An Efficient Synthesis of Aminocyclopentitols via the Stereoselective Amination of Polybenzyl Ethers Using Chlorosulfonyl Isocyanate

In Su Kim; Qing Ri Li; Jae Koo Lee; Sang Hwi Lee; Jae Kyung Lim; Ok Pyo Zee; Young Hoon Jung

doi:10.1055/s-2007-984518

LETTER

An Efficient Synthesis of Aminocyclopentitols via the Stereoselective Amination of Polybenzyl Ethers Using Chlorosulfonyl Isocyanate

In Su Kim, Qing Ri Li, Jae Koo Lee, Sang Hwi Lee, Jae Kyung Lim, 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;

Abstract

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Abstract

An efficient stereoselective route for the preparation of stereoisomeric aminocyclopentitols 3-5 was achieved using a six-step sequence starting from the corresponding d-sugars. Key steps of the synthesis of the title compounds involved the regioselective and diastereoselective amination of cinnamylic 1,2-anti- or 1,2-syn-tribenzyl ethers using chlorosulfonyl isocyanate (CSI), intramolecular olefin metathesis, and diastereoselective dihydroxylation.

Key words

aminocyclopentitol - chlorosulfonyl isocyanate - amination - mannostatin - dihydroxylation

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References

References and Notes

1a Asano N. Curr. Top. Med. Chem. 2003, 3: 471

1b Elbein AD. FASEB J. 1991, 5: 3055

1c Asano N. Nash RJ. Molyneux RJ. Fleet GWJ. Tetrahedron: Asymmetry 2000, 11: 1645

2a Somsak L. Nagya V. Hadady Z. Docsa T. Gergely P. Curr. Pharm. Des. 2003, 9: 1177

2b Johnson PS. Lebovitz HE. Coniff RF. Simonson DC. Raskin P. Munera CL. J. Clin. Endocrinol. Metab. 1998, 83: 1515

3a Greimel P. Spreitz J. Stutz AE. Wrodnigg TM. Curr. Top. Med. Chem. 2003, 3: 513

3b Fleet GWJ. Karpas A. Dwek RA. Fellows LE. Tyms AS. Peturrson S. Namgoong SK. Ramsden NG. Smith PW. Son JC. Wilson F. Witty DR. Jacob GS. Rademacher TW. FEBS Lett. 1988, 237: 128

3c Gruters RA. Neefjes JJ. Tersmette M. de Goede REY. Tulp A. Huisman HG. Miedema F. Ploegh HL. Nature (London) 1987, 330: 74

4 Bitonti AJ, Sjoersma A, and McCann PP. inventors; Eur. Patent Appl. EP423728.

5a Nishimura Y. Curr. Top. Med. Chem. 2003, 3: 575

5b Ostrander GK. Scribner NK. Rohrschneider LR. Cancer Res. 1988, 48: 1091

5c Tsuruoka T. Fukuyasu H. Ishii M. Usui T. Shibahara S. Inouye S. J. Antibiot. 1996, 49: 155

6 For a recent review of synthetic and biological features of the mannostatins, see: Berecibar A. Grandjean C. Siriwardena A. Chem. Rev. 1999, 99: 779

7a Ando O. Nakajima M. Hamano K. Itoi K. Takahashi S. Takamatsu Y. Sato A. Enokita R. Haruyama H. J. Antibiot. 1993, 46: 1116

7b Ando O. Satake H. Itoi K. Sato A. Nakajima M. Takahashi S. Haruyama H. J. Antibiot. 1991, 44: 1165

8 Aoyagi T. Yamamoto T. Kojiri K. Morishima H. Nagai M. Hamada M. Takeuchi T. Umezawa H. J. Antibiot. 1989, 42: 883

9a Kim JD. Kim IS. Hua JC. Zee OP. Jung YH. Tetrahedron Lett. 2005, 46: 1079

9b Jung YH. Kim JD. Arch. Pharm. Res. 2005, 28: 382

9c Kim JD. Zee OP. Jung YH. J. Org. Chem. 2003, 68: 3721

9d Kim JD. Han G. Zee OP. Jung YH. Tetrahedron Lett. 2003, 44: 733

9e Jung YH. Kim JD. Arch. Pharm. Res. 2003, 26: 667

9f Kim JD. Han G. Jeong LS. Park H.-J. Zee OP. Jung YH. Tetrahedron 2002, 58: 4395

