Ethanol → HCID 46193183, compound

HRID 1293574Notes

Reaction equation

HRID 1293574 reaction equation
C([C@@H]([O:12][C:13](=[O:44])[CH2:14][C@H:15]([O:36][Si:37]([C:40]([CH3:43])([CH3:42])[CH3:41])([CH3:39])[CH3:38])[C:16]([CH3:35])([CH3:34])[C:17](=[O:33])[C@H:18]([CH3:32])[C@@H:19]([O:24][Si:25]([C:28]([CH3:31])([CH3:30])[CH3:29])([CH3:27])[CH3:26])[C@@H:20]([CH3:23])[CH:21]=C)C/C=C(/C)\CC=C)(=O)C.S[C:46]1N=CC=CC=1C(O)=O.[CH3:55][CH2:56][CH2:57][CH2:58][CH2:59][CH3:60].[CH2:61]([OH:63])[CH3:62]>C1(C)C=CC=CC=1.Cl[Ru](=C1N(C2C(C)=CC(C)=CC=2C)CCN1C1C(C)=CC(C)=CC=1C)(Cl)(=CC1C=CC=CC=1)[P](C1CCCCC1)(C1CCCCC1)C1CCCCC1>[C:61]([C@H:55]1[O:44][C:13](=[O:12])[CH2:14][C@H:15]([O:36][Si:37]([C:40]([CH3:41])([CH3:42])[CH3:43])([CH3:39])[CH3:38])[C:16]([CH3:34])([CH3:35])[C:17](=[O:33])[C@H:18]([CH3:32])[C@@H:19]([O:24][Si:25]([C:28]([CH3:30])([CH3:29])[CH3:31])([CH3:27])[CH3:26])[C@@H:20]([CH3:23])[CH:21]=[CH:60][CH2:59][C:58]([CH3:46])=[CH:57][CH2:56]1)(=[O:63])[CH3:62]

Participants

7

Reactant 4

HCID 702EthanolHCID 8058HexaneHCID 58733754HCID 58733754, compoundHCID 178524460HCID 178524460, compound

Product 1

HCID 46193183HCID 46193183, compoundYield 45%

Reagents, catalysts & solvents 2

HCID 178425456HCID 178425456, compoundCatalystHCID 1140TolueneSolvent2×

Procedure

A solution of 0.50 g (0.77 mmol) of (3S,6R,7S,8S)-3,7-bis-(tert-butyl-dimethyl-silanyloxy)-4,4,6,8-tetramethyl-5-oxo-dec-9-enoic acid (Z)-(S)-1-acetyl-4-methyl-hepta-3,6-dienyl ester in 1.9 l toluene was heated at reflux. A solution of 97.8 mg (0.12 mmol) of [RuCl2(PCy3)(ImH2Mes)(benzylidene)] (Grubbs 2nd generation RCM catalyst, commercially available from Sigma-Aldrich Corp. St. Louis, Mo. 63103) in 100 ml toluene was added and the resulting yellow solution stirred for 30 min at reflux. 18.06 mg (0.12 mmol) 2-mercaptonicotinic acid was added, and after 5 min the hot reaction solution was filtered over a silica gel pad. The filtrate was evaporated to dryness. To remove residual toluene, the crude product was dissolved in 60 ml ethanol and the formed solution evaporated to dryness to yield 409.0 mg of crude product with 59% purity (HPLC method: Chirobiotic V column, 4.6×250 mm, solvent A: n-hexane, B: ethanol, gradient from A/B 95/5 to 50/50 within 5 min and 4 min at 50/50, flow 0.5 ml/min, 18° C., 210 nm. Retention times: Starting material 5.8 min, product 6.6 min). Silica gel chromatographic purification of the crude product (hexane/ethylacetate 9:1) yielded 231.5 mg (combined fractions) of the title compound as an off-white solid with 93% purity (45% yield). M.p.: 85° C. MS: 622.4 (M+). 1H-NMR (300 MHz, CDCl3): −0.15 (s, 3H); −0.10 (s, 3H); −0.03 (s, 3H); 0.00 (s, 3H); 0.75 (s, 9H); 0.83 (s, 9H); 0.93 (d, 3H, J=7.0 Hz); 1.01 (s, 3H); 1.02 (d, 3H, J=7 Hz); 1.08 (s, 3H); 1.58 (s, 3H); 2.12 (s, 3H); 2.15–2.85 (m, 2H); 2.87–2.53 (m, 2H); 2.62 (dd, 1H, J=15.5, 2.6 Hz); 2.84 (dd, 2H, J=15.5, 8.0 Hz); 2.97 (dd, 1H, J=15.1, 4.8 Hz); 3.84 (d, 1H, J=8.6 Hz); 4.11 (dd, 1H, J=8.6, 2.4 Hz); 489 (dd, 1H, J=8.5, 2.5 Hz); 5.06 (t, 1H, J=7.5 Hz); 5.20–5.30 (m, 1H); 5.52 (dd, 1H, J=16.1, 8.5 Hz). Anal. calcd. for C34H62O6Si2: C, 65.55; H, 10.03; Si, 9.02. Found: C, 64.76; H, 9.84; Si, 8.96.

Workup

  1. temperatureat reflux
  2. temperatureat reflux
  3. filtrationafter 5 min the hot reaction solution was filtered over a silica gel pad
  4. customThe filtrate was evaporated to dryness
  5. customTo remove residual toluene
  6. dissolutionthe crude product was dissolved in 60 ml ethanol
  7. customthe formed solution evaporated to dryness
  8. customto yield 409.0 mg of crude product with 59% purity (HPLC method
  9. custom4 min
  10. custom0.5 ml/min, 18° C., 210 nm
  11. custommaterial 5.8 min, product 6.6 min
  12. customSilica gel chromatographic purification of the crude product (hexane/ethylacetate 9:1)

Sources & evidence

ORD record
ord-9882660fde4e461598d355223ce1386b
Source dataset
uspto-grants-2007_07
Patent number
US07238816B2

Reaction notes

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