JP5342163B2 - アルキルβ−D−(チオ)グルコピラノシド誘導体の位置選択的保護基導入方法 - Google Patents
アルキルβ−D−(チオ)グルコピラノシド誘導体の位置選択的保護基導入方法 Download PDFInfo
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Description
(2)一般式[4]で示される化合物とTBDPSX1(式中、TBDPS及びX1は前記に同じ。)とを反応させることにより、一般式[5]で示される化合物を形成し、次いで、これと二炭酸 ジ-tert-ブチルを、一般式[2]で示される触媒の存在下で反応させることにより、一般式[6]で示される化合物を形成し、更に、これとBOMX1(式中、BOMはベンジルオキシメチル基を表し、X1は前記に同じ)を反応させることを特徴とする、一般式[7]
反応時間は、通常1〜50時間、好ましくは5〜30時間である。
反応時間は、通常10分〜10時間、好ましくは10分〜5時間である。
反応時間は、通常1〜30時間である。
反応時間は、通常1〜30時間である。
メタノール(50 mL)中に、L-ピログルタミン酸(5.00 g, 38.7 mmol)、濃塩酸の触媒量(50 μL)を室温で21時間撹拌させた。反応終了後、溶媒を除去し、(S)-メチル 2-ピロリドン-5-カルボキシレート (5.56 g)を得た。次いで、ジオキサン (30 mL)中で、得られた(S)-メチル 2-ピロリドン-5-カルボキシレート (2.00 g, 14.0 mmol)と、4-ブロモピリジン 塩酸塩(4-bromopyridine-HCl) (5.40 g, 28.0 mmol)、ヨウ化第一銅 (1.33 g, 7.0 mmol)及び炭酸セシウム (11.4 g, 35.0 mmol)を混合し、アルゴン雰囲気下、15分間撹拌反応させた。得られた混合液を、アルゴン雰囲気下、ジオキサンで23時間加熱還流させた。還流後、室温まで冷却した後、得られた混合物を濾過し、ジオキサンで洗浄した。得られた濾液を真空下で濃縮させた。残留物をシリカカラムクロマトグラフィー(酢酸エチル:メタノール=10:1)により精製し、(S)-メチル 5-オキソ-1-(ピリジン-4-イル)ピロリジン-2-カルボキシレート (2.10 g, 68%)を得た。
[α]D 21 = -48 (c 1.0, CHCl3); 1H NMR (CDCl3) δ 8.47 (dd, 4.9, 1.6, 2H), 7.45 (dd, 4.9, 1.6, 2H), 4.72 (dd, 9.0, 2.4, H), 3.73 (s, 3H), 2.39-3.72 (m, 3H), 2.11-2.25 (m, H). 13C NMR (CDCl3) δ 174.8, 171.61, 150.68, 145.17, 113.14, 60.02, 53.12, 31.26, 23.04. IR (neat) 3000, 1722, 1712, 1590, 1500, 1380 cm-1. EI-MS m/z (rel intensity) 220 (M+, 25), 161 (100), 133 (15), 105 (10), 78 (10); Anal Calcd for C11H12N2O3: C, 59.99; H, 5.49; N, 12.72 %. Found: C, 59.70; H, 5.58; N, 12.57 %
−78℃に冷却した、(S)-メチル 5-オキソ-1-(ピリジン-4-イル)ピロリジン-2-カルボキシレート (3.10 g, 14.1 mmol)のテトラヒドロフラン(THF) (50 mL)溶液中に、三フッ化ホウ素エチルエーテル(BF3・Et2O) (1.90 ml, 15.0 mmol)を添加し、次いで水素化ジイソブチルアルミニウム(DIBAH) (0.94 mol/L ヘキサン溶液, 30 mL, 28.2 mmol)を添加し、90分間撹拌反応させた。反応終了後、反応混合物を酒石酸カリウムナトリウム溶液 (39 g, 水 120 mL)に添加し、得られた混合物を室温で1時間撹拌反応させた。得られた混合物を酢酸エチルで抽出し、得られた有機層を飽和炭酸水素ナトリウムで洗浄し、硫酸マグネシウムで乾燥、濾過、溶媒留去した後、粗生物を得た。これをジクロロメタン(80 mL)に溶解し、次いでこの溶液に、アルゴン雰囲気下0℃で、トリメチルシリルシアニド(TMSCN) (4.70 ml, 35.3 mmol)及びトリフルオロメタンスルホン酸トリメチルシリル(TMSOTf) (6.40 ml, 35.3 mmol)を添加した。冷却槽を除去した後、混合物を室温で12時間撹拌反応させた。得られた混合物を飽和炭酸水素ナトリウム溶液へ添加し、更に30分間撹拌させた。混合物を酢酸エチルで抽出し、得られた有機層を飽和炭酸水素ナトリウムで洗浄し、硫酸ナトリウムで乾燥、濾過、溶媒流去した。残渣をシリカカラムクロマトグラフィー(CHCl3:MeOH=100:0〜100:1)により精製し、目的とする(2S,5S)-メチル 5-シアノ-1-(ピリジン-4-イル)-ピロリジン-2-カルボキシレート (0.75 g, 23% overall)を得た。〔(2S,5R)-異性体 (0.93 g, 29% overall)〕
[α]D 21 = -235 (c 1.0, CHCl3). 1H NMR (CDCl3) δ 8.37 (dd, 4.8, 1.7, 2H), 6.50 (dd, 4.8, 1.7, 2H), 4.68 (m, H), 4.45 (m, H), 3.76 (s, 3H), 2.25-2.62 (m, 4H). 13C NMR (CDCl3) δ 172.15, 150.43, 148.90, 117.96, 108.19, 59.93, 52.91, 48.77, 29.65, 29.53. IR (neat) 1740, 1595, 1510, 1380 cm-1. EI-MS m/z (rel intensity) 231 (M+, 35), 172 (100), 145 (61), 105 (10); HRMS calculated for C12H13N3O2; 231.10077, found 231.1006.
[α]D 21 = +79 (c 1.0, CHCl3). 1H NMR (CDCl3) δ 8.30 (dd, 4.9, 1.6, 2H), 6.47 (dd, 4.9, 1.8, 2H), 4.55 (m, H), 4.37 (m, H), 3.73 (s, 3H), 2.30-2.60 (m, 4H). 13C NMR (CDCl3) δ 171.81, 150.14, 148.87, 117.40, 107.70, 60.43, 52.66, 48.54, 30.00, 29.15. IR (neat) 1740, 1600, 1510, 1380 cm-1. EI-MS m/z (rel intensity) 231 (M+, 20), 172 (100), 145 (25); HRMS calculated for C12H13N3O2; 231.10077, found 231.1010.