9g Kim JD. Lee MH. Han G. Park H. Zee OP. Jung YH. Tetrahedron 2001, 57: 8257

9h Jung YH. Kim JD. Arch. Pharm. Res. 2001, 24: 371

9i Kim JD. Lee MH. Lee MJ. Jung YH. Tetrahedron Lett. 2000, 41: 5073

9j Jung YH. Kim JD. Arch. Pharm. Res. 2000, 23: 574

10a Kim IS. Oh JS. Zee OP. Jung YH. Tetrahedron 2007, 63: 2622

10b Kim IS. Ji YJ. Jung YH. Tetrahedron Lett. 2006, 47: 7289

10c Kim IS. Zee OP. Jung YH. Org. Lett. 2006, 8: 4101

10d Kim IS. Kim JD. Ryu CB. Zee OP. Jung YH. Tetrahedron 2006, 62: 9349

10e Kim JD. Kim IS. Jin CH. Zee OP. Jung YH. Org. Lett. 2005, 7: 4025

11a Krow GR. Yuan J. Lin G. Sonnet PE. Org. Lett. 2002, 4: 1259

11b Roberts DD. J. Org. Chem. 1997, 62: 1857

11c Winstein S. Allred E. Heck R. Grick R. Tetrahedron 1958, 3: 1

12a For a recent review of Wittig olefination, see: Maryanoff BE. Reitz AB. Chem. Rev. 1989, 89: 863

12b Choi WJ. Park JK. Yoo SJ. Kim HO. Moon HR. Chun MW. Jung YH. Jeong LS. J. Org. Chem. 2001, 66: 6490

13

Characterization data for 7a-c:
7a: (Z:E = 2.5:1, anti:syn = 24:1); [α]_D ³⁰ -14.9 (c = 1.0, CHCl₃). ¹H NMR (500 MHz, CDCl₃): δ = 3.50-3.53 (t, J = 4.5 Hz, 0.71 H), 3.60-3.61 (br, 0.29 H), 3.91-4.01 (m, 1 H), 4.32 (d, J = 11.5 Hz, 0.29 H), 4.33 (d, J = 12.0 Hz, 0.71 H), 4.60-4.77 (m, 3.29 H), 5.01-5.15 (m, 4.13 H), 5.29 (d, J = 17.0 Hz, 0.29 H), 5.38 (d, J = 10.0 Hz, 0.29 H), 5.53 (t, J = 10.0, 12.0 Hz, 0.71 H), 5.70-5.84 (m, 1.71 H), 5.90-5.99 (m, 0.29 H),6.00 (dd, J = 7.5, 15.5 Hz, 0.29 H), 6.52 (d, J = 15.5 Hz, 0.29 H), 6.53 (d, J = 15.5 Hz, 0.71 H), 7.23-7.36 (m, 20 H). ¹³C NMR (125 MHz, CDCl₃): δ = 49.69, 66.67, 70.64, 73.65, 81.66, 81.94, 119.76, 120.06, 126.80, 127.51, 127.94, 127.99, 128.09, 128.17, 128.40, 128.55, 128.66, 128.69, 132.55, 132.85, 134.88, 135.12, 136.58, 137.05, 138.14, 138.33, 155.99. HRMS (FAB): m/z [M + H⁺] calcd for C₃₅H₃₆NO₄: 534.2644; found: 534.2639.
7b: (Z:E = 2.6:1, anti:syn = 18:1); [α]_D ²⁵ -79.6 (c = 0.1, CHCl₃). ¹H NMR (500 MHz, CDCl₃): δ = 3.68-3.73 (br, 0.56 H), 3.80 (t, J = 7.0 Hz, 0.72 H), 3.88-3.92 (m, 0.72 H), 4.29 (d, J = 11.5 Hz, 0.28 H), 3.39 (d, J = 11.5 Hz, 0.72 H), 4.47 (d, J = 11.5 Hz, 0.28 H), 4.54 (d, J = 11.5 Hz, 0.72 H), 4.57 (d, J = 11.5 Hz, 0.28 H), 4.61 (d, J = 11.5 Hz, 0.72 H), 4.63 (d, J = 11.5 Hz, 0.28 H), 4.67 (d, J = 11.5 Hz, 0.72 H), 4.89 (br, 0.28 H), 5.06-5.16 (m, 2 H), 5.25 (t, J = 8.0 Hz, 0.72 H), 5.35-5.44 (m, 3 H), 5.76 (dd, J = 10.0, 10.5 Hz, 0.72 H), 5.85-5.94 (m, 1 H), 6.17 (dd, J = 8.0, 15.5 Hz, 0.28 H), 6.49 (d, J = 15.5 Hz, 0.28 H), 6.63 (d, J = 10.5 Hz, 0.72 H), 7.03-7.46 (m, 20 H). ¹³C NMR (125 MHz, CDCl₃): δ = 50.32, 66.87, 70.47, 70.53, 74.49, 81.12, 81.34, 83.20, 83.50, 119.70, 120.25, 126.78, 127.53, 127.60, 127.85, 128.01, 128.15, 128.23, 128.37, 128.58, 128.65, 128.68, 128.76, 128.90, 132.74, 132.82, 136.18, 136.58, 138.25, 155.60. HRMS (FAB): m/z [M + H⁺] calcd for C₃₅H₃₆NO₄: 534.2644; found: 534.2640.
7c: (Z:E = 2.8:1, anti:syn = 1:5); [a]_D ²⁵ +1.2 (c = 1.0, CHCl₃). ¹H NMR (500 MHz, CDCl₃): δ = 3.56 (t, J = 7.5 Hz, 0.74 H), 3.71 (dd, J = 3.5, 6.5 Hz, 0.26 H), 3.88-3.93 (m, 1 H), 4.30 (d, J = 11.5 Hz, 0.26 H), 4.45-4.64 (m, 3.46 H), 4.76 (d, J = 11.5 Hz, 0.26 H), 4.91-4.93 (br, 0.26 H), 5.09-5.14 (m, 2.74 H), 5.31-5.64 (m, 3 H), 5.84 (dd, J = 10.0, 11.0 Hz, 0.74 H), 5.84-5.87 (m, 1 H), 6.18 (dd, J = 8.0, 16.0 Hz, 0.26 H), 6.53 (d, J = 11.0 Hz, 0.74 H), 6.56 (d, J = 16.0 Hz, 0.26 H), 7.06-7.49 (m, 20 H). ¹³C NMR (125 MHz, CDCl₃): δ = 54.78, 66.88, 70.52, 74.50, 74.66, 81.11, 83.47, 120.33, 126.06, 126.81, 127.82, 127.87, 127.97, 128.14, 128.17, 128.27, 128.35, 128.53, 128.67, 128.69, 128.72, 128.79, 132.76, 136.18, 136.86, 137.01, 138.30, 155.80. HRMS (FAB): m/z [M + H⁺] calcd for C₃₅H₃₆NO₄: 534.2644; found: 534.2654.

