Triethylamine → HCID 89123914, compound

HRID 1505297Notes

Reaction equation

HRID 1505297 reaction equation
C([N:8]1[C@H:17](CO)[CH2:16][C:15]2[C:10](=[C:11]3[CH:31]=[CH:30][C:29]([O:32][CH3:33])=[CH:28][C:12]3=[C:13]3[CH:23]=[C:22]([O:24][CH3:25])[C:21]([O:26][CH3:27])=[CH:20][C:14]3=2)[CH2:9]1)(OC(C)(C)C)=O.CCN([CH2:39][CH3:40])CC.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C[C:61]([O-:64])(C)C.[K+]>C(Cl)Cl.CS(C)=O.C(Cl)(Cl)Cl>[CH3:27][O:26][C:21]1[C:22]([O:24][CH3:25])=[CH:23][C:13]2[C:14]([CH:20]=1)=[C:15]1[C:10](=[C:11]3[CH:31]=[CH:30][C:29]([O:32][CH3:33])=[CH:28][C:12]=23)[CH2:9][NH:8][C@H:17](/[CH:40]=[CH:39]/[O:64][CH3:61])[CH2:16]1

Participants

8

Reactant 4

HCID 8471TriethylamineHCID 11776TriphenylphosphineHCID 23665647Potassium tert-butoxideHCID 88957575HCID 88957575, compound

Product 1

HCID 89123914HCID 89123914, compoundYield 78%

Reagents, catalysts & solvents 3

HCID 679Dimethyl SulfoxideSolventHCID 6212ChloroformSolventHCID 6344DichloromethaneSolvent2×

Procedure

N-Boc-alcohol 2 (1.812 g, 4 mmol) was dissolved in CH2Cl2 (50 ml) and Et3N (1.95 ml, 14 mmol) at 0° C., to which Py.SO3 (2.23 g, 14 mmol) in 10 ml of DMSO was added dropwise. The ice bath was then removed and the mixture was stirred at r.t. until alcohol disappeared by TLC. HCl (1N) was added, and the organic layer was then separated and washed with sat. NaHCO3, brine, and dried over MgSO4. In another flask, Ph3P+CH2OMeCl− (2.74 g, 8 mmol) was added to KOtBu (875 mg, 7.8 mmol) at 0° C. under N2, which was stirred for 0.5 h. The aldehyde in 20 ml of CH2Cl2 was added dropwise, followed by removal of ice bath. The reaction was kept for 2-3 h before sat. NH4Cl was poured into the mixture. CH2Cl2 was used for extraction and the organic layers were washed with sat. NaHCO3 and brine, dried over MgSO4. Chromatography afforded 1.5 g of light yellow solid. Yield: 78% for two steps. mp 150-152° C.; [α]23D=108.1° (c 0.59, CHCl3); 1H NMR (400 MHz, CDCl3, E/Z=2.5:1): δ 7.94-7.91 (m, 2H), 7.88 (d, J=9.2 Hz, 1H), 7.29 (s, 1H), 7.26-7.22 (m, 1H), 6.30 (d, J=12.8 Hz, 0.68H, E isomer), 5.86 (dd, J=6.4 Hz, J=1.6 Hz, 0.28 Hz, Z isomer), 5.72 (m, 0.31H, Z isomer), 5.30-5.25 (d, J=16.8 Hz, 1H+0.67H, E isomer), 4.80 (dd, J=12.8 Hz, J=8.4 Hz, 0.71H, E isomer), 4.59 (d, J=17.2 Hz, 1H), 4.42 (dd, J=8.0 Hz, J=6.4 Hz, 0.29H, Z isomer), 4.12-4.11 (m, 3H), 4.05-4.04 (m, 3H), 4.03-4.02 (m, 3H), 3.62 (s, 0.7111, Z isomer), 3.44-3.32 (m, 1H), 3.36 (s, 211, E isomer), 3.13 (d, J=16.0 Hz, 1H), 1.55 (s, 9H); ESI MS m/z 480.05 (M+H)+.

Workup

  1. customThe ice bath was then removed
  2. additionHCl (1N) was added
  3. customthe organic layer was then separated
  4. washwashed with sat. NaHCO3, brine
  5. dry with materialdried over MgSO4
  6. stirringwhich was stirred for 0.5 h
  7. customfollowed by removal of ice bath
  8. additionwas poured into the mixture
  9. extractionCH2Cl2 was used for extraction
  10. washthe organic layers were washed with sat. NaHCO3 and brine
  11. dry with materialdried over MgSO4
  12. customChromatography afforded 1.5 g of light yellow solid

Sources & evidence

ORD record
ord-4c0638f5a67643a9b68e755e6ea6335f
Source dataset
uspto-grants-2015_12
Patent number
US09216977B2

Reaction notes

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