濃塩酸 (3.0 mL)中に、(2S,5S)-メチル 5-シアノ-1-(ピリジン-4-イル)-ピロリジン-2-カルボキシレート (0.75 g, 3.24 mmol)を溶解させ、85℃で8時間加熱させた。室温に冷却後、得られた晶析物を濾過し、アセトンで洗浄し、(2S,5S)-1-(ピリジン-4-イル)ピロリジン-2,5-ジカルボン酸塩酸塩(0.88 g, quant)を無色針状晶として得た。
m.p. 225-235 ℃. 1H NMR (D2O) δ 8.03 (d, 6.5, 2H), 6.74 (d, 6.5, 2H), 4.65 (m, partially overlapping with water signal), 2.15-2.50 (m, 4H). 13C NMR (D2O) δ 174.08, 155.62, 138.90, 108.44, 62.01, 28.48; IR (KBr) 1740, 1640, 1595, 1540 cm-1. FAB-MS m/z 237 (MH+); Anal Calcd for C11H12N2O4: C, 48.45; H, 4.81; N, 10.27. Found: C, 48.28; H, 4.92; N, 10.33.
無色結晶 m.p.200-207℃. [α]D 21 = -15 (c 1.0, CH3OH). 1H NMR (400 MHz, CD3OD) δ 7.53 (dd, J = 8.0, 1.0 Hz, 1H), 7.39 (dd, J = 8.0, 1.0 Hz, 1H), 7.20 (s, 1H), 7.14 (ddd, J = 8.0, 7.0, 1.0 Hz, 1H), 7.06 (ddd, J = 8.0, 7.0, 1.0 Hz, 1H), 4.87 (br s, 3H), 4.30 (dd, J = 7.0, 6.3 Hz, 1H), 4.15 (dt, J = 10.8, 6.8 Hz, 1H), 4.10 (dt, J = 10.8, 6.8 Hz, 1H), 3.43 (dd, J = 14.9, 6.3 Hz, 1H), 3.36 (dd, J = 14.9, 7.0 Hz, 1H), 1.52 (quintet, J = 6.8 Hz, 2H), 1.40-1.15 (m, 10H), 0.90 (t, J = 7.0 Hz, 3H). 13C NMR (100 MHz, CD3OD) δ 170.61, 138.34, 128.30, 125.50, 122.97, 120.32, 118.87, 112.74, 107.69, 67.69, 54.76, 32.98, 30.29, 30.28, 29.40, 27.84, 26.80, 23.72, 14.46. IR (KBr) 3280, 2901, 1732, 1579, 1435 cm-1. MS m/z (rel intensity) 317 (MH+, 100), 317 (50), 289 (10), 188 (10), 130 (60). HRMS calcd for C19H29N2O2 (MH): 317.2229, Found, 317.2230. Anal Calcd for C19H29ClN2O2 (HCl salt): C, 64.67; H, 8.28; N, 7.94. Found: C, 64.45; H, 8.23; N, 8.03.
m.p.191-193℃. [α]D 20 = -60 (c 1.0, CH3OH). 1H NMR (400 MHz, CD3OD) δ 7.45 (d, J = 8.0 Hz, 2H), 7.39 (br s, 2H), 7.24 (d, J = 8.0 Hz, 2H), 7.00 (s, 2H), 6.98 (d, J = 8.0 Hz, 2H), 6.90 (t, J = 7.4 Hz, 2H), 5.57 (br d, J = 5.1 Hz, 2H), 4.65 (dd, J = 10.0, 4.8 Hz, 2H), 4.13 (d, J = 8.0 Hz, 2H), 4.02 (dd, J = 10.8, 6.5 Hz, 2H), 3.96 (dd, J = 10.8, 6.5 Hz, 2H), 3.27 (dd, J = 14.8, 4.8 Hz, 2H), 3.04 (dd, J = 14.8, 10.0 Hz, 2H), 2.20-2.10 (m, 2H), 1.90-1.80 (m, 2H), 1.46 (br t, J = 6.3 Hz, 4H), 1.28-1.10 (m, 20H), 0.79 (t, J = 6.8 Hz, 6H). 13C NMR (100 MHz, CD3OD) δ 174.21, 173.23, 152.66, 148.43, 138.07, 128.68, 124.48, 122.57, 120.02, 119.16, 112.48, 110.99, 109.17, 66.52, 63.21, 54.74, 32.98, 30.35, 30.32, 29.67, 28.25, 26.97, 23.71, 14.47. IR (KBr) 3308, 2855, 1735, 1657, 1601 cm-1. MS m/z (rel intensity) 833 (MH+, 100), 675 (10), 489 (40), 145 (70). HRMS calcd for C49H65N6O6 (MH): 833.4965, found, 833.4963.
白色固体 m.p. 74-76℃. [α]D 21 = -27.5 (c 1.00, CHCl3). 1H NMR (400 MHz, CDCl3) δ 4.85 (t, J = 9.7 Hz, 1H), 4.32 (d, J = 7.8 Hz, 1H), 3.89 (dt, J = 9.4, 7.0 Hz, 1H), 3.69 (t, J = 8.8 Hz, 2H), 3.53 (dt, J = 9.4, 7.0 Hz, 1H), 3.48-3.40 (m, 3H), 2.65 (br s, 1H), 2.62 (hept, J = 7.0, 1H), 1.63 (quint, 7.0 Hz, 2H), 1.40-1.20 (m, 10H), 1.191 (d, J = 7.0 Hz, 3H), 1.188 (d, J = 7.0 Hz, 3H), 0.88 (t, J = 6.9 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ 177.52, 102.59, 74.41, 74.23, 74.16, 70.60, 70.42, 61.46, 34.05, 31.83, 29.60, 29.41, 29.26, 25.93, 22.66, 19.00, 18.85, 14.10. IR (KBr) 3501, 2925, 2857, 1742, 1469 cm-1. MS m/z (rel intensity) 363 (M++H, 10), 233 (100), 215 (5). HRMS Calcd for C18H35O7: 363.2382, Found, 363.2383.
