HCID 53891718, compound → HCID 67693793, compound

HRID 1648680Notes

Reaction equation

HRID 1648680 reaction equation
C(C1C=C(/C(=C/CCC2C=CC(OC)=C(C34CC5CC(CC(C5)C3)C4)C=2)/CO)C=CC=1)(OCC)=O.[O:36]([CH2:44]/[C:45](/[C:73]1[CH:78]=[CH:77][CH:76]=[C:75]([C:79]([O:81][CH2:82][CH3:83])=[O:80])[CH:74]=1)=[CH:46]\[CH2:47][CH2:48][C:49]1[CH:54]=[CH:53][C:52]([O:55][Si:56]([C:59]([CH3:62])([CH3:61])[CH3:60])([CH3:58])[CH3:57])=[C:51]([C:63]23[CH2:72][CH:67]4[CH2:68][CH:69]([CH2:71][CH:65]([CH2:66]4)[CH2:64]2)[CH2:70]3)[CH:50]=1)[Si](C(C)(C)C)(C)C.O(CC(C1C=CC=CC=1)=CCCC1C=CC(O[Si](C(C)(C)C)(C)C)=C(C23CC4CC(CC(C4)C2)C3)C=1)[Si](C(C)(C)C)(C)C>C(O)(=O)C.C1COCC1.O>[C:79]([C:75]1[CH:74]=[C:73](/[C:45](=[CH:46]/[CH2:47][CH2:48][C:49]2[CH:54]=[CH:53][C:52]([O:55][Si:56]([C:59]([CH3:60])([CH3:62])[CH3:61])([CH3:57])[CH3:58])=[C:51]([C:63]34[CH2:64][CH:65]5[CH2:66][CH:67]([CH2:68][CH:69]([CH2:71]5)[CH2:70]3)[CH2:72]4)[CH:50]=2)/[CH2:44][OH:36])[CH:78]=[CH:77][CH:76]=1)([O:81][CH2:82][CH3:83])=[O:80]

Participants

5

Reactant 3

HCID 53891718HCID 53891718, compoundHCID 67693795HCID 67693795, compoundHCID 67807452HCID 67807452, compound

Product 1

HCID 67693793HCID 67693793, compound

Reagents, catalysts & solvents 1

HCID 21877175AcOH THF waterSolvent

Procedure

For (Z)-2-(3-Carboethoxyphenyl)-5-[3-(1-adamantyl)-4-methoxyphenyl]-2-pentenol (8j). A ~1:1 mixture of 7j (3:1, Z:E) and 1-(t-butyldimethylsiloxy)-2-phenyl-5-[3-(1-adamantyl)-4-t-butyldimethylsiloxyphenyl]-2-pentene (3:1, Z:E) (1.6 g) was dissolved in 30 mL of 3:1:1 acetic acid/THF/H2O, and stirred for 48 h. The solvent was removed in vacuo. The residue was purified by column chromatography on silica gel (elution with methylene chloride to 5% methanol/methylene chloride) to give 0.490 g of pure (Z)-2-(3-carboethoxyphenyl)-5-[3-(1-adamantyl)-4-t-butyldimethylsiloxyphenyl]-2-pentenol (74% based on ca. 800 mg of 7j in the starting mixture): 1H NMR (300 MHz, CDCl3) δ7.96 (dt, J=8, 1 Hz, 1H, 2-ArH), 7.89 (t, J=1 Hz, 1H, 2-ArH), 7.38 (t, J=8 Hz, 1H, 2-ArH), 7.22 (m, 1H, 2-ArH), 6.91 (d, J=2 Hz, 1H, 5-ArH), 6.77 (dd, J=2, 8 Hz, 1H, 5- ArH), 6.63 (d, J=8 Hz, 1H, 5-ArH), 5.82 (t, J=8 Hz, 1H, C=CH), 4.23-4.40 (m, 4H, CH2OH and CO2CH2CH3), 2.59 (t, J= 8 Hz, 2H, ArCH2), 2.26 (q, J=8 Hz, 2H, ArCH2CH2), 2.08 (s, 9H, adamantyl), 1.76 (s, 6H, adamantyl), 1.39 (t, J=8 Hz, 3H, CO2CH2CH3), 1.01 (s, 9H, SiC(CH3)3), and 0.31 (s, 6H, Si(CH3)2). (Z)-2-(3-Carboethoxyphenyl)-5-[3-(1-adamantyl)-4-t-butyldimethylsiloxyphenyl]-2-pentenol (490 mg) was converted in two steps to 8j via treatment with tetrabutylammonium fluoride and then alkylation with dimethyl sulfate as described in the synthesis of 5×. Purification of 8j by column chromatography on silica gel (elution with 30% ethyl acetate/hexane) gave 0.150 g of pure 8j (37% for two steps): 1H NMR (300 MHz, CDCl3) δ7.96 (dt, J=1, 8 Hz, 1H, 2-ArH), 7.89 (t, J=1 Hz, 1H, 2-ArH), 7.39 (t, J=8 Hz, 1H, 2-ArH), 7.28 (m, 1H, 2-ArH), 6.92 (d, J=2 Hz, 1H, 5-ArH), 6.89 (dd, J=2, 8 Hz, 1H, 5- ArH), 6.76 (d, J=8 Hz, 1H, 5-ArH), 5.83 (t, J=8 Hz, 1H, C=CH), 4.33-4.42 (m, 4H, CH2OH and CO2CH2CH3), 3.80 (s, 3H, OCH3), 2.61 (t, J=8 Hz, 2H, ArCH2), 2.29 (q, J=8 Hz, 2H, ArCH2CH2), 2.06 (s, 9H, adamantyl), 1.76 (s, 6H, adamantyl), and 1.40 (t, J=8 Hz, 3H, CO2CH2CH3).

Workup

  1. customThe solvent was removed in vacuo
  2. customThe residue was purified by column chromatography on silica gel (elution with methylene chloride to 5% methanol/methylene chloride)

Sources & evidence

ORD record
ord-5711e7c25375465489ced79cd9b215b4
Source dataset
uspto-grants-1995_07
Patent number
US05436369

Reaction notes

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