 cm^-1. Anal. Calcd for C₂₀H₂₃NO₈(405):
C, 59.25; H, 5.72. Found: C, 59.27; H, 5.68. The ¹H and ¹³C NMR spectra of this compound showed complex patterns due to keto-enol tautomerism and doubling of signals associated with the NCbz functionality.
3,6-Dideoxy-3,6-( N -benzylamino)-5,7-di- O -benzyl-1,2- O -isopropylidene-α- d -glycero-d-glucohepto-1,4-furanose ( 10): yield: 68%; white solid; mp 96-97 °C; R _f 0.70 (n-hexane-EtOAc, 19:1); [α]_D +48.57 (c = 0.7, CHCl₃). IR (KBr): 1452, 1369, 1124, 1074, 698 cm^-1. ¹H NMR (300 MHz, CDCl₃): δ = 1.23 (s, 3 H), 1.45 (s, 3 H), 3.21 (ddd, app q, J = 5.7, 6.3, 6.6 Hz, 1 H), 3.39 (d, J = 5.4 Hz, 1 H), 3.55 (dd, J = 6.3, 9.3 Hz, 1 H), 3.80 (dd, J = 5.7, 9.3 Hz, 1 H), 3.83 (d, J = 14.0 Hz, 1 H), 3.93 (dd, J = 4.8, 6.6 Hz, 1 H), 4.00 (d, J = 14.0 Hz, 1 H), 4.15 (d, J = 3.6 Hz, 1 H), 4.45 (AB q, J = 12.0 Hz, 2 H), 4.53 (d, J = 12.0 Hz, 1 H), 4.75 (d, J = 12.0 Hz, 1 H), 4.78 (dd, J = 4.8, 5.4 Hz, 1 H), 5.85 (d, J = 3.6 Hz, 1 H), 7.20-7.40 (m, 15 H). ¹³C NMR (75 MHz, CDCl₃): δ = 26.6, 27.5, 57.7, 65.0, 70.8, 71.3, 72.7, 73.2, 78.0, 82.3, 84.8, 107.2, 112.0, 127.0, 127.3, 127.5, 127.7, 128.1, 129.2, 137.7, 138.0, 138.3. Anal. Calcd for C₃₁H₃₅NO₅ (501.61): C, 74.23; H, 7.03. Found: C, 74.22; H, 7.00.
2,5-Dideoxy-2,5-imino-1,3-di- O -benzyl-l-glycero-α- d -galactoheptitol ( 11): yield: 81%; viscous liquid; R _f 0.40 (n-hexane-EtOAc, 9:1); [α]_D +3.07 (c = 0.65, CHCl₃). IR (neat): 3100-3550, 1639, 1456, 1369 cm^-1. ¹H NMR (300 MHz, CDCl₃ + D₂O): δ = 3.02-3.12 (m, 2 H, H-3), 3.16 (ddd, J = 2.1, 4.2, 8.1 Hz, 1 H), 3.36 (dd, J = 2.7, 9.3 Hz, 1 H), 3.58 (d, J = 13.5 Hz, 1 H), 3.66 (dd, J = 4.5, 11.4 Hz, 1 H), 3.77 (dd, J = 4.5, 11.4 Hz, 1 H), 3.96 (ddd, app q, J = 4.5, 4.8, 9.6 Hz, 1 H), 4.01 (d, J = 13.5 Hz, 1 H), 4.05 (dd, J = 4.8, 8.1 Hz, 1 H), 4.22 (dd, J = 4.8, 5.1 Hz, 1 H), 4.44 (AB q, J = 12.0 Hz, 2 H), 4.45 (d, J = 11.7 Hz, 1 H), 4.68 (d, J = 11.7 Hz, 1 H), 7.20-7.40 (m, 15 H). ¹³C NMR (75 MHz, CDCl₃ + D₂O): δ = 60.3, 63.3, 64.8, 67.1, 68.4, 69.4, 69.9, 71.9, 73.5, 77.7, 127.2, 127.5, 127.6, 127.7, 128.3, 129.7, 137.0, 137.7, 138.5. Anal. Calcd for C₂₈H₃₃NO₅ (463.57): C, 72.55; H, 7.18. Found: C, 72.49; H, 7.15.
2,5-Dideoxy-2,5-imino-l-glycero-α- d -galactoheptitol ( 12): yield: 85%; viscous liquid; R _f 0.10 (MeOH);
[α]_D -86.66 (c = 0.6, H₂O). IR (nujol): 3200-3600(br) cm^-1. ¹H NMR (300 MHz, D₂O): δ = 3.27 (dd, J = 5.7, 6.0 Hz, 1 H), 3.46 (ddd, app q, J = 5.8, 6.4, 6.6 Hz, 1 H), 3.63 (dd, J = 6.6, 12.0 Hz, 1 H), 3.72-3.78 (m, 2 H, H-7b), 3.83 (dd, J = 5.1, 11.4 Hz, 1 H), 3.97 (ddd, J = 3.3, 6.3, 9.9 Hz, 1 H), 4.29 (dd, J = 4.8, 5.7 Hz, 1 H), 4.35 (dd, J = 4.8, 6.6 Hz, 1 H). ¹³C NMR (75 MHz, D₂O): δ = 62.1, 62.3, 62.4, 65.8, 71.9, 73.7, 73.7. Anal. Calcd for C₇H₁₅NO₅ (193.2): C, 43.52; H, 7.83. Found: C, 43.50; H, 7.81.
2,5-Dideoxy-2,5-imino- d -galactitol ( 14): yield: 83%; viscous liquid; R _f 0.10 (MeOH). IR (nujol): 3200-3600(br) cm^-1. ¹H NMR (300 MHz, D₂O): δ = 3.75-3.83 (m, 2 H, H-2), 3.92 (dd, J = 8.4, 12.3 Hz, 2 H), 4.01 (dd, J = 5.1, 12.3 Hz, 2 H) 4.50 (dd, J = 1.5, 4.5 Hz, 2 H). ¹³C NMR (75 MHz, D₂O): δ = 60.2, 63.8, 72.3. Anal. Calcd for C₆H₁₃NO₄ (163): C, 44.16; H, 8.03. Found: C, 44.17; H, 8.05.
2,5-Dideoxy-2,5-imino- d -galactitol Hydrochloride ( 15): yield: 89%; semi solid. IR (nujol): 3200-3600(br) cm^-1. ¹H NMR (300 MHz, D₂O): δ = 3.73-3.81 (m, 2 H), 3.90 (dd, J = 8.1, 12.0 Hz, 2 H), 4.01 (dd, J = 4.8, 12.0 Hz, 2 H), 4.48 (d, J = 5.1 Hz, 2 H). ¹³C NMR (75 MHz, D₂O): δ = 57.8, 61.4, 70.0. Anal. Calcd for C₆H₁₄NO₄Cl (199.5): C, 36.10; H, 7.07. Found: C, 36.12; H, 7.07.