無色油状物 [α]D 21 = -1.8 (c 1.00, CHCl3). 1H NMR (400 MHz, CDCl3) δ 4.90 (t, J = 9.3 Hz, 1H), 4.37 (d, J = 7.8 Hz, 1H), 3.94-3.80 (m, 2H), 3.90 (dt, J = 9.4, 6.8 Hz, 1H), 3.67 (br t, J = 9.3 Hz, 1H), 3.56 (dt, J = 9.4, 6.8 Hz, 1H), 3.49 (br t, J = 8.7 Hz, 1H) 3.42 (ddd, J = 9.7, 4.6, 3.6 Hz) 3.12 (br s, 1H), 2.67 (hept, J = 7.0 Hz, 1H), 2.52 (br s, 1H), 1.81 (br s, 1H), 1.65-1.59 (m, 2H), 1.38-1.18 (m, 10H), 1.22 (d, J = 7.0 Hz, 3H), 1.21 (d, J = 7.0 Hz, 3H), 0.88 (t, J = 6.9 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ 178.96, 102.81, 78.03, 75.72, 72.20, 70.53, 69.79, 62.34, 34.15, 31.80, 29.61, 29.36, 29.22, 25.93, 22.64, 18.95, 18.92, 14.09. IR (neat) 3438, 2928, 2857, 1731, 1469 cm-1. MS m/z (rel intensity) 363 (M++H, 20), 233 (100), 215 (10), 185 (20), 145 (80). HRMS Calcd for C18H35O7: 363.2383, Found, 363.2387.
無色油状物 [α]D 22 = -10.0 (c 1.25, CHCl3). 1H NMR (400 MHz, CDCl3) δ 7.71-7.64 (m, 4H), 7.44-7.33 (m, 6H), 4.91 (t, J = 9.6 Hz, 1H), 4.30 (d, J = 7.8 Hz, 1H), 3.92 (dt, J = 9.4, 6.9 Hz, 1H), 3.75 (dd, J = 11.4, 5.4 Hz, 1H), 3.71 (dd, J = 11.4, 2.2 Hz, 1H), 3.65 (t, J = 9.2 Hz, 1H), 3.55 (dt, J = 9.4, 6.9 Hz, 1H), 3.52 (ddd, J = 9.6, 5.4, 2.2 Hz, 1H), 3.46 (dd, J = 9.2, 7.8 Hz, 1H), 2.78 (br s, 1H), 2.63 (br s, 1H), 2.49 (hept, J = 7.0 Hz, 1H), 1.71-1.63 (m, 2H), 1.40-1.20 (m, 10H), 1.12 (d, J = 7.0 Hz, 3H), 1.06 (d, J = 7.0 Hz, 3H), 1.04 (s, 9H), 0.88 (t, J = 6.9 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ 176.97, 135.68 (2), 135.58 (2), 133.32, 129.67, 129.66, 127.67 (3), 127.61 (2), 102.15, 75.13, 74.92, 74.58, 70.75, 69.96, 62.90, 33.98, 31.83, 29.67, 29.41, 29.26, 26.66 (3), 26.07, 22.66, 19.24, 18.85, 18.79, 14.11. IR (neat) 3410, 3050, 2929, 1742, 1470 cm-1. MS m/z (rel intensity) 601 (M++H, 1), 563 (1), 461 (1), 277 (10), 185 (100). HRMS Calcd for C34H53O7Si: 601.3560, Found, 601.3549.
無色油状物 [α]D 21 = -3.6 (c 1.12, CHCl3). 1H NMR (400 MHz, CDCl3) δ 7.71-7.64 (m, 4H), 7.40-7.33 (m, 6H), 5.00 (t, J = 9.6 Hz, 1H), 4.63 (dd, J = 9.6, 7.9 Hz, 1H), 4.42 (d, J = 8.0 Hz, 1H), 3.89 (dt, J = 9.4, 6.3 Hz, 1H), 3.78-3.69 (m, 3H), 3.50 (br s, 1H), 3.48 (dt, J = 9.4, 6.8 Hz, 1H), 2.50 (hept, J = 7.0 Hz, 1H), 1.65-1.58 (m, 2H), 1.50 (s, 9H), 1.40-1.20 (m, 10H), 1.12 (d, J = 7.0 Hz, 3H), 1.08 (d, J = 7.0 Hz, 3H), 1.03 (s, 9H), 0.88 (t, J = 6.8 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ 176.89, 153.07, 135.72 (2), 135.57 (2), 133.30, 133.18, 129.68, 129.66, 127.67 (2), 127.61 (2), 100.52, 82.84, 77.15, 74.63, 74.12, 70.90, 69.72, 62.62, 33.97, 31.84, 29.61, 29.41, 29.27, 27.70 (3), 26.64 (3), 25.98, 22.67, 19.22, 18.84, 18.82, 14.09. IR (neat) 3516, 3050, 2930, 1749, 1471 cm-1. MS m/z (rel intensity) 723 (M++Na, 10), 437 (50), 365 (90), 269 (80), 199 (90), 135 (100). HRMS Calcd for C39H60O9SiNa: 723.3905, Found, 723.3911. Anal Calcd for C39H60O9Si: C, 66.82; H, 8.63. Found: C, 66.78; H, 8.70.
無色油状物 [α]D 21 = 9.0 (c 1.64, CHCl3). 1H NMR (400 MHz, CDCl3) δ 7.70-7.64 (m, 4H), 7.43-7.33 (m, 6H), 5.05 (t, J = 9.7 Hz, 1H), 4.88 (t, J = 9.6 Hz, 1H), 4.35 (d, J = 7.8 Hz, 1H), 3.92 (dt, J = 9.4, 6.9 Hz, 1H), 3.73 (dd, J = 11.5, 5.7 Hz, 1H), 3.67 (dd, J = 11.5, 2.1 Hz, 1H), 3.59 (t, J = 9.2 Hz, 1H), 3.58-3.51 (m, 2H), 2.47 (br s, 1H), 2.41 (hept, J = 7.0 Hz, 1H), 1.75-1.60 (m, 2H), 1.46 (s, 9H), 1.40-1.20 (m, 10H), 1.06 (d, J = 7.0 Hz, 3H), 1.03 (s, 9H), 1.02 (d, J = 7.0 Hz, 3H), 0.88 (t, J = 6.9 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ 175.28, 153.34, 135.65 (2), 135.57 (2), 133.27, 129.66 (2), 127.66 (3), 127.61 (2), 102.44, 82.64, 77.66, 74.95, 72.43, 70.09, 68.30, 62.74, 33.84, 31.81, 29.60, 29.37, 29.25, 27.68 (3), 26.64 (3), 26.03, 22.65, 19.22, 18.83, 18.64, 14.09. IR (neat) 3504, 3050, 2930, 1750, 1471 cm-1. MS m/z (rel intensity) 720 (M++Na, 10), 437 (30), 365 (50), 269 (60), 199 (80), 135 (100). HRMS Calcd for C39H60O9SiNa: 723.3905, Found, 723.3911.
