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 and Notes

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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.

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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.

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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.

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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.