Triethylsilane → HCID 86652148, compound

HRID 1258142Notes

Reaction equation

HRID 1258142 reaction equation
[CH2:1]([O:8][C:9]([CH3:29])([CH3:28])/[CH:10]=[CH:11]/[CH2:12][C@:13]1([C:18]([O:20]CC2C=CC=CC=2)=[O:19])[CH2:16][C:15](=[O:17])[O:14]1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C([SiH](CC)CC)C>CC([O-])=O.CC([O-])=O.[Pd+2]>[CH2:1]([O:8][C:9]([CH3:29])([CH3:28])/[CH:10]=[CH:11]/[CH2:12][C@:13]1([C:18]([OH:20])=[O:19])[CH2:16][C:15](=[O:17])[O:14]1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

4

Reactant 2

HCID 12052TriethylsilaneHCID 24879674HCID 24879674, compound

Product 1

HCID 86652148HCID 86652148, compoundYield 85%

Reagents, catalysts & solvents 1

HCID 167845palladium(II) acetateCatalyst

Conditions

Temperature
23 °C

Procedure

To a solution of benzyl ester 85 (52.8 mg, 0.134 mmol, 1.00 equiv.) were added TEA (3.0 μL, 0.0214 mmol, 0.16 equiv.), triethylsilane (32.1 μL, 0.201 mmol, 1.50 equiv.), and Pd(OAc)2 (1.6 mg, 0.0071 mmol, 0.053 equiv.). The resulting black solution was stirred at 23° C. for 1 h then partitioned between 10 mL sat'd NH4Cl solution and 10 mL CH2Cl2. The phases were separated and the aqueous phase was extracted with 2×10 mL CH2Cl2. The combined aqueous phases were dried over MgSO4 and solvent removal by rotary evaporation left a brown oil that upon purification by silica gel column chromatography (4% HOAc in 1:1 hex:EtOAc) yielded acid 86 (34.4 mg, 85%) as a clear, colorless oil. Rf=0.17 (4% HOAc in 1:1 hex:EtOAc); 1H NMR (500 MHz, CDCl3) δ 10.09 (br s, 1H, CO2H), 7.33-7.23 (m, 5H, aryl H), 5.81 (d, 1H, J=15.9 Hz, (CH3)2CCH), 5.62 (m, 1H, CH2CH), 4.35 (s, 2H, PhCH2), 3.57 (d, 1H, J=16.6 Hz, C(O)CH2), 3.36 (d, 1H, J=16.6, Hz, C(O)CH2), 2.87 (dd, 1H, J=14.6, 7.1 Hz), 2.74 (dd, 1H, J=14.7, 7.3 Hz), 1.35 (s, 6H, (CH3)2); 13C NMR (125 MHz, CDCl3) δ 173.48, 165.44, 143.27, 139.13, 128.48, 127.66, 127.53, 120.34, 75.85, 65.24, 46.06, 37.57, 26.51, 26.29; IR (neat film) 3500-2500 (br m), 3031 (w), 2977 (m), 1843 (s), 1745 (s), 1497 (w), 1453 (w), 1149 (m) cm−1; LRMS (ESI) calc'd for C17H20O5Na 327.1; found 326.9.

Workup

  1. customthen partitioned between 10 mL
  2. customThe phases were separated
  3. extractionthe aqueous phase was extracted with 2×10 mL CH2Cl2
  4. dry with materialThe combined aqueous phases were dried over MgSO4 and solvent removal by rotary evaporation
  5. waitleft a brown oil that
  6. customupon purification by silica gel column chromatography (4% HOAc in 1:1 hex:EtOAc)

Sources & evidence

ORD record
ord-6e1fcebc29fe4cc1850d5c7ce426a2a8
Source dataset
uspto-grants-2013_06
Patent number
US08466142B2

Reaction notes

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