Tetrahydrofuran → HCID 77985821, compound

HRID 1523004Notes

Reaction equation

HRID 1523004 reaction equation
C([S:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH:13]([CH:19]([CH2:25][CH2:26][CH2:27][CH2:28][CH2:29][CH2:30][CH2:31][CH2:32][S:33]C(=O)C)[CH2:20][C:21](OC)=[O:22])[CH2:14][C:15](OC)=[O:16])(=O)C.C1COCC1.CC(C[AlH]CC(C)C)C>C1(C)C=CC=CC=1>[SH:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH:13]([CH:19]([CH2:25][CH2:26][CH2:27][CH2:28][CH2:29][CH2:30][CH2:31][CH2:32][SH:33])[CH2:20][CH2:21][OH:22])[CH2:14][CH2:15][OH:16]

Participants

5

Reactant 3

HCID 8028TetrahydrofuranHCID 14487Diisobutylaluminum hydrideHCID 89262239HCID 89262239, compound

Product 1

HCID 77985821HCID 77985821, compoundYield 30%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

To a flame-dried 20 mL vial fitted with a screw-top septa cap was charged with dimethyl 3,4-bis(8-(acetylthio)octyl)hexanedioate (1 equiv, 0.34 mmol, 187 mg, mixture of stereoisomers) and THF (4.5 mL). DIBAl-H (12 equiv, 4.1 mmol, 2.7 mL of a nominally 1.5 M solution in toluene) was added dropwise. The reaction was stirred for 3 h at rt, quenched by careful addition of 2 N HCl (5 mL), diluted with 10 mL sat. aq. NH4Cl (10 mL), and extracted with Et2O (3×15 mL). The combined organic layers were washed with brine (1×15 mL), dried with Na2SO4, concentrated in vacuo, and purified by flash column chromatography (35% EtOAc/Hex) to afford rac-3,4-Bis(8-mercaptooctyl)hexane-1,6-diol (41 mg, 30%) and meso-3,4-Bis(8-mercaptooctyl)hexane-1,6-diol (49 mg, 49%). TLC rac-Rf=0.57 (50% EtOAc/Hex), meso-Rf=0.38 (50% EtOAc/Hex); rac: 1HNMR (400 MHz): δ 3.60-3.79 (4H), 2.54 (q, 4H, J=7.3 Hz), 1.14-1.68 (38H); 13CNMR (100 MHz): δ 61.6, 35.8, 34.0, 33.7, 30.7, 30.0, 29.5, 29.1, 28.3, 28.0, 24.6; FTIR: 3323, 2922, 2852, 1463, 1051, 722 cm−1; HRMS-ESI: calc. for C22H46NaO2S2 (M+Na)+: 429.2837. found: 429.2825; meso: 1HNMR (400 MHz): δ 3.59-3.76 (4H), 2.54 (q, 4H, J=7.3 Hz), 1.87 (bs, 2H), 1.08-1.68 (36H); 13CNMR (100 MHz): δ 61.9, 36.7, 34.0, 33.8, 30.7, 30.0, 29.5, 29.1, 28.4, 28.0, 24.7; FTIR: 3329, 2922, 2852, 1463, 1051, 721 cm−1; HRMS-ESI: calc. for C22H46NaO2S2 (M+Na)+: 429.2837. found: 429.2829.

Workup

  1. customTo a flame-dried 20 mL vial fitted with a screw-top septa
  2. customcap
  3. customquenched by careful addition of 2 N HCl (5 mL)
  4. additiondiluted with 10 mL sat. aq. NH4Cl (10 mL)
  5. extractionextracted with Et2O (3×15 mL)
  6. washThe combined organic layers were washed with brine (1×15 mL)
  7. dry with materialdried with Na2SO4
  8. concentrationconcentrated in vacuo
  9. custompurified by flash column chromatography (35% EtOAc/Hex)

Sources & evidence

ORD record
ord-57c28fa96ca94f93950a97feb3c1d6a5
Source dataset
uspto-grants-2015_07
Patent number
US09079835B2

Reaction notes

Loading…