無色油状物 [α]D 23 = 13.1 (c 1.07, CHCl3). 1H NMR (400 MHz, CDCl3) δ 7.71-7.65 (m, 4H), 7.43-7.24 (m, 11H), 5.11 (t, J = 9.6 Hz, 1H), 4.75 (t, J = 8.8 Hz, 1H), 4.76 (d, J = 7.2 Hz, 1H), 4.74 (d, J = 7.2 Hz, 1H), 4.65 (d, J = 11.9 Hz, 1H), 4.46 (d, J = 11.9 Hz, 1H), 4.45 (d, J = 8.0 Hz, 1H), 3.92 (dt, J = 9.4, 6.3 Hz, 1H), 3.90 (t, J = 9.3 Hz, 1H), 3.71 (dd, J = 11.5, 5.9 Hz, 1H), 3.63 (dd, J = 11.5, 2.1 Hz, 1H), 3.51-3.43 (m, 2H), 2.38 (hept, J = 7.0 Hz, 1H), 1.70-1.55 (m, 2H), 1.43 (s, 9H), 1.40-1.20 (m, 10H), 1.04 (s, 9H), 1.03 (d, J = 7.0 Hz, 3H), 1.00 (d, J = 7.0 Hz, 3H), 0.88 (t, J = 6.9 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ .23, 152.46, 137.61, 135.68 (2), 135.60 (2), 133.29, 133.28, 129.62 (2), 128.35 (2), 127.96 (2), 127.67, 127.64 (2), 127.59 (2), 100.94, 94.90, 82.44, 78.04, 75.77, 74.99, 70.17, 69.67, 69.53, 62.64, 33.90, 31.85, 29.61, 29.42, 29.26, 27.64 (3), 26.64 (3), 25.98, 22.66, 19.19, 18.98, 18.59, 14.09. IR (neat) 3050, 2930, 2857, 1756, 1470, 1369 cm-1. MS m/z (rel intensity) 820 (M+, 1), 763 (5), 677 (20), 437 (30), 269 (80), 199 (100). HRMS Calcd for C47H68O10Si: 820.4582, Found, 820.4597. Anal Calcd for C47H68O10Si: C, 68.75; H, 8.35. Found: C, 68.78; H, 8.36.
無色油状物 [α]D 21 = -37.7 (c 1.09, CHCl3). 1H NMR (400 MHz, CDCl3) δ 7.38-7.28 (m, 5H), 4.98 (d, J = 7.3 Hz, 1H), 4.77 (d, J = 7.3 Hz, 1H), 4.76 (d, J = 11.6 Hz, 1H), 4.65 (t, J = 8.5 Hz, 1H), 4.61 (d, J = 11.6 Hz, 1H), 4.40 (dd, J = 11.9, 1.8 Hz, 1H), 4.38 (d, J = 8.0 Hz, 1H), 4.34-4.28 (m, 1H), 4.18 (br s, 1H), 3.86 (dt, J = 9.4, 6.3 Hz, 1H), 3.56-3.49 (m, 1H), 3.48-3.40 (m, 3H), 2.60 (hept, J = 7.0 Hz, 1H), 1.70-1.50 (m, 2H), 1.48 (s, 9H), 1.40-1.20 (m, 10H), 1.18 (d, J = 7.0 Hz, 3H), 1.17 (d, J = 7.0 Hz, 3H), 0.87 (t, J = 6.8 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ 177.26, 152.56, 136.64, 128.61 (2), 128.16, 128.07 (2), 101.03, 96.20, 84.81, 82.57, 74.92, 73.77, 70.47, 70.01, 69.83, 63.20, 33.96, 31.84, 29.56, 29.39, 29.24, 27.71 (3), 25.87, 22.66, 19.04, 18.93, 14.09. IR (neat) 3481, 2929, 2857, 1753, 1457 cm-1. MS m/z (rel intensity) 582 (M+, 1), 419 (10), 289 (10), 150 (10), 91 (100). HRMS Calcd for C31H50O10: 582.3404, Found, 582.3422. Anal Calcd for C31H50O10: C, 63.90; H, 8.65. Found: C, 63.63; H, 8.48.
無色油状物 [α]D 22 = -22.8 (c 1.06, CHCl3). 1H NMR (400 MHz, CDCl3) δ 7.73-7.69 (m, 4H), 7.44-7.26 (m, 11H), 4.99 (d, J = 7.1 Hz, 1H), 4.79 (d, J = 7.1 Hz, 1H), 4.76 (d, J = 11.7 Hz, 1H), 4.77 (dd, J = 9.4, 8.2 Hz, 1H), 4.60 (d, J = 11.7 Hz, 1H), 4.39 (d, J = 8.2 Hz, 1H), 4.03 (br d, J = 1.0 Hz, 1H), 3.97 (dd, J = 11.0, 3.3 Hz, 1H), 3.91 (dd, J = 11.0, 5.0 Hz, 1H), 3.87 (dt, J = 9.4, 6.4 Hz, 1H), 3.68 (t, J = 8.8 Hz, 1H), 3.56 (dd, J = 9.4, 8.7 Hz, 1H), 3.44 (dt, J = 9.4, 6.9 Hz, 1H), 3.37 (ddd, J = 8.8, 5.0, 3.3 Hz, 1H), 1.70-1.50 (m, 2H), 1.48 (s, 9H), 1.40-1.20 (m, 10H), 1.05 (s, 9H), 0.87 (t, J = 6.8 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ 152.71, 136.85, 135.72 (2), 135.63 (2), 133.44, 133.29, 129.66, 129.64, 128.54 (2), 128.10 (2), 128.03, 127.67 (2), 127.63 (2), 100.85, 96.06, 84.71, 82.41, 75.65, 75.14, 70.51, 70.30, 69.62, 63.85, 31.85, 29.61, 29.42, 29.26, 27.72 (3), 26.76 (3), 25.94, 22.66, 19.28, 14.09. IR (neat) 3431, 3049, 2929, 2857, 1754, 1460 cm-1. MS m/z (rel intensity) 773 (M++Na, 1), 565 (1), 367 (1), 221 (10), 199 (10), 135 (20), 91 (100). HRMS Calcd for C43H62O9SiNa: 773.4061, Found, 773.4059. Anal Calcd for C43H62O9Si: C, 68.77; H, 8.32. Found: C, 68.54; H, 8.32.
