A Concise Synthesis of (+)-Polyoxamic
Acid and (+)-5-O-Carbamoyl Polyoxamic
Acid

In Su Kim; Qing Ri Li; Guang Ri Dong; Seol Hee Woo; Hyun-ju Park; Ok Pyo Zee; Young Hoon Jung

doi:10.1055/s-0028-1083629

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 2008(19): 2985-2988
DOI: 10.1055/s-0028-1083629

LETTER

A Concise Synthesis of (+)-Polyoxamic Acid and (+)-5-O-Carbamoyl Polyoxamic Acid

In Su Kim, Qing Ri Li, Guang Ri Dong, Seol Hee Woo, Hyun-ju Park, Ok Pyo Zee, Young Hoon Jung*
College of Pharmacy, Sungkyunkwan University, Suwon 440-746, Korea
Fax: +82(31)2907773; e-Mail: yhjung@skku.ac.kr;

Further Information

Publication History

Received 12 August 2008
Publication Date:
12 November 2008 (online)

Abstract
Full Text
References

Permissions and Reprints All articles of this category

Abstract

We report the concise synthesis of (+)-polyoxamic acid and (+)-5-O-carbamoyl polyoxamic acid from l-xylose in seven or six steps, respectively. The key steps include a diastereoselective amination of syn-1,2-polybenzyl ethers using chlorosulfonyl isocyanate (CSI) and the one-pot introduction of carbamates into the allylic benzyl ether and primary hydroxyl moieties.

Key words

polyoxamic acid - polyoxin - chlorosulfonyl isocyanate - amination - sugar

References and Notes

1a Hunt S. Chemistry and Biochemistry of the Amino Acids Barrett GC. Chapman and Hall; London: 1985. p.55

Google Scholar
1b Barrett GC. Amino Acids, Peptides and Proteins Vol. 13: The Chemical Society; London: 1980. p.1

Google Scholar
2 For a recent review, see: Nájera C. Sansano JM. Chem. Rev. 2007, 107: 4584 ; and references therein

Crossref Google Scholar
3a Isono K. Asahi K. Suzuki S. J. Am. Chem. Soc. 1969, 91: 7490

Google Scholar
3b Isono K. Suzuki S. Heterocycles 1979, 13: 333

Google Scholar
4 Shenbagamurthi P. Smith HA. Becker JM. Steinfeld A. Naider F. J. Med. Chem. 1983, 26: 1518

Crossref Google Scholar
5a Joo J.-E. Pham V.-T. Tian Y.-S. Chung Y.-S. Oh C.-Y. Lee K.-Y. Ham W.-H. Org. Biomol. Chem. 2008, 6: 1498

Google Scholar
5b Collet M. Genisson Y. Baltas M. Tetrahedron: Asymmetry 2007, 18: 1320

Google Scholar
5c Enders D. Vrettou M. Synthesis 2006, 2155

Google Scholar
5d Li S. Hui XP. Yang SB. Jia ZJ. Xu PF. Lu TJ. Tetrahedron: Asymmetry 2005, 16: 1729

Google Scholar
5e Tarrade A. Dauban P. Dodd RH. J. Org. Chem. 2003, 68: 9521

Google Scholar
5f Raghavan S. Joseph S. Tetrahedron Lett. 2003, 44: 6713

Google Scholar
5g Pepper AG. Procter G. Voyle M. Chem. Commun. 2002, 1066

Google Scholar
5h Kim K.-S. Lee Y.-J. Kim J.-H. Sung D.-K. Chem. Commun. 2002, 1116

Google Scholar
5i Bose AK. Banik BK. Mathur C. Wagle DR. Manhas MS. Tetrahedron 2000, 56: 5603

Google Scholar
5j Uchida K. Kato K. Yamaguchi K. Akita H. Heterocycles 2000, 53: 2253