For recent reviews of ring-closing metathesis, see:

14a Trnka TM. Grubbs RH. Acc. Chem. Res. 2001, 34: 18

14b Fürstner A. Angew. Chem. Int. Ed. 2000, 39: 3012

15

Characterization data for 10a-c:
10a: [α]_D ²⁹ -32.9 (c = 1.0, CHCl₃). ¹H NMR (500 MHz, CDCl₃): δ = 4.09 (br t, J = 5.5 Hz, 1 H), 4.52-4.61 (m, 5 H), 4.90-4.93 (br, 1 H), 5.12 (s, 2 H), 5.19 (d, J = 7.5 Hz, 1 H), 5.95 (d, J = 6.0 Hz, 1 H), 6.03 (d, J = 5.5 Hz, 1 H), 7.27-7.40 (m, 15 H). ¹³C NMR (125 MHz, CDCl₃): δ = 55.67, 66.99, 71.92, 72.79, 82.56, 86.81, 128.00, 128.09, 128.17, 128.22, 128.34, 128.61, 128.67, 128.72, 128.74, 132.89, 134.65, 136.76, 137.77, 138.37, 156.37. HRMS (FAB): m/z [M + H⁺] calcd for C₂₇H₂₈NO₄: 430.2018; found: 430.2020.
10b: [α]_D ²⁵ -79.6 (c = 0.1, CHCl₃). ¹H NMR (500 MHz, CDCl₃): δ = 4.02 (t, J = 5.5 Hz, 1 H), 4.30 (dd, J = 2.5, 5.0 Hz, 1 H), 4.64 (d, J = 12.0 Hz, 1 H), 4.65 (d, J = 12.0 Hz, 1 H), 4.69-4.71 (br, 1 H), 4.72 (d, J = 12.0 Hz, 1 H), 4.79 (d, J = 12.0 Hz, 1 H), 5.12 (s, 2 H), 5.29 (d, J = 9.0 Hz, 1 H), 6.05 (dd, J = 2.0, 6.0 Hz, 1 H), 6.09 (dd, J = 3.0, 6.0 Hz, 1 H), 7.27-7.38 (m, 15 H). ¹³C NMR (125 MHz, CDCl₃): δ = 54.65, 66.88, 72.31, 72.58, 78.42, 80.03, 127.86, 127.90, 128.02, 128.05, 128.22, 128.61, 128.69, 133.06, 135.08, 136.90, 138.30, 138.79, 156.36. HRMS (FAB): m/z [M + H⁺] calcd for C₂₇H₂₈NO₄: 430.2018; found: 430.2013.
10c: [α]_D ²⁹ +6.2 (c = 1.0, CHCl₃). ¹H NMR (500 MHz, CDCl₃): δ = 4.02 (t, J = 5.5 Hz, 1 H), 4.30 (dd, J = 2.5, 5.0 Hz, 1 H), 4.64 (d, J = 12.0 Hz, 1 H), 4.65 (d, J = 12.0 Hz, 1 H), 4.70-4.73 (br m, 2 H), 4.79 (d, J = 12.0 Hz, 1 H), 5.12 (s, 2 H), 5.28 (d, J = 9.0 Hz, 1 H), 6.05 (dd, J = 1.5, 6.0 Hz, 1 H), 6.08 (dd, J = 2.5, 6.5 Hz, 1 H), 7.27-7.41 (m, 15 H). ¹³C NMR (125 MHz, CDCl₃): δ = 54.65, 66.87, 72.31, 72.58, 78.44, 80.03, 127.84, 127.90, 128.01, 128.03, 128.21, 128.60, 128.69, 133.05, 135.08, 136.91, 138.30, 143.67, 156.35. HRMS (FAB): m/z [M + H⁺] calcd for C₂₇H₂₈NO₄: 430.2018; found: 430.2019.

