Chlorotrimethylsilane → HCID 71520077, compound

HRID 633663Notes

Reaction equation

HRID 633663 reaction equation
C1COCC1.[CH3:6][O:7][C:8]1[C@:15]2([CH2:18][CH:19]=[C:20]([CH3:22])[CH3:21])[C:16](=[O:17])[C@@H:11]([C@:12]([CH3:42])([CH2:28][CH2:29][CH2:30][C:31]([CH3:41])([O:33][Si:34]([CH2:39][CH3:40])([CH2:37][CH3:38])[CH2:35][CH3:36])[CH3:32])[C@@H:13]([CH2:23][CH:24]=[C:25]([CH3:27])[CH3:26])[CH2:14]2)[C:10](=[O:43])[CH:9]=1.Cl[Si:45]([CH3:48])([CH3:47])[CH3:46].[Li]N1C(C)(C)CCCC1(C)C>CCOC(C)=O.CCCCCC>[CH3:6][O:7][C:8]1[C@:15]2([CH2:18][CH:19]=[C:20]([CH3:22])[CH3:21])[C:16](=[O:17])[C@@H:11]([C@:12]([CH3:42])([CH2:28][CH2:29][CH2:30][C:31]([CH3:41])([O:33][Si:34]([CH2:37][CH3:38])([CH2:35][CH3:36])[CH2:39][CH3:40])[CH3:32])[C@@H:13]([CH2:23][CH:24]=[C:25]([CH3:27])[CH3:26])[CH2:14]2)[C:10](=[O:43])[C:9]=1[Si:45]([CH3:48])([CH3:47])[CH3:46]

Participants

7

Reactant 4

HCID 6397ChlorotrimethylsilaneHCID 8028Tetrahydrofuran2×HCID 71499447HCID 71499447, compoundHCID 178418821HCID 178418821, compound

Product 1

HCID 71520077HCID 71520077, compoundYield 90.2%

Reagents, catalysts & solvents 2

HCID 8058HexaneSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
0 °C

Procedure

A THF (1 mL) solution of 44 (22.9 mg, 42.0 μmol, 1 equiv.) was cooled to −78° C. in a 10-mL test tube, and chlorotrimethylsilane (53 μL, 0.42 mmol, 10 equiv.) and a freshly prepared THF solution of lithium tetramethylpiperidide (0.50 M, 420 μL, 0.21 mmol, 5 equiv.) were sequentially added. The golden yellow solution was slowly warmed to 0° C. over 1 h and quenched at 0° C. with saturated aqueous NaHCO3. The mixture was warmed to room temperature and extracted thrice with EtOAc. The organic extracts were combined, washed with H2O and brine, dried over Na2SO4, filtered, and concentrated in vacuo to a yellow oil. Flash column chromatography (20 mL SiO2, 98:2 hexane:EtOAc) afforded 23.4 mg (37.9 μmol, 90% yield) of 45 as a colorless oil. TLC Rf 0.40 (95:5 hexane:EtOAc). 1H NMR (600 MHz; CDCl3): δ 5.02-4.97 (m, 2H), 3.83 (s, 3H), 3.11 (s, 1H), 2.51 (dd, J=14.4, 6.3 Hz, 1H), 2.37 (dd, J=14.5, 7.5 Hz, 1H), 2.15-2.11 (m, 1H), 1.99 (dd, J=14.0, 3.7 Hz, 1H), 1.69 (s, 3H), 1.68-1.63 (m, 9H), 1.57 (s, 3H), 1.48 (td, J=12.7, 3.9 Hz, 1H), 1.46-1.37 (m, 2H), 1.30 (td, J=12.2, 4.1 Hz, 1H), 1.26-1.24 (m, 1H), 1.21 (s, 3H), 1.21 (s, 3H), 1.14 (td, J=12.6, 4.2 Hz, 1H), 0.94 (t, J=7.9 Hz, 9H), 0.80 (s, 3H), 0.57 (q, J=8.1 Hz, 6H), 0.23 (s, 9H). 13C NMR (126 MHz; CDCl3): δ 207.9, 198.6, 185.7, 133.70, 133.59, 127.7, 122.8, 120.0, 73.7, 72.6, 64.1, 59.7, 46.7, 45.7, 41.8, 39.29, 39.27, 30.6, 30.0, 29.7, 27.6, 26.02, 25.97, 18.21, 18.14, 17.88, 17.83, 7.4, 7.0, 0.8. HRMS-ESI (m/z): [M+H]+ calculated for C36H64O4Si2, 617.4416. found, 617.4395.

Workup

  1. customquenched at 0° C. with saturated aqueous NaHCO3
  2. temperatureThe mixture was warmed to room temperature
  3. extractionextracted thrice with EtOAc
  4. washwashed with H2O and brine
  5. dry with materialdried over Na2SO4
  6. filtrationfiltered
  7. concentrationconcentrated in vacuo to a yellow oil

Sources & evidence

ORD record
ord-4e136f600d114db5a39e164def4dcd16
Source dataset
uspto-grants-2016_04
Patent number
US09321713B2

Reaction notes

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