HCID 86602902, compound → HCID 86602904, compound

HRID 2252502Notes

Reaction equation

HRID 2252502 reaction equation
[Si:1]([O:8][C@@H:9]([C@@H:35]([CH3:82])/[CH:36]=[CH:37]\[C@@H:38]([O:74][Si:75]([C:78]([CH3:81])([CH3:80])[CH3:79])([CH3:77])[CH3:76])[CH2:39][C@H:40]([O:66][Si:67]([C:70]([CH3:73])([CH3:72])[CH3:71])([CH3:69])[CH3:68])[C@H:41]([CH3:65])/[CH:42]=[CH:43]/[CH2:44][O:45][C:46]([C:59]1[CH:64]=[CH:63][CH:62]=[CH:61][CH:60]=1)([C:53]1[CH:58]=[CH:57][CH:56]=[CH:55][CH:54]=1)[C:47]1[CH:52]=[CH:51][CH:50]=[CH:49][CH:48]=1)[C@@H:10]([CH3:34])[CH2:11][CH2:12][CH2:13][CH2:14][C:15](=[O:33])[C@@H:16]([C@@H:18]1[C@@H:23]([CH3:24])[CH2:22][O:21][CH:20]([C:25]2[CH:30]=[CH:29][C:28]([O:31][CH3:32])=[CH:27][CH:26]=2)[O:19]1)[CH3:17])([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2]>C1COCC1>[Si:1]([O:8][C@@H:9]([C@@H:35]([CH3:82])/[CH:36]=[CH:37]\[C@@H:38]([O:74][Si:75]([C:78]([CH3:81])([CH3:80])[CH3:79])([CH3:77])[CH3:76])[CH2:39][C@H:40]([O:66][Si:67]([C:70]([CH3:73])([CH3:72])[CH3:71])([CH3:68])[CH3:69])[C@H:41]([CH3:65])/[CH:42]=[CH:43]/[CH2:44][O:45][C:46]([C:47]1[CH:52]=[CH:51][CH:50]=[CH:49][CH:48]=1)([C:59]1[CH:64]=[CH:63][CH:62]=[CH:61][CH:60]=1)[C:53]1[CH:54]=[CH:55][CH:56]=[CH:57][CH:58]=1)[C@@H:10]([CH3:34])[CH2:11][CH2:12][CH2:13][CH2:14][C@@H:15]([OH:33])[C@@H:16]([C@@H:18]1[C@@H:23]([CH3:24])[CH2:22][O:21][CH:20]([C:25]2[CH:30]=[CH:29][C:28]([O:31][CH3:32])=[CH:27][CH:26]=2)[O:19]1)[CH3:17])([C:4]([CH3:5])([CH3:6])[CH3:7])([CH3:2])[CH3:3]

Participants

3

Reactant 1

HCID 86602902HCID 86602902, compound

Product 1

HCID 86602904HCID 86602904, compoundYield 95%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

LiAl(O-t-Bu)3H (2.0 mL, 1.0 M solution in THF) was added to a solution of 70 (0.80 g, 0.68 mmol) in THF (7 mL). After 30 min of stirring at room temperature, the reaction was quenched with saturated aqueous NH4Cl (1 mL), stirring for 1 h, dried over MgSO4, filtered, concentrated in vacuo, and chromatographed (EtOAc/hexane 3:17) to provide the β isomer of 71 (0.76 g, 95%) as a colorless oil: IR (CHCl3) 3538, 2929, 2855, 1615, 1518, 1461, 1385, 1251, 1072, 835, 773, 734 cm−1; 1H NMR (300 MHz, CDCl3) δ 7.70-7.66 (m, 6H), 7.59-7.56 (m, 2H), 7.52-7.39 (m, 9H), 7.08-7.05 (m, 2H), 5.93-5.77 (m, 2H), 5.71 (s, 1H), 5.67 (t, J=10.2 Hz, 1H), 5.55-5.48 (m, 1H), 4.78 (m, 1H), 4.30 (dd, J=11.4, 4.8 Hz, 1H), 4.15 (m, 1H), 4.09 (m, 1H), 3.94 (s, 3H), 3.88 (dd, J=10.0, 1.5 Hz, 1H), 3.79 (d, J=3.9 Hz, 2H), 3.70 (t, J=11.1 Hz, 1H), 3.64 (m, 1H), 3.38 (br, 1H), 2.84 (m, 1H), 2.65 (m, 1H), 2.33 (m, 1H), 2.22-1.91 (m, 2H), 1.86-1.71 (m, 3H), 1.66-1.54 (m, 4H), 1.49-1.34 (m, 3H), 1.24 (d, J=7.0 Hz, 3H), 1.21 (d, J=6.6 Hz, 3H), 1.15-1.08 (m, 21H), 1.09 (d, J=6.9 Hz, 3H), 1.04 (m, 9H), 0.94 (d, J=6.7 Hz, 3H), 0.34-0.25 (m, 18H); 13C NMR (75 MHz, CDCl3) δ 160.0, 144.4, 144.3, 134.3, 132.8, 132.2, 130.6, 128.6, 127.6, 127.1, 126.7, 113.6, 101.1, 88.9, 86.7, 80.1, 76.2, 73.0, 72.2, 66.4, 65.0, 55.1, 42.3, 41.6, 38.2, 37.4, 35.7, 35.0, 33.6, 30.3, 28.0, 26.5, 26.1, 25.91, 25.87, 19.5, 18.4, 18.05, 17.99, 15.0, 13.2, 11.8, 5.6, −3.0, −3.7, −3.8, −4.2, −4.3; LRMS (ESI) 1199.7 [M+Na]+, 937.6, 782.4, 413.2; HRMS (ESI) calcd for C71H112O8Si3Na 1199.7563 [M+Na]+, found 1199.7538; [α]20D+8.9 (c 0.46, CHCl3).

Workup

  1. customthe reaction was quenched with saturated aqueous NH4Cl (1 mL)
  2. stirringstirring for 1 h
  3. dry with materialdried over MgSO4
  4. filtrationfiltered
  5. concentrationconcentrated in vacuo
  6. customchromatographed (EtOAc/hexane 3:17)

Sources & evidence

ORD record
ord-9803af5dac6040c483362ca5f1a41f55
Source dataset
uspto-grants-2008_01
Patent number
US07321046B2

Reaction notes

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