無色油状物 [α]D 20 = 11.3 (c 1.05, CHCl3). 1H NMR (400 MHz, CDCl3) δ 7.71-7.65 (m, 4H), 7.43-7.26 (m, 11H), 5.01 (dd, J = 9.9, 9.0 Hz, 1H), 4.91 (d, J = 7.0 Hz, 1H), 4.76 (d, J = 11.9 Hz, 1H), 4.72 (d, J = 7.0 Hz, 1H), 4.56 (d, J = 11.9 Hz, 1H), 4.35 (d, J = 7.3 Hz, 1H), 3.93 (dt, J = 9.4, 7.0 Hz, 1H), 3.73 (dd, J = 11.4, 6.3 Hz, 1H), 3.6405 (dd, J = 11.4, 1.9 Hz, 1H), 3.6402 (br s, 1H), 3.62-3.55 (m, 1H), 3.58 (dt, J = 9.4, 7.0 Hz, 1H), 3.54 (t, J = 9.0 Hz, 1H), 3.48 (ddd, J = 9.9, 6.3, 1.9 Hz, 1H), 2.40 (hept, J = 7.0 Hz, 1H), 1.69 (quint, J = 7.0 Hz, 2H), 1.40-1.10 (m, 10H), 1.042 (d, J = 7.0 Hz, 3H), 1.039 (s, 9H), 1.00 (d, J = 7.0 Hz, 3H), 0.87 (t, J = 7.0 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ 175.50, 136.90, 135.65 (2), 135.60 (2), 133.42, 133.29, 129.63 (2), 128.50 (2), 127.96 (3), 127.65 (2), 127.60 (2), 102.48, 95.82, 84.32, 75.03, 73.28, 70.18, 69.91, 69.07, 62.97, 33.91, 31.82, 29.68, 29.41, 29.26, 26.66 (3), 26.06, 22.65, 19.22, 18.85, 18.82, 14.10. IR (neat) 3461, 3070, 2929, 1744, 1470 cm-1. MS m/z (rel intensity) 720 (M+, 1), 663 (30), 437 (80), 269 (100), 199 (90). HRMS Calcd for C42H60O8Si: 720.4057, Found, 720.4036. Anal Calcd for C42H60O8Si: C, 69.96; H, 8.39. Found: C, 69.78; H, 8.49.
無色油状物 [α]D 23 = 31.0 (c 0.62, CHCl3). 1H NMR (400 MHz, CDCl3) δ 7.74-7.69 (m, 4H), 7.44-7.24 (m, 11H), 4.91 (d, J = 6.8 Hz, 1H), 4.86 (d, J = 6.8 Hz, 1H), 4.79 (t, J = 9.4,Hz, 1H), 4.74 (dd, J = 9.7, 8.0 Hz, 1H), 4.72 (d, J = 12.1 Hz, 1H), 4.56 (d, J = 12.1 Hz, 1H), 4.42 (d, J = 8.0 Hz, 1H), 3.97 (dd, J = 11.7, 1.9 Hz, 1H), 3.91-3.85 (m, 1H), 3.90 (t, J = 9.4 Hz, 1H), 3.87 (dd, J = 11.7, 4.4 Hz, 1H), 3.45 (ddd, J = 9.9, 4.4, 1.9 Hz, 1H), 3.42 (dt, J = 9.4, 6.8 Hz, 1H), 2.94 (s, 3H), 1.65-1.55 (m, 2H), 1.43 (s, 9H), 1.40-1.20 (m, 10H), 1.07 (s, 9H), 0.88 (t, J = 6.8 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ 152.32, 137.54, 135.94 (2), 135.62 (2), 133.38, 132.93, 129.70 (2), 128.40 (2), 127.89 (2), 127.73, 127.69 (2), 127.58 (2), 100.88, 95.79, 82.70, 78.32, 77.25, 75.66, 74.34, 70.15, 69.81, 62.14, 38.76, 31.85, 29.55, 29.42, 29.24, 27.62 (3), 26.73 (3), 25.94, 22.65, 19.26, 14.09. IR (neat) 3070, 2930, 2857, 1755, 1459, 1368 cm-1. MS m/z (rel intensity) 851 (M++Na, 1), 445 (1), 347 (1), 257 (20), 199 (10), 91 (100). HRMS Calcd for C44H64O11SiSNa: 851.3836, Found, 851.3832. Anal Calcd for C44H64O11SiS: C, 63.74; H, 7.78. Found: C, 63.79; H, 7.81.
無色油状物 [α]D 19 = -35.8 (c 1.59, CHCl3). 1H NMR (400 MHz, CDCl3) δ 4.87 (t, J = 9.7 Hz, 1H), 4.37 (d, J = 9.7 Hz, 1H), 3.71 (t, J = 9.2 Hz, 2H), 3.60-3.54 (m, 1H), 3.50-3.15 (m, 2H), 3.16 (br s, 1H), 2.99 (br s, 1H), 2.71 (t, J = 7.5 Hz, 2H), 2.62 (hept, J = 7.0 Hz, 1H), 2.47 (br s, 1H), 1.68-1.59 (m, 2H), 1.45-1.20 (m, 10H), 1.20 (d, J = 7.0 Hz, 3H), 1.19 (d, J = 7.0 Hz, 3H), 0.88 (t, J = 6.9 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ 177.51, 86.01, 78.35, 75.99, 73.06, 70.36, 61.67, 34.05, 31.79, 30.41, 30.13, 29.17 (2), 28.88, 22.65, 18.97, 18.85, 14.09. IR (neat) 3438, 2926, 2855, 1739, 1469 cm-1. MS m/z (rel intensity) 378 (M+, 1), 360 (5), 215 (70), 145 (30), 71 (100). HRMS Calcd for C18H34O6S: 378.2077, Found, 378.2090.
白色固体 m.p.39-40℃. [α]D 20 = -22.1 (c 0.61, CHCl3). 1H NMR (400 MHz, CDCl3) δ 4.92 (t, J = 9.2 Hz, 1H), 4.42 (d, J = 9.7 Hz, 1H), 3.93 (ddd, J = 11.9, 5.8, 3.6 Hz, 1H), 3.81 (ddd, J = 11.9, 7.3, 4.8 Hz, 1H), 3.68 (ddd, J = 9.7, 9.4, 5.1 Hz, 1H), 3.51 (dd, J = 9.4, 2.7 Hz, 1H), 3.45 (ddd, J = 9.7, 4.8, 3.6 Hz, 1H), 2.96 (d, J = 5.1 Hz, 1H), 2.71 (t, J = 7.3 Hz, 2H), 2.67 (hept, J = 7.0 Hz, 1H), 2.57 (d, J = 2.7 Hz, 1H), 2.15 (t, J = 6.7 Hz, 1H), 1.68-1.59 (m, 2H), 1.45-1.20 (m, 10H), 1.224 (d, J = 7.0 Hz, 3H), 1.221 (d, J = 7.0 Hz, 3H), 0.88 (t, J = 6.9 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ 178.98, 86.74, 79.90, 79.31, 71.01, 69.66, 62.46, 34.18, 31.78, 30.77, 30.14, 29.15, 29.13, 28.81, 22.64, 18.94 (2), 14.09. IR (neat) 3321, 2926, 2854, 1731, 1463 cm-1. MS m/z (rel intensity) 379 (M++H, 5), 233 (40), 215 (10), 145 (100), 97 (30). HRMS Calcd for C18H35O6S: 379.2154, Found, 379.2148. Anal Calcd for C18H34O6S: C, 57.11; H, 9.05. Found: C, 56.91; H, 8.86.