Google Scholar
5k Ghosh AK. Wang Y. Tetrahedron 1999, 55: 13369

Google Scholar
5l Uchida K. Kato K. Akita H. Synthesis 1999, 1678

Google Scholar
5m Ghosh AK. Wang Y. J. Org. Chem. 1999, 64: 2789

Google Scholar
5n Savage I. Thomas EJ. Wilson PD. J. Chem. Soc., Perkin Trans. 1 1999, 3291

Google Scholar
5o Harwood LM. Robertson SM. Chem. Commun. 1998, 2641

Google Scholar
5p Veeresa G. Datta A. Tetrahedron Lett. 1998, 39: 119

Google Scholar
5q Trost BM. Krueger AC. Bunt RC. Zambrano J. J. Am. Chem. Soc. 1996, 118: 6520

Google Scholar
5r Kang S.-H. Choi H.-W. Chem. Commun. 1996, 1521

Google Scholar
5s Matsuura F. Hamada Y. Shioiri T. Tetrahedron Lett. 1994, 35: 733

Google Scholar
5t Chida N. Koizumi K. Kitada Y. Yokoyama C. Ogawa SJ. J. Chem. Soc., Chem. Commun. 1994, 111

Google Scholar
5u Jackson RFW. Palmer NJ. Wythes MJ. J. Chem. Soc., Chem. Commun. 1994, 95

Google Scholar
5v Casiraghi G. Passu G. Spanu P. Pinna L. Tetrahedron Lett. 1994, 35: 2423

Google Scholar
5w Ariza J. Diaz M. Font J. Ortuno RM. Tetrahedron 1993, 49: 1315

Google Scholar
5x Banik BK. Manhas MS. Bose AK. J. Org. Chem. 1993, 58: 307

Google Scholar
5y Saksena AK. Lovey RG. Girijavallabhan VM. Ganguly AK. J. Org. Chem. 1986, 51: 5024

Google Scholar
5z Isono K. Asahi K. Suzuki S. J. Am. Chem. Soc. 1969, 91: 7499

Google Scholar
6a Kim JD. Kim IS. Jin CH. Zee OP. Jung YH. Tetrahedron Lett. 2005, 46: 1079

Google Scholar
6b Jung YH. Kim JD. Arch. Pharm. Res. 2005, 28: 382

Google Scholar
6c Kim JD. Zee OP. Jung YH. J. Org. Chem. 2003, 68: 3721

Google Scholar
6d Kim JD. Han G. Zee OP. Jung YH. Tetrahedron Lett. 2003, 44: 733

Google Scholar
6e Jung YH. Kim JD. Arch. Pharm. Res. 2003, 26: 667

Google Scholar
6f Kim JD. Han G. Jeong LS. Park H.-J. Zee OP. Jung YH. Tetrahedron 2002, 58: 4395

Google Scholar
6g Kim JD. Lee MH. Han G. Park H. Zee OP. Jung YH. Tetrahedron 2001, 57: 8257

Google Scholar
6h Jung YH. Kim JD. Arch. Pharm. Res. 2001, 24: 371

Google Scholar
6i Kim JD. Lee MH. Lee MJ. Jung YH. Tetrahedron Lett. 2000, 41: 5073

Google Scholar
6j Jung YH. Kim JD. Arch. Pharm. Res. 2000, 23: 574

Google Scholar
7a Kim IS. Ryu CB. Li QR. Zee OP. Jung YH. Tetrahedron Lett. 2007, 48: 6258

Google Scholar
7b Kim IS. Li QR. Lee JK. Lee SH. Lim JK. Zee OP. Jung YH. Synlett 2007, 1711

Google Scholar
7c Kim IS. Lee HY. Jung YH. Heterocycles 2007, 71: 1787

Google Scholar
7d Kim IS. Kim SJ. Lee JK. Li QR. Jung YH. Carbohydr. Res. 2007, 342: 1502

