Tetrahydrofuran → HCID 58196032, compound

HRID 1468735Notes

Reaction equation

HRID 1468735 reaction equation
[OH:1][C@:2]([CH2:18][CH:19]=[C:20]([CH3:22])[CH3:21])([CH2:13][C:14]([O:16][CH3:17])=[O:15])[C:3]([O:5][CH2:6][C:7]1[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=1)=[O:4].C1COCC1.[BH4-].[Na+].[OH-].[Na+]>[Hg](OC(C)=O)OC(C)=O.CCOC(C)=O.O>[CH3:17][O:16][C:14](=[O:15])[CH2:13][C@@:2]1([C:3]([O:5][CH2:6][C:7]2[CH:8]=[CH:9][CH:10]=[CH:11][CH:12]=2)=[O:4])[CH2:18][CH2:19][C:20]([CH3:22])([CH3:21])[O:1]1

Participants

8

Reactant 4

HCID 8028TetrahydrofuranHCID 14798Sodium HydroxideHCID 4311764Sodium borohydrideHCID 24879670HCID 24879670, compound

Product 1

HCID 58196032HCID 58196032, compound

Reagents, catalysts & solvents 3

HCID 16683746DiacetyloxymercuryCatalystHCID 962WaterSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
23 °C

Procedure

To a solution of alcohol 77 (183.6 mg, 0.599 mmol, 1.00 equiv) in 1:1 THF:H2O (9.2 mL) was added Hg(OAc)2 (382 mg, 1.199 mmol, 2.00 equiv). The resulting solution was stirred at 23° C. for 45 minutes. A 0.5M solution of NaBH4 in 3M NaOH (1.2 mL, 0.599 mmol, 1.00 equiv) was then added by syringe, resulting in an immediate precipitation of Hg0. After stirring for 5 minutes, the suspension was partitioned between 20 mL sat'd NH4Cl soln. and 20 mL EtOAc. The phases were separated and the aqueous phase was extracted with 2×20 mL EtOAc. The combined organic phases were dried over MgSO4 and solvent removal yielded a grey suspension that was purified by silica gel column chromatography (5:1 hex:EtOAc) to yield tetrahydrofuran S12 (141.6 mg, 77%) as a clear, colorless oil. Rf=0.58 (2:1 hex:EtOAc); 1H NMR (500 MHz, CDCl3) δ 7.34 (m, 5H, aryl H), 5.21 (d, 1H, J=12.3 Hz, PhCH2), 5.17 (d, 1H, J=12.3 Hz, PhCH2), 3.59 (s, 3H, OCH3), 2.91 (d, 1H, J=15.4 Hz, C(O)CH2), 2.81 (d, 1H, J=15.4 Hz, C(O)CH2), 2.41 (m, 1H, CH2), 2.16 (m, 1H, CH2), 1.85 (m, 1H, CH2), 1.78 (m, 1H, CH2), 1.30 (s, 3H, C(CH3)2), 1.24 (s, 3H, (CCH3)2); 13C NMR (125 MHz, CDCl3) δ 173.70, 170.54, 135.93, 128.59, 128.43, 128.32, 84.26, 83.96, 67.10, 51.80, 43.93, 37.88, 35.58, 29.09, 28.33; IR (neat film) 3036 (w), 2973 (m), 1743 (s), 1500 (w), 1458 (m), 1440 (m), 701 (m) cm−1; LRMS (ESI) calc'd for C17H22O5Na (M+Na+) 329.2, found 329.1.

Workup

  1. customresulting in an immediate precipitation of Hg0
  2. stirringAfter stirring for 5 minutes
  3. customthe suspension was partitioned between 20 mL
  4. customThe phases were separated
  5. extractionthe aqueous phase was extracted with 2×20 mL EtOAc
  6. dry with materialThe combined organic phases were dried over MgSO4 and solvent removal
  7. customyielded a grey suspension that
  8. customwas purified by silica gel column chromatography (5:1 hex:EtOAc)
  9. customto yield tetrahydrofuran S12 (141.6 mg, 77%) as a clear, colorless oil

Sources & evidence

ORD record
ord-4998f28c03a54ac3a8fe072718ec4a7f
Source dataset
uspto-grants-2015_04
Patent number
US09006231B2

Reaction notes

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