無色油状物 [α]D 19 = -6.4 (c 1.08, CHCl3). 1H NMR (400 MHz, CDCl3) δ 7.72-7.65 (m, 4H), 7.44-7.34 (m, 6H), 4.99 (t, J = 9.7 Hz, 1H), 4.35 (d, J = 9.7 Hz, 1H), 3.73 (d, J = 3.6 Hz, 2H), 3.66 (t, J = 9.1 Hz, 1H), 3.54 (dt, J = 9.9, 3.6 Hz, 1H), 3.49 (t, J = 9.2 Hz, 1H), 2.87 (br s, 1H), 2.76 (dt, J = 12.1, 7.3 Hz, 1H), 2.71 (dt, J = 12.1, 7.4 Hz, 1H), 2.64 (br s, 1H), 2.50 (hept, J = 7.0 Hz, 1H), 1.70-1.60 (m, 2H), 1.40-1.20 (m, 10H), 1.12 (d, J = 7.0 Hz, 3H), 1.06 (d, J = 7.0 Hz, 3H), 1.04 (s, 9H), 0.87 (t, J = 6.9 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ 177.07, 135.70 (2), 135.60 (2), 133.23, 133.18, 129.70, 129.66, 127.67 (2), 127.63 (2), 85.23, 78.88, 76.74, 73.27, 70.40, 62.84, 33.99, 31.78, 30.12, 29.64, 29.18, 29.12, 28.98, 26.67 (3), 22.64, 19.22, 18.83, 18.81, 14.09. IR (neat) 3357, 3050, 2928, 1741, 1470 cm-1. MS m/z (rel intensity) 720 (M++Na, 30), 471 (10), 365 (20), 199 (50), 135 (100). HRMS Calcd for C34H52O6SiSNa: 639.3152, Found, 639.3160. Anal Calcd for C34H52O6SiS: C, 66.19; H, 8.50. Found: C, 66.20; H, 8.34.
無色油状物 [α]D 25 = -26.6 (c 1.04, CHCl3). 1H NMR (400 MHz, CDCl3) δ 4.93 (t, J = 9.2 Hz, 1H), 4.36 (d, J = 9.7 Hz, 1H), 3.93 (d, J = 4.6 Hz, 2H), 3.74 (td, J = 9.4, 3.6 Hz, 1H), 3.48 (dd, J = 9.2, 2.7 Hz, 1H), 3.46 (dt, J = 9.4, 4.6 Hz, 1H), 2.94 (d, J = 3.6 Hz. 1H), 2.75-2.62 (m, 1H), 2.71 (dt, J = 12.0, 7.0 Hz, 1H), 2.70 (dt, J = 12.0, 7.2 Hz, 1H), 2.52 (d, J = 2.7 Hz, 1H), 1.66-1.57 (m, 2H), 1.40-1.20 (m, 10H), 1.23 (d, J = 7.0 Hz, 3H), 1.22 (d, J = 7.0 Hz, 3H), 1.05 (s, 9H), 0.87 (t, J = 6.9 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ 178.57, 135.67 (2), 135.60 (2), 132.94, 132.85, 129.86 (2), 127.79 (2), 127.77 (2), 86.09, 79.39, 79.00, 70.97, 70.60, 64.51, 34.16, 31.78, 30.03, 29.95, 29.15, 29.10, 28.88, 26.81 (3), 22.63, 19.22, 19.02, 18.93, 14.09. IR (neat) 3447, 3050, 2929, 1720, 1470 cm-1. MS m/z (rel intensity) 720 (M++H, 5), 471 (10), 365 (20), 185 (90), 135 (40), 93 (100). HRMS Calcd for C34H53O6SiS: 617.3333, Found, 617.3322. Anal Calcd for C34H52O6SiS: C, 66.19; H, 8.50. Found: C, 66.19; H, 8.54.
無色油状物 [α]D 24 = 6.6 (c 1.00, CHCl3). 1H NMR (400 MHz, CDCl3) δ 7.72-7.64 (m, 4H), 7.44-7.33 (m, 6H), 5.06 (t, J = 9.7 Hz, 1H), 4.69 (t, J = 9.4 Hz, 1H), 4.43 (d, J = 9.9 Hz, 1H), 3.79-3.69 (m, 3H), 3.51 (ddd, J = 9.7, 4.4, 2.2 Hz, 1H), 2.75 (dt, J = 12.1, 7.8 Hz, 1H), 2.71 (dt, J = 12.1, 7.8 Hz, 1H), 2.66 (d, J = 6.1 Hz, 1H), 2.50 (hept, J = 7.0 Hz, 1H), 1.68-1.55 (m, 2H), 1.52 (s, 9H), 1.40-1.20 (m, 10H), 1.12 (d, J = 7.0 Hz, 3H), 1.07 (d, J = 7.0 Hz, 3H), 1.04 (s, 9H), 0.87 (t, J = 6.9 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ 177.02, 152.87, 135.70 (2), 135.58 (2), 133.20, 133.05, 129.70, 129.67, 127.68 (2), 127.64 (2), 83.09, 82.82, 78.71, 75.59, 75.37, 70.59, 62.58, 33.97, 31.79, 29.57, 29.35, 29.18, 29.14, 28.97, 27.72 (3), 26.65 (3), 22.65, 19.21, 18.82 (2), 14.09. IR (neat) 3497, 3050, 2929, 1751, 1470 cm-1. MS m/z (rel intensity) 717 (M++H, 20), 661 (50), 515 (100), 461 (40), 369 (80). HRMS Calcd for C39H61O8SiS: 717.3857, Found, 717.3871. Anal Calcd for C39H60O8SiS: C, 65.33; H, 8.43. Found: C, 65.56; H, 8.40.