16a Cha JK. Christ WJ. Kishi Y. Tetrahedron Lett. 1983, 24: 3947

16b Cha JK. Christ WJ. Kishi Y. Tetrahedron Lett. 1983, 24: 3943

16c VanRheenen V. Kelly RC. Cha DY. Tetrahedron Lett. 1976, 17: 1973

17

Characterization data for 11a-13a and 11b:
11a: [α]_D ²³ +1.0 (c = 0.22, CHCl₃). ¹H NMR (500 MHz, CDCl₃): δ = 3.92-4.25 (m, 5 H), 4.46 (d, J = 11.0 Hz, 1 H), 4.53 (d, J = 12.0 Hz, 1 H), 4.57 (d, J = 11.0 Hz, 1 H), 4.65 (d, J = 12.0 Hz, 1 H), 5.11 (d, J = 12.5 Hz, 1 H), 5.16 (d, J = 12.5 Hz, 1 H), 5.54-5.59 (br, 1 H), 7.22-7.36 (m, 15 H). ¹³C NMR (125 MHz, CDCl₃): δ = 53.83, 67.33, 72.06, 72.71, 73.41, 80.22, 82.63, 88.40, 128.04, 128.09, 128.24, 128.39, 128.45, 128.71, 128.78, 128.81, 136.52, 137.20, 137.92, 154.56. HRMS (FAB): m/z [M + H⁺] calcd for C₂₇H₃₀NO₆: 464.2073; found: 464.2068.
11b: [α]_D ²² -18.2 (c = 0.08, CHCl₃). ¹H NMR (500 MHz, CDCl₃): δ = 1.58-1.64 (br, 1 H), 2.84-2.88 (br, 1 H), 3.86 (dd, J = 4.0, 4.5 Hz, 1 H), 3.93 (t, J = 6.5 Hz, 1 H), 4.01-4.21 (m, 3 H), 4.78 (d, J = 11.5 Hz, 1 H), 4.52-4.60 (m, 2 H), 4.71 (d, J = 11.5 Hz, 1 H), 5.12 (s, 2 H), 5.52 (br s, 1 H), 7.24-7.48 (m, 15 H). ¹³C NMR (125 MHz, CDCl₃): δ = 57.16, 67.41, 69.13, 72.46, 73.06, 77.49, 80.21, 82.78, 128.22, 128.28, 128.33, 128.42, 128.49, 128.79, 136.41, 137.42, 137.57, 157.66. HRMS (FAB): m/z [M + Na⁺] calcd for C₂₇H₂₉NO₆Na: 486.1893; found: 486.1896.
12a: [α]_D ²³ +7.3 (c = 0.44, CHCl₃). ¹H NMR (500 MHz, CDCl₃): δ = 1.82 (br s, 1 H), 3.09 (br s, 1 H), 3.91-3.99 (m, 3 H), 4.17 (dd, J = 4.5, 5.5 Hz, 1 H), 4.23 (br d, J = 3.0 Hz, 1 H), 4.52 (d, J = 12.0 Hz, 1 H), 4.68 (d, J = 12.0 Hz, 1 H), 4.76 (d, J = 12.0 Hz, 1 H), 4.79 (d, J = 12.0 Hz, 1 H), 5.14 (d, J = 12.5 Hz, 1 H), 5.10 (d, J = 12.5 Hz, 1 H), 5.62 (d, J = 6.0 Hz, 1 H), 7.27-7.40 (m, 15 H). ¹³C NMR (125 MHz, CDCl₃): δ = 58.34, 67.35, 72.63, 73.27, 73.59, 76.42, 77.58, 84.59, 127.94, 128.01, 128.21, 128.37, 128.50, 128.69, 128.76, 128.82, 136.45, 138.04, 138.29, 157.59. HRMS (FAB): m/z [M + H⁺] calcd for C₂₇H₃₀NO₆: 464.2073; found: 464.2083.
13a: [α]_D ²⁹ -2.5 (c = 1.0, CHCl₃). ¹H NMR (300 MHz, CDCl₃): δ = 2.98-3.22 (br, 2 H), 3.90-3.98 (br m, 2 H), 4.21-4.26 (br m, 3 H), 4.51 (d, J = 11.7 Hz, 1 H), 4.71 (d, J = 12.0 Hz, 1 H), 4.79 (d, J = 12.0 Hz, 1 H), 4.82 (d, J = 11.7 Hz, 1 H), 5.17 (s, 2 H), 5.63 (br d, J = 5.7 Hz, 1 H), 7.23-7.65 (m, 15 H). ¹³C NMR (125 MHz, CDCl₃): δ = 58.41, 67.34, 72.66, 73.31, 73.61, 76.46, 77.52, 84.55, 127.91, 127.98, 128.17, 128.34, 128.47, 128.66, 128.74, 128.80, 136.44, 138.00, 138.29, 157.69. HRMS (FAB): m/z
[M + H⁺] calcd for C₂₇H₃₀NO₆: 464.2073; found: 464.2072.