Google Scholar
7e Kim IS. Oh JS. Zee OP. Jung YH. Tetrahedron 2007, 63: 2622

Google Scholar
7f Kim IS. Ji YJ. Jung YH. Tetrahedron Lett. 2006, 47: 7289

Google Scholar
7g Kim IS. Zee OP. Jung YH. Org. Lett. 2006, 8: 4101

Google Scholar
7h Kim IS. Kim JD. Ryu CB. Zee OP. Jung YH. Tetrahedron 2006, 62: 9349

Google Scholar
7i Kim JD. Kim IS. Jin CH. Zee OP. Jung YH. Org. Lett. 2005, 7: 4025

Google Scholar
12 Bal BS. Childers WE. Pinnick HW. Tetrahedron 1981, 37: 2091

Crossref Google Scholar

8

Characterization data for 5: [α]_D ^²5 -25.8 (c 1.0, CHCl₃). IR (CH₂Cl₂): 3450, 3011, 2866, 1513, 1494, 1055 cm^-¹. cis-Isomer: ^¹H NMR (500 MHz, CDCl₃): δ = 2.22-2.24 (br, 1 H), 3.45 (dd, J = 12.5, 3.5 Hz, 1 H), 3.68 (dd, J = 11.5, 3.5 Hz, 1 H), 3.78-3.83 (m, 2 H), 4.19 (d, J = 12.0 Hz, 1 H), 4.57-4.82 (m, 6 H), 5.88 (dd, J = 12.0, 10.0 Hz, 1 H), 6.78 (d, J = 12.0 Hz, 1 H), 7.07-7.40 (m, 20 H). ^¹³C NMR (125 MHz, CDCl₃): δ = 61.63, 70.40, 73.15, 73.21, 75.38, 80.27, 82.47, 126.85, 127.54, 127.88, 127.98, 128.13, 128.31, 128.55, 128.56, 128.61, 128.77, 129.12, 133.99, 136.66, 137.82, 138.48. trans-Isomer: ^¹H NMR (500 MHz, CDCl₃): δ = 2.22-2.24 (br, 1 H), 3.61 (dd, J = 11.5, 3.5 Hz, 1 H), 3.72-3.77 (m, 3 H), 4.30 (dd, J = 7.5, 4.0 Hz, 1 H), 4.45 (d, J = 11.5 Hz, 1 H), 4.60-4.82 (m, 5 H), 6.22 (d, J = 16.0, 7.5 Hz, 1 H), 6.59 (d, J = 16.0 Hz, 1 H), 7.07-7.40 (m, 20 H). ^¹³C NMR (125 MHz, CDCl₃): δ = 61.78, 71.03, 72.96, 75.15, 79.70, 80.49, 82.22, 126.84, 127.53, 127.87, 127.94, 127.97, 128.04, 128.17, 128.42, 128.56, 128.60, 128.65, 128.77, 128.83, 129.94, 133.82, 133.99, 138.68. HRMS (FAB): m/z [M + H⁺] calcd for C₃₃H₃₅O₄: 495.2535; found: 495.2525.