無色油状物 [α]D 24 = 0.6 (c 0.62, CHCl3). 1H NMR (400 MHz, CDCl3) δ 7.71-7.64 (m, 4H), 7.43-7.25 (m, 6H), 5.13 (t, J = 9.7 Hz, 1H), 4.88 (t, J = 9.3 Hz, 1H), 4.40 (d, J = 9.7 Hz, 1H), 3.69 (d, J = 3.6 Hz, 2H), 3.62 (td, J = 9.4, 2.2 Hz, 1H), 3.56 (dt, J = 9.9, 3.6 Hz, 1H), 2.75 (dt, J = 12.8, 7.9 Hz, 1H), 2.70 (dt, J = 12.8, 7.6 Hz, 1H), 2.55 (d, J = 2.2 Hz), 2.42 (hept, J = 6.9 Hz, 1H), 1.70-1.61 (m, 2H), 1.46 (s, 9H), 1.40-1.20 (m, 10H), 1.07 (d, J = 6.9 Hz, 3H), 1.032 (d, J = 6.9 Hz, 3H), 1.030 (s, 9H), 0.87 (t, J = 6.9 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ175.19, 153.36, 135.67 (2), 135.60 (2), 133.18, 133.15, 129.67, 129.65, 127.66 (2), 127.63 (2), 85.72, 82.73, 79.08, 79.03, 71.12, 67.87, 62.67, 33.85, 31.77, 30.12, 29.58, 29.17, 29.08, 28.93, 27.68 (3), 26.64 (3), 22.63, 19.19, 18.87, 18.64, 14.09. IR (neat) 3490, 3050, 2929, 1747, 1471 cm-1. MS m/z (rel intensity) 717 (M++H, 10), 661 (30), 515 (100), 437 (70), 365 (30). HRMS Calcd for C39H61O8SiS: 717.3857, Found, 717.3844. Anal Calcd for C39H60O8SiS: C, 65.33; H, 8.43. Found: C, 65.03; H, 8.43.
無色油状物 [α]D 23 = 11.9 (c 1.18, CHCl3). 1H NMR (400 MHz, CDCl3) δ 7.72-7.65 (m, 4H), 7.43-7.25 (m, 11H), 5.16 (t, J = 9.6 Hz, 1H), 4.79 (t, J = 9.7 Hz, 1H), 4.76 (s, 2H), 4.64 (d, J = 11.9 Hz, 1H), 4.47 (d, J = 11.9 Hz, 1H), 4.46 (d, J = 9.9 Hz, 1H), 3.91 (t, J = 9.2 Hz, 1H), 3.69 (dd, J = 11.6, 4.8 Hz, 1H), 3.65 (dd, J = 11.6, 2.7 Hz, 1H), 3.48 (ddd, J = 9.9, 4.8, 2.7 Hz, 1H), 2.76 (dt, J = 12.1, 7.4 Hz, 1H), 2.73 (dt, J = 12.1, 7.5 Hz, 1H), 2.37 (hept, J = 7.0 Hz, 1H), 1.66-1.57 (m, 2H), 1.44 (s, 9H), 1.40-1.15 (m, 10H), 1.04 (s, 9H), 1.02 (d, J = 7.0 Hz, 3H), 0.98 (d, J = 7.0 Hz, 3H), 0.87 (t, J = 6.9 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ 175.17, 152.45, 137.58, 135.69 (2), 135.64 (3), 133.18, 129.66, 129.63, 128.44 (2), 127.95 (2), 127.69, 127.65 (2), 127.63 (2), 95.04, 83.27, 82.82, 79.45, 79.17, 74.30, 69.80, 69.59, 62.62, 33.89, 31.79, 29.46, 29.35, 29.19, 29.14, 28.95, 27.67 (3), 26.65 (3), 22.65, 19.18, 18.97, 18.59, 14.10. IR (neat) 3049, 2929, 2856, 1752, 1471, 1369 cm-1. MS m/z (rel intensity) 837 (M++H, 1), 737 (1), 515 (10), 437 (20), 369 (30), 277 (100). HRMS Calcd for C47H69O9SiS: 837.4432, Found, 837.4431. Anal Calcd for C47H68O9SiS: C, 67.43; H, 8.19. Found: C, 67.49; H, 8.16.
無色油状物 [α]D 23 = -38.0 (c 1.04, CHCl3). 1H NMR (400 MHz, CDCl3) δ 7.38-7.29 (m, 5H), 4.98 (d, J = 7.0 Hz, 1H), 4.78 (d, J = 7.0 Hz, 1H), 4.77 (d, J = 11.9 Hz, 1H), 4.68 (dd, J = 10.2, 9.0 Hz, 1H), 4.61 (d, J = 11.9 Hz, 1H), 4.41 (dd, J = 12.1, 1.2 Hz, 1H), 4.40 (d, J = 10.2 Hz, 1H), 4.31-4.16 (m, 1H), 4.17 (br s, 1H), 3.57-3.43 (m, 3H), 2.69 (dt, J = 12.4, 7.5 Hz, 1H), 2.65 (dt, J = 12.4, 7.5 Hz, 1H), 2.59 (hept, J = 7.0 Hz, 1H), 1.65-1.55 (m, 2H), 1.49 (s, 9H), 1.40-1.20 (m, 10H), 1.18 (d, J = 7.0 Hz, 3H), 1.17 (d, J = 7.0 Hz, 3H), 0.88 (t, J = 6.9 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ 177.17, 152.55, 136.60, 128.62 (2), 128.18, 128.06 (2), 96.20, 85.90, 83.64, 82.92, 77.94, 73.42, 70.49, 69.66, 63.38, 33.95, 31.81, 29.96, 29.61, 29.20, 29.13, 28.86, 27.72 (3), 22.65, 19.01, 18.96, 14.09. IR (neat) 3469, 2927, 2856, 1749, 1469, 1370 cm-1. MS m/z (rel intensity) 599 (M++H, 1), 367 (90), 277 (50), 237 (70), 159 (100). HRMS Calcd for C31H51O9S: 599.3254, Found, 599.3246. Anal Calcd for C31H50O9S: C, 62.18; H, 8.42. Found: C, 61.94; H, 8.43.