18 Donohoe TJ. Blades K. Moore PR. Waring MJ. Winter JJG. Helliwell M. Newcombe NJ. Stemp G. J. Org. Chem. 2002, 67: 7946

19 Poli G. Tetrahedron Lett. 1989, 30: 7385

20

Characterization data for 3-5:
3: [α]_D ²³ +6.3 (c = 0.79, MeOH). ¹H NMR (500 MHz, D₂O): δ = 3.22 (t, J = 3.0 Hz, 1 H), 3.73 (dd, J = 4.0, 7.5 Hz, 1 H), 3.80 (dd, J = 3.0, 7.5 Hz, 1 H), 3.91-3.94 (m, 2 H). ¹³C NMR (125 MHz, D₂O): δ = 51.91, 73.32, 75.91, 76.01, 83.35. HRMS (FAB): m/z [M + H⁺] calcd for C₅H₁₂NO₄: 150.0766; found: 150.0766.
4: [α]_D ²³ -11.9 (c = 0.23, MeOH). ¹H NMR (500 MHz, D₂O): δ = 3.35 (t, J = 8.0 Hz, 1 H), 3.86-3.92 (m, 2 H), 3.99 (t, J = 4.5 Hz, 1 H), 4.07 (dd, J = 6.0, 8.0 Hz, 1 H). ¹³C NMR (125 MHz, D₂O): δ = 56.37, 71.18, 73.37, 74.80, 76.84. HRMS (FAB): m/z [M + H⁺] calcd for C₅H₁₂NO₄: 150.0766; found: 150.0767.
5: [α]_D ²² -2.3 (c = 1.0, MeOH). ¹H NMR (500 MHz, D₂O): δ = 3.46 (t, J = 6.0 Hz, 1 H), 3.96 (t, J = 5.0 Hz, 1 H), 4.00 (dd, J = 6.0, 6.5 Hz, 1 H), 4.19 (t, J = 7.0 Hz, 1 H), 4.22 (dd, J = 4.5, 5.5 Hz, 1 H). ¹³C NMR (125 MHz, D₂O): δ = 57.19, 67.83, 71.83, 73.85, 76.39. HRMS (FAB): m/z [M + H⁺] calcd for C₅H₁₂NO₄: 150.0766; found: 150.0767.