Chlorotrimethylsilane → HCID 90123880, compound

HRID 633653Notes

Reaction equation

HRID 633653 reaction equation
C1COCC1.FC(F)(F)S(O[C@H:12]1[CH2:19][C@@:18]2([CH2:22][CH:23]=[C:24]([CH3:26])[CH3:25])[C:20](=[O:21])[C@H:14]([C:15](=[O:29])[CH:16]=[C:17]2[O:27][CH3:28])[C@:13]1([CH3:36])[CH2:30][CH2:31][CH:32]=[C:33]([CH3:35])[CH3:34])(=O)=O.Cl[Si:40]([CH3:43])([CH3:42])[CH3:41].C([N-]C(C)C)(C)C.[Li+]>CCOC(C)=O.CCCCCC>[CH3:28][O:27][C:17]1[C:18]2([CH2:22][CH:23]=[C:24]([CH3:26])[CH3:25])[C:20](=[O:21])[C:14]3([C:15](=[O:29])[C:16]=1[Si:40]([CH3:43])([CH3:42])[CH3:41])[CH:12]([C:13]3([CH3:36])[CH2:30][CH2:31][CH:32]=[C:33]([CH3:35])[CH3:34])[CH2:19]2

Participants

7

Reactant 4

HCID 6397ChlorotrimethylsilaneHCID 8028Tetrahydrofuran2×HCID 2724682Lithium diisopropylamideHCID 86718444HCID 86718444, compound

Product 1

HCID 90123880HCID 90123880, compoundYield 56%

Reagents, catalysts & solvents 2

HCID 8058HexaneSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
-78 °C

Procedure

A THF (6 mL) solution of 21 (148 mg, 0.300 mmol, 1 equiv.) and chlorotrimethylsilane (1.9 mL, 15 mmol, 50 equiv.) was cooled to −78° C. in a 25-mL recovery flask, and a freshly prepared THF solution of lithium diisopropylamide (0.50 M, 3.0 mL, 1.5 mmol, 5 equiv.) was added slowly. The resulting yellow-orange solution was stirred at −78° C. for 30 min and subsequently quenched at −78° C. with saturated aqueous NaHCO3. After warming to room temperature, the mixture was extracted thrice with EtOAc. The organic extracts were combined, washed with H2O and brine, dried over Na2SO4, filtered, and concentrated in vacuo to give an orange oil. Flash column chromatography (100 mL SiO2, 95:5 hexane:EtOAc) afforded 69.7 mg (0.168 mmol, 56% yield) of 22 as a faint yellow oil. TLC Rf 0.52 (8:2 hexane:EtOAc). 1H NMR (600 MHz; C6D6): δ 5.41 (t, J=7.4 Hz, 1H), 5.28 (t, J=7.1 Hz, 1H), 3.22 (s, 3H), 2.59 (dd, J=15.1, 6.4 Hz, 1H), 2.53-2.49 (m, 1H), 2.48 (dd, J=15.1, 8.4 Hz, 1H), 2.18 (m, 1H), 1.86 (ddd, J=13.5, 11.2, 5.2 Hz, 1H), 1.79 (ddd, J=13.5, 11.2, 5.4 Hz, 1H), 1.74 (dd, J=14.0, 5.4 Hz, 1H), 1.68-1.66 (m, 1H), 1.66 (s, 3H), 1.65 (s, 3H), 1.61 (s, 3H), 1.54 (s, 3H), 1.07 (s, 3H), 0.98 (dd, J=7.9, 5.4 Hz, 1H), 0.35 (s, 9H). 13C NMR (126 MHz; C6D6): δ 200.2, 194.7, 184.3, 134.4, 131.56, 131.55, 124.6, 119.5, 74.1, 61.8, 56.8, 48.0, 38.7, 37.7, 27.7, 26.21, 26.10, 25.8, 17.92, 17.77, 16.3, 0.7. FTIR (thin film) νmax: 2968, 2918, 2860, 1762, 1664, 1523, 1451, 1438, 1386, 1233, 1201, 1157, 1042, 962, 845, 761, 691 cm−1. HRMS-ESI (m/z): [M+H]+ calculated for C25H38O3Si, 415.2663. found, 415.2650.

Workup

  1. customsubsequently quenched at −78° C. with saturated aqueous NaHCO3
  2. temperatureAfter warming to room temperature
  3. extractionthe mixture was extracted thrice with EtOAc
  4. washwashed with H2O and brine
  5. dry with materialdried over Na2SO4
  6. filtrationfiltered
  7. concentrationconcentrated in vacuo
  8. customto give an orange oil

Sources & evidence

ORD record
ord-8ffd645956d04f66b8aa37e42afd51eb
Source dataset
uspto-grants-2016_04
Patent number
US09321713B2

Reaction notes

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