無色油状物 [α]D 23 = -26.4 (c 1.01, CHCl3). 1H NMR (400 MHz, CDCl3) δ 7.73-7.70 (m, 4H), 7.44-7.26 (m, 11H), 5.00 (d, J = 7.0 Hz, 1H), 4.81 (d, J = 7.0 Hz, 1H), 4.76 (d, J = 11.9 Hz, 1H), 4.73 (t, J = 9.6 Hz, 1H), 4.61 (d, J = 11.9 Hz, 1H), 4.40 (d, J = 9.9 Hz, 1H), 3.98 (br s, 1H), 3.96 (dd, J = 10.9, 3.4 Hz, 1H), 3.92 (dd, J = 10.9, 4.6 Hz, 1H), 3.74 (t, J = 9.1 Hz, 1H), 3.59 (t, J = 8.8 Hz, 1H), 3.38 (ddd, J = 9.4, 4.6, 3.4 Hz, 1H), 2.73 (dt, J = 11.9, 7.5 Hz, 1H), 2.69 (dt, J = 11.9, 7.5 Hz, 1H), 1.66-1.53 (m, 2H), 1.49 (s, 9H), 1.40-1.18 (m, 10H), 1.05 (s, 9H), 0.86 (t, J = 6.9 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ 152.69, 136.84, 135.69 (2), 135.62 (2), 133.33, 133.18, 129.67 (2), 128.54 (2), 128.10 (2), 128.04, 127.69 (2), 127.67 (2), 96.06, 85.64, 83.08, 82.73, 79.79, 73.54, 70.32, 70.23, 63.76, 31.78, 29.51, 29.27, 29.14, 29.13, 28.92, 27.72 (3), 26.76 (3), 22.64, 19.27, 14.09. IR (neat) 3434, 3069, 2928, 1750, 1456 cm-1. MS m/z (rel intensity) 767 (M++H, 1), 645 (5), 553 (10), 461 (10), 369 (30), 277 (100). HRMS Calcd for C43H63O8SiS: 767.4013, Found, 767.4026. Anal Calcd for C43H62O8SiS: C, 67.33; H, 8.15. Found: C, 67.31; H, 8.13.
無色油状物 [α]D 23 = 2.1 (c 0.73, CHCl3). 1H NMR (400 MHz, CDCl3) δ 7.71-7.63 (m, 4H), 7.43-7.26 (m, 11H), 5.06 (t, J = 9.4 Hz, 1H), 4.93 (d, J = 7.0 Hz, 1H), 4.77 (d, J = 12.0 Hz, 1H), 4.73 (d, J = 7.0 Hz, 1H), 4.57 (d, J = 12.0 Hz, 1H), 4.41 (d, J = 9.2 Hz, 1H), 3.88 (br s, 1H), 3.71 (dd, J = 11.6, 5.8 Hz, 1H), 3.64 (dd, J = 11.6, 2.0 Hz, 1H), 3.57 (t, J = 8.5 Hz, 1H), 3.55 (t, J = 7.3 Hz, 1H), 3.49 (ddd, J = 10.2, 5.8, 2.0 Hz, 1H), 2.78 (dt, J = 12.6, 7.6 Hz, 1H), 2.73 (dt, J = 12.6, 7.6 Hz, 1H), 2.39 (hept, J = 7.0 Hz, 1H), 1.71-1.63 (m, 2H), 1.45-1.15 (m, 10H), 1.05 (d, J = 7.0 Hz, 3H), 1.04 (s, 9H), 1.00 (d, J = 7.0 Hz, 3H), 0.87 (t, J = 6.9 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ 175.41, 136.76, 135.67 (2), 135.62 (2), 133.28, 133.21, 129.65, 129.63, 128.55 (2), 128.04, 128.00 (2), 127.65 (2), 127.62 (2), 95.97, 85.93, 85.14, 79.16, 72.26, 70.35, 68.70, 62.98, 33.90, 31.79, 29.96, 29.75, 29.19, 29.15, 29.03, 26.66 (3), 22.64, 19.19, 18.85, 18.82, 14.09. IR (neat) 3431, 2928, 2856, 1744, 1459 cm-1. MS m/z (rel intensity) 737 (M++H, 5), 629 (20), 365 (70), 269 (100), 249 (90). HRMS Calcd for C42H61O7SiS: 737.3908, Found, 737.3903.
Claims (5)
- 一般式[4]
(式中、R1は炭素数1〜20のアルキル基又は炭素数7〜10のアラルキル基を表し、R2は置換基を有していてもよいアシル基を表し、Xは酸素原子又は硫黄原子を表す。)で示される化合物とTBDPSX1(式中、TBDPSはtert−ブチルジフェニルシリル基を表し、X1はハロゲン原子を表す。)とを反応させることにより、一般式[5]
(式中、R1、R2、X及びTBDPSは前記に同じ。)で示される化合物を形成し、次いで、これと二炭酸ジ−tert−ブチルを、一般式[2]
(式中、R3及びR5は、夫々独立して水素原子又は炭素数1〜10のアルコキシカルボニル基であり、R4及びR6は、夫々独立して水素原子又は炭素原子6〜10の芳香族炭化水素基或いは炭素数6〜10の芳香族複素環基で置換されていてもよい炭素数1〜6のアルキル基であり、R3とR4とが同時に水素原子になることはなく、R5とR6が同時に水素原子になることはなく、また、R3とR5が同じであり且つR4とR6が同じである場合、ピロリジン環の2位の立体配置と5位の立体配置は共にS配置或いはR配置である。)で示される触媒の存在下で反応させることを特徴とする、一般式[6]
(式中、BOCはtert−ブトキシカルボニル基を表し、R1、R2、X及びTBDPSは前記に同じ。)で示される化合物の製造方法。 - 一般式[4]
(式中、R1は炭素数1〜20のアルキル基又は炭素数7〜10のアラルキル基を表し、R2は置換基を有していてもよいアシル基を表し、Xは酸素原子又は硫黄原子を表す。)で示される化合物とTBDPSX1(式中、TBDPSはtert−ブチルジフェニルシリル基を表し、X1はハロゲン原子を表す。)とを反応させることにより、一般式[5]
(式中、R1、R2、X及びTBDPSは前記に同じ。)で示される化合物を形成し、次いで、これと二炭酸ジ−tert−ブチルを、一般式[2]
(式中、R3及びR5は、夫々独立して水素原子又は炭素数1〜10のアルコキシカルボニル基であり、R4及びR6は、夫々独立して水素原子又は炭素原子6〜10の芳香族炭化水素基或いは炭素数6〜10の芳香族複素環基で置換されていてもよい炭素数1〜6のアルキル基であり、R3とR4とが同時に水素原子になることはなく、R5とR6が同時に水素原子になることはなく、また、R3とR5が同じであり且つR4とR6が同じである場合、ピロリジン環の2位の立体配置と5位の立体配置は共にS配置或いはR配置である。)で示される触媒の存在下で反応させることにより一般式[6]
(式中、BOCはtert−ブトキシカルボニル基を表し、R1、R2、X及びTBDPSは前記に同じ。)で示される化合物を形成し、更に、これとBOMX1(式中、BOMはベンジルオキシメチル基を表し、X1は前記に同じ。)を反応させることを特徴とする、一般式[7]
(式中、R1、R2、X、TBDPS、BOC及びBOMは前記に同じ。)で示される化合物の製造方法。 - 一般式[2]に於けるR3及びR5が共にn−オクチル基であり、R4及びR6が共にインドリルメチル基である、請求項2に記載の製造法。
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