9

Characterization data for 6: [α]_D ^²5 -33.8 (c 0.5, CHCl₃). IR (CH₂Cl₂): 2864, 2360, 1541, 1496, 1454, 1395, 1352, 1027, 1089, 1028, 914, 806, 736 cm^-¹. cis-Isomer: ^¹H NMR (500 MHz, CDCl₃): δ = 3.23 (d, J = 9.0 Hz, 1 H), 3.57-3.59 (m, 1 H), 3.92 (br s, 2 H), 4.12 (d, J = 12.0 Hz, 1 H), 4.25 (d, J = 12.0 Hz, 1 H), 4.41-4.88 (m, 7 H), 5.89 (t, J = 10.0 Hz, 1 H), 6.77 (d, J = 10.0 Hz, 1 H), 7.01-7.39 (m, 25 H). ^¹³C NMR (125 MHz, CDCl₃): δ = 69.59, 70.16, 73.17, 73.47, 75.74, 78.90, 82.51, 126.85, 127.43, 127.72, 127.75, 127.89, 128.03, 128.31, 128.43, 128.52, 128.59, 128.62, 128.78, 129.22, 130.48, 133.55, 136.78, 138.10, 138.95. trans-Isomer: ^¹H NMR (500 MHz, CDCl₃): δ = 3.60-3.66 (m, 2 H), 3.64 (dd, J = 10.0, 4.5 Hz, 1 H), 3.76 (dd, J = 6.0, 4.5 Hz, 1 H), 4.29-4.39 (m, 1 H), 4.41-4.88 (m, 8 H), 6.16 (dd, J = 12.5, 7.5 Hz, 1 H), 6.52 (d, J = 12.5 Hz, 1 H), 7.01-7.39 (m, 25 H). ^¹³C NMR (125 MHz, CDCl₃): δ = 70.36, 70.95, 73.34, 73.56, 75.43, 80.14, 81.21, 81.97, 116.53, 127.30, 127.56, 127.76, 127.84, 127.99, 128.20, 128.42, 128.50, 128.55, 128.61, 128.72, 128.96, 130.47, 133.71, 136.84, 138.51, 139.12. HRMS (FAB): m/z [M + H⁺] calcd for C₄₀H₄₁O₄: 585.3005; found: 585.3010.

10

Characterization data for 7: [α]_D ^²5 +25.8 (c 1.0, CHCl₃). IR (CH₂Cl₂): 3030, 2867, 1719, 1491, 1454, 1214, 1090, 1027, 967, 737, 697 cm^-¹. cis-Isomer: ^¹H NMR (500 MHz, CDCl₃): δ = 3.53-3.73 (m, 3 H), 3.85 (dd, J = 7.0, 2.0 Hz, 1 H), 4.35 (d, J = 12.0 Hz, 1 H), 4.48-6.63 (m, 4 H), 4.82 (d, J = 11.0 Hz, 1 H), 5.06 (br m, 3 H), 5.37 (d, J = 8.0 Hz, 1 H), 5.72 (dd, J = 12.0, 9.5 Hz, 1 H), 6.52 (d, J = 12.0 Hz, 1 H), 7.18-7.44 (m, 25 H). ^¹³C NMR (125 MHz, CDCl₃): δ = 49.83, 66.97, 69.39, 73.27, 73.59, 75.64, 80.25, 82.21, 127.38, 127.74, 127.83, 128.01, 128.08, 128.29, 128.51, 128.54, 128.59, 128.72, 128.97, 130.85, 131.02, 136.61, 138.48, 138.71, 155.86. trans-Isomer: ^¹H NMR (500 MHz, CDCl₃): δ = 3.68 (br, 1 H), 3.78 (br m, 2 H), 3.86 (br, 1 H), 4.54-4.66 (m, 5 H), 4.72 (d, J = 12.0 Hz, 1 H), 4.79 (d, J = 12.0 Hz, 1 H), 5.11 (s, 2 H), 5.44 (br, 1 H), 6.15 (dd, J = 16.0, 5.5 Hz, 1 H), 6.50 (d, J = 16.0 Hz, 1 H), 7.25-7.36 (m, 25 H). ^¹³C NMR (125 MHz, CDCl₃ ): δ = 53.79, 67.07, 69.79, 73.40, 73.75, 75.22, 80.24, 81.30, 126.73, 127.78, 127.83, 127.90, 128.00, 128.04, 128.11, 128.36, 128.43, 128.58, 128.61, 128.63, 128.71, 128.75, 131.00, 136.75, 136.95, 138.38, 138.75, 156.04. HRMS (FAB): m/z [M + H⁺] calcd for C₄₁H₄₂NO₅: 628.3063; found: 628.3062.

