Tributylstannane → HCID 11824879, compound

HRID 478878Notes

Reaction equation

HRID 478878 reaction equation
C([Cu])#N.C([Li])CCC.[SnH:9]([CH2:18][CH2:19][CH2:20][CH3:21])([CH2:14][CH2:15][CH2:16][CH3:17])[CH2:10][CH2:11][CH2:12][CH3:13].[H][H].[CH2:24]([OH:29])/[CH:25]=[CH:26]/[C:27]#[CH:28].[NH4+].[OH-].[NH4+].[Cl-]>C1COCC1>[CH2:18]([Sn:9]([CH2:10][CH2:11][CH2:12][CH3:13])([CH2:14][CH2:15][CH2:16][CH3:17])/[CH:28]=[CH:27]/[CH:26]=[CH:25]/[CH2:24][OH:29])[CH2:19][CH2:20][CH3:21]

Participants

8

Reactant 6

HCID 5948TributylstannaneHCID 5463308HCID 5463308, compoundHCID 21863491Ammonium chloride ammonium hydroxideHCID 178418339ButyllithiumHCID 178418361HCID 178418361, compoundHCID 178418546HCID 178418546, compound

Product 1

HCID 11824879HCID 11824879, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-78 °C

Procedure

CuCN (0.63 g, 7.06 mmol) is introduced into a round-bottomed flask placed under argon, THF (18 ml) is then added and the mixture is cooled to −78° C. n-Butyl-lithium (1.6M, 8.8 ml, 14.01 mmol) is then added dropwise and the mixture is allowed to return slowly to room temperature. The mixture is again cooled to −78° C. and n-Bu3SnH (3.8 ml, 14.01 mmol) is added, and the mixture is stirred for 10 minutes, during which the hydrogen is discharged. (2E)-Pent-2-en-4-yn-1-ol (0.50 g, 6.09 mmol) is then added and the reaction mixture is left stirring for 45 minutes before being poured into 200 ml of an NH4OH/NH4Cl (10/90) solution. Extraction is carried out with ether (3×100 ml), drying is carried out over Na2SO4 and evaporation is carried out under vacuum, in order to obtain, after silica chromatography, elution being carried out with a hexane/ethyl acetate/triethylamine (89/10/1) mixture, 1.52 g of the expected product (67%) in the form of an oil. 1H NMR (250.13 MHz, CDCl3) δ 0.8-1.1 (m, 15H, n-Bu), 1.2-1.4 (m, 6H, n-Bu), 1.4-1.6 (m, 6H, n-Bu), 4.20 (br s, 2H, 2H1), 5.79 (dt, J=15.6 and 5.8 Hz, 1H, H2), 6.21 (dd, J=15.6 and 10.0 Hz, 1H, H3), 6.26 (d, J=18.5 Hz, 2JSn-H=67.2 Hz, 1H, H5), 6.54 (dd, J=18.5 and 10.0 Hz, 3JSn-H=59.2 Hz, 1H, H4) ppm; 13C NMR (62.89 MHz, CDCl3) δ 9.6 (t, 1JSn-C=344.2/330.6 Hz, 3×), 13.8 (q, 3×), 27.4 (t, 2JSn-C=53.7 Hz, 3×), 29.3 (t, 3Sn-C=20.3 Hz, 3×), 63.5 (t, C1), 131.0 (d), 134.9 (d, 1JSn-C=315.4 Hz, C5), 135.4 (d), 146.2 (d) ppm; MS (EI+) m/e (relative intensity) 317 ([M-Bu+1]+, 100), 315 (75), 313 (42), 261 (48), 259 (37), 257 (21), 251 (31), 249 (23), 247 (16), 205 (56), 203 (47), 201 (29), 137 (64), 135 (49), 133 (29), 121 (36), 119 (28), 117 (16); HRMS (EI+) calc. for C17H35OSn 373.1704, found: 373.1693; FTIR (CHCl3) ν 3600-3200 (br, —OH), 2960 (s, C—H), 2925 (s, C—H), 2864 (s, C—H), 1579 (w, C═C), 1456 (m, C—O), 1006 (m) cm−1.

Workup

  1. additionis then added dropwise
  2. customto return slowly to room temperature
  3. waitthe reaction mixture is left
  4. extractionExtraction
  5. customdrying
  6. customis carried out over Na2SO4 and evaporation
  7. customto obtain
  8. washafter silica chromatography, elution

Sources & evidence

ORD record
ord-fae99551454948d4a670ede92056ebe9
Source dataset
uspto-grants-2003_11
Patent number
US06642273B2

Reaction notes

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