Diisobutylaluminum hydride → HCID 86602891, compound

HRID 2252488Notes

Reaction equation

HRID 2252488 reaction equation
CC(C[AlH]CC(C)C)C.[Si:10]([O:17][C@H:18]([CH2:36][CH2:37][C@H:38]([CH3:99])[CH2:39][C@H:40]([CH3:98])[C@@H:41]([O:90][Si:91]([C:94]([CH3:97])([CH3:96])[CH3:95])([CH3:93])[CH3:92])[C@@H:42]([CH3:89])/[CH:43]=[CH:44]\[C@@H:45]([O:81][Si:82]([C:85]([CH3:88])([CH3:87])[CH3:86])([CH3:84])[CH3:83])[CH2:46][C@H:47]([O:73][Si:74]([C:77]([CH3:80])([CH3:79])[CH3:78])([CH3:76])[CH3:75])[C@H:48]([CH3:72])/[CH:49]=[CH:50]/[CH2:51][O:52][C:53]([C:66]1[CH:71]=[CH:70][CH:69]=[CH:68][CH:67]=1)([C:60]1[CH:65]=[CH:64][CH:63]=[CH:62][CH:61]=1)[C:54]1[CH:59]=[CH:58][CH:57]=[CH:56][CH:55]=1)[C@@H:19]([C@@H:21]1[C@@H:26]([CH3:27])[CH2:25][O:24][CH:23]([C:28]2[CH:33]=[CH:32][C:31]([O:34][CH3:35])=[CH:30][CH:29]=2)[O:22]1)[CH3:20])([C:13]([CH3:16])([CH3:15])[CH3:14])([CH3:12])[CH3:11]>C(Cl)Cl>[CH3:35][O:34][C:31]1[CH:30]=[CH:29][C:28]([CH2:23][O:22][C@H:21]([C@@H:19]([CH3:20])[C@H:18]([O:17][Si:10]([C:13]([CH3:14])([CH3:15])[CH3:16])([CH3:11])[CH3:12])[CH2:36][CH2:37][C@H:38]([CH3:99])[CH2:39][C@H:40]([CH3:98])[C@@H:41]([O:90][Si:91]([C:94]([CH3:97])([CH3:96])[CH3:95])([CH3:93])[CH3:92])[C@@H:42]([CH3:89])/[CH:43]=[CH:44]\[C@@H:45]([O:81][Si:82]([C:85]([CH3:86])([CH3:87])[CH3:88])([CH3:84])[CH3:83])[CH2:46][C@H:47]([O:73][Si:74]([C:77]([CH3:80])([CH3:79])[CH3:78])([CH3:76])[CH3:75])[C@H:48]([CH3:72])/[CH:49]=[CH:50]/[CH2:51][O:52][C:53]([C:54]2[CH:59]=[CH:58][CH:57]=[CH:56][CH:55]=2)([C:60]2[CH:61]=[CH:62][CH:63]=[CH:64][CH:65]=2)[C:66]2[CH:71]=[CH:70][CH:69]=[CH:68][CH:67]=2)[C@@H:26]([CH3:27])[CH2:25][OH:24])=[CH:33][CH:32]=1

Participants

4

Reactant 2

HCID 14487Diisobutylaluminum hydrideHCID 86602892HCID 86602892, compound

Product 1

HCID 86602891HCID 86602891, compoundYield 88.2%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Conditions

Temperature
0 °C

Procedure

DIBAL-H (1.0 M in hexane, 11.7 mL, 11.7 mmol) was added dropwise to a stirred solution of TBS protected acetal 42 (1.53 g, 1.17 mmol) in anhydrous CH2Cl2 (2.3 mL) under an atmosphere of N2 at 0° C. After stirring for additional 30 min at 0° C. the reaction mixture was quenched by the careful addition of aqueous saturated aqueous potassium sodium tartrate (30 mL). The resulting mixture was stirred for 3 h at room temperature. The organic layer was separated, and the aqueous layer was extracted by CH2Cl2 (20 mL). The combined organic layers were washed with brine and dried over MgSO4 followed by the evaporation of the organic solution under reduced pressure. The residue was purified by column chromatography (EtOAc/hexane 1:9) to obtain pure 43 (1.35 g, 88%) as a colorless oil: IR (CHCl3) 3464, 2956, 2929, 2856, 1613, 1514, 1471, 1252, 1087, 836, 773 cm−1; 1H NMR (300 MHz, CDCl3) δ 7.46 (m, 6H), 7.28 (m, 1H), 6.88 (m, 2H), 5.61 (m, 2H), 5.39 (m, 1H), 5.28 (m, 1H), 4.57 (m, 1H), 4.53 (s, 2H), 3.92 (m, 2H), 3.83 (m, 1H), 3.80 (s, 3H), 3.60 (m, 2H), 3.56 (m, 2H), 3.46 (dd, J=6.2, 4.5 Hz, 1H), 3.37 (m, 1H), 3.03 (m, 1H), 2.86 (m 1H), 2.59 (m, 1H), 2.41 (m, 1H), 1.93 (m, 1H), 1.88 (m, 1H), 1.66 (m, 3H), 1.35 (m, 5H), 1.11 (d, J=7.0 Hz, 3H), 1.01 (d, J=6.8 Hz, 3H), 0.97 (d, J=6.8 Hz, 3H), 0.92 (m, 27H), 0.85 (m, 10H), 0.81 (s, 9H), 0.11 (s, 3H), 0.09 (s, 3H), 0.07 (s, 3H), 0.06 (s, 6H), 0.05 (s, 6H), 0.04 (s, 3H); 13C NMR (75 MHz, CDCl3) δ 159.2, 144.4, 144.3, 134.3, 133.0, 132.4, 130.5, 129.1, 128.6, 127.6, 126.7, 113.8, 86.7, 85.4, 79.8, 75.1, 73.8, 72.2, 66.4, 65.0, 55.0, 42.3, 41.6, 41.5, 40.5, 37.1, 35.8, 34.8, 32.0, 31.9, 30.7, 26.2, 25.94, 25.86, 20.3, 19.2, 18.4, 18.1, 18.0, 15.6, 15.2, 13.2, 10.0, −3.0, −3.4, −3.8, −3.9, −4.2, −4.28, −4.34, −4.4; LRMS (ESI) 1329.8 [M+Na]+, 707.3, 413.2, 243.1; HRMS (ESI) calcd for C78H130O8Si4Na 1329.8741 [M+Na]+, found 1329.8779; [α]20D−8.9 (c 0.46, CHCl3).

Workup

  1. customat 0° C
  2. customwas quenched by the careful addition of aqueous saturated aqueous potassium sodium tartrate (30 mL)
  3. stirringThe resulting mixture was stirred for 3 h at room temperature
  4. customThe organic layer was separated
  5. extractionthe aqueous layer was extracted by CH2Cl2 (20 mL)
  6. washThe combined organic layers were washed with brine
  7. dry with materialdried over MgSO4
  8. customfollowed by the evaporation of the organic solution under reduced pressure
  9. customThe residue was purified by column chromatography (EtOAc/hexane 1:9)

Sources & evidence

ORD record
ord-a0009d3770fe47388d31f141d1a47dea
Source dataset
uspto-grants-2008_01
Patent number
US07321046B2

Reaction notes

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