11

Characterization data for 8: [α]_D ^²5 -7.5 (c 1.0, CHCl₃). IR (CH₂Cl₂): 3060, 1717, 1541, 1508, 1456, 1091, 697 cm^-¹. ^¹H NMR (300 MHz, CDCl₃): δ = 3.58-3.66 (m, 3 H), 3.72-3.78 (m, 1 H), 4.34 (br, 1 H), 4.44 (d, J = 11.7 Hz, 1 H), 4.46 (s, 2 H), 4.59 (d, J = 11.7 Hz, 1 H), 4.73 (s, 2 H), 5.12 (d, J = 15.6 Hz, 1 H), 5.16 (d, J = 15.6 Hz, 1 H), 5.62 (br d, J = 5.7 Hz, 1 H), 7.27-7.41 (m, 20 H), 9.73 (s, 1 H). ^¹³C NMR (125 MHz, CDCl₃): δ = 60.19, 67.41, 69.67, 73.05, 73.71, 74.23, 76.69, 78.59, 128.01, 128.14, 128.36, 128.52, 128.59, 128.67, 128.72, 128.75, 128.81, 136.29, 137.62, 137.70, 138.10, 156.38, 197.629. HRMS (FAB): m/z [M + H⁺] calcd for C₃₄H₃₆NO₆: 554.2543; found: 554.2543.

13

Characterization data for 9: [α]_D ^²5 -12.5 (c 0.5, CHCl₃). IR (CH₂Cl₂): 3421, 3031, 2870, 2360, 1716, 1507, 1455, 1397, 1214, 1092, 737, 698 cm^-¹. ^¹H NMR (300 MHz, CDCl₃): δ = 3.60-3.86 (m, 4 H), 4.40-4.78 (m, 7 H), 5.14 (s, 2 H), 5.61 (br, 1 H), 7.30-7.36 (m, 20 H). ^¹³C NMR (125 MHz, CDCl₃): δ = 54.21, 67.49, 69.18, 73.32, 73.70, 75.13, 76.68, 78.31, 78.69, 127.95, 128.30, 128.43, 128.59, 128.63, 128.70, 128.76, 132.36, 136.29, 137.34, 138.14, 156.65, 174.37. HRMS (FAB): m/z [M + H⁺] calcd for C₃₄H₃₆NO₇: 570.2498; found: 570.2492.

14

Characterization data for 1: [α]_D ^²5 +2.2 (c 1.0, H₂O); mp 170-174 ˚C (dec.). ^¹H NMR (300 MHz, D₂O): δ = 4.21 (dd, J = 3.3, 2.7 Hz, 1 H), 3.93-3.87 (m, 2 H), 3.72-3.60 (m, 2 H). ^¹³C NMR (125 MHz, D₂O): δ = 172.83, 73.33, 68.26, 62.63, 58.16. HRMS (CI): m/z [M + H⁺] calcd for C₅H₁₂NO₅: 166.0715; found: 166.0716.

15

Characterization data for 10: [α]_D ^²5 +35.6 (c 0.5, CHCl₃). IR (CH₂Cl₂): 3425, 2939, 2865, 2360, 1716, 1507, 1456, 1339, 1067, 697 cm^-¹. cis-Isomer: ^¹H NMR (300 MHz, CDCl₃): δ = 3.64-3.72 (m, 2 H), 4.17 (br s, 2 H), 4.55 (d, J = 11.1 Hz, 1 H), 4.61 (d, J = 11.1 Hz, 1 H), 4.65 (d, J = 11.1 Hz, 1 H), 4.85 (d, J = 11.1 Hz, 1 H), 5.10 (s, 2 H), 5.18 (t, J = 8.4 Hz, 1 H), 5.47 (d, J = 7.2 Hz, 1 H), 5.75 (dd, J = 11.4, 9.3 Hz, 1 H), 6.54 (d, J = 11.4 Hz, 1 H), 7.23-7.42 (m, 20 H). ^¹³C NMR (125 MHz, CDCl₃): δ = 49.43, 62.86, 67.22, 73.43, 75.95, 78.70, 83.19, 126.78, 127.48, 127.91, 128.09, 128.21, 128.36, 128.53, 128.77, 130.84, 131.64, 136.74, 136.86, 138.07, 138.13, 138.25, 156.15, 156.52. trans-Isomer: ^¹H NMR (300 MHz, CDCl₃): δ = 3.80-3.90 (m, 2 H), 4.32-4.37 (m, 2 H), 4.61-4.85 (m, 5 H), 5.13 (s, 2 H), 5.48-5.50 (m, 1 H), 6.15 (dd, J = 15.6, 6.0 Hz, 1 H), 6.58 (d, J = 15.6 Hz, 1 H), 7.23-7.42 (m, 20 H). ^¹³C NMR (125 MHz, CDCl₃): δ = 53.43, 63.13, 66.84, 73.07, 75.47, 77.71, 78.59, 82.01, 126.08, 126.85, 127.90, 128.03, 128.17, 128.29, 128.30, 128.67, 128.81, 131.24, 136.76, 136.85, 137.61, 138.07, 156.26, 156.68. HRMS (FAB): m/z [M + H⁺] calcd for C₃₅H₃₇N₂O₆: 581.2652; found: 581.2655.

16

Characterization data for 11: [α]_D ^²5 -7.5 (c 1.0, CHCl₃). IR (CH₂Cl₂): 3444, 2972, 2360, 1716, 1508, 1456, 1418, 1339, 1067, 739, 698 cm^-¹. ^¹H NMR (300 MHz, CDCl₃): δ = 3.72-3.73 (m 1 H), 4.17-4.74 (m, 9 H), 5.10-5.15 (m, 2 H), 5.64 (d, J = 6.5 Hz, 1 H), 7.27-7.42 (m, 15 H), 9.67 (s, 1 H). ^¹³C NMR (125 MHz, CDCl₃): δ = 60.03, 62.83, 67.53, 73.10, 74.33, 75.79, 77.91, 128.30, 128.34, 128.47, 128.55, 128.65, 128.69, 128.77, 128.84, 136.24, 137.32, 137.39, 156.39, 156.61, 198.01. HRMS (FAB): m/z [M + H⁺] calcd for C₂₈H₃₁N₂O₇: 507.2131; found: 507.2142.

17

Characterization data for 12: [α]_D ^²5 -10.4 (c 1.0, CHCl₃). IR (CH₂Cl₂): 3365, 3032, 2965, 2360, 1716, 1508, 1456, 1339, 1220, 1066, 740, 698 cm^-¹. ^¹H NMR (500 MHz, CD₃OD): δ = 3.79 (br, 1 H), 4.08 (dd, J = 12.0, 5.0 Hz, 1 H), 4.30 (d, J = 7.0 Hz, 1 H), 4.41 (br d, J = 12.0 Hz, 1 H), 4.51 (s, 1 H), 4.57-4.73 (m, 4 H), 5.08-5.14 (m, 2 H), 7.24-7.37 (m, 15 H). ^¹³C NMR (125 MHz, CD₃OD): δ = 63.26, 66.68, 72.88, 74.66, 78.79, 79.33, 127.50, 127.64, 127.80, 127.96, 128.06, 128.13, 128.29, 136.98, 138.29, 138.47, 157.75, 158.39, 176.12. HRMS (FAB): m/z [M + Na⁺] calcd for C₂₈H₃₀N₂O₈Na: 545.1900; found: 545.1903.

18

Characterization data for 2: [α]_D ^²5 +1.2 (c 1.0, H₂O); mp 215-220 ˚C (dec.). ^¹H NMR (500 MHz, D₂O): δ = 4.17 (br m, 1 H), 4.09-4.04 (m, 3 H), 3.82 (br m, 1 H). ^¹³C NMR (125 MHz, D₂O): δ = 172.95, 159.35, 71.07, 68.28, 65.76, 58.13. HRMS (FAB): m/z [M + H⁺] calcd for C₆H₁₃N₂O₆: 209.0774; found: 209.0776.