4-Methylmorpholine → HCID 15444416, compound

HRID 1093088Notes

Reaction equation

HRID 1093088 reaction equation
CN1CCOCC1.[Si:8]([O:25][CH2:26][C@H:27]1[CH2:31][CH2:30][C@:29]([CH2:33][OH:34])([CH3:32])[C:28]1([CH3:36])[CH3:35])([C:21]([CH3:24])([CH3:23])[CH3:22])([C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1)[C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1>C(Cl)Cl.[Ru]([O-])(=O)(=O)=O.C([N+](CCC)(CCC)CCC)CC>[Si:8]([O:25][CH2:26][C@H:27]1[CH2:31][CH2:30][C@@:29]([CH3:32])([CH:33]=[O:34])[C:28]1([CH3:36])[CH3:35])([C:21]([CH3:23])([CH3:24])[CH3:22])([C:15]1[CH:16]=[CH:17][CH:18]=[CH:19][CH:20]=1)[C:9]1[CH:10]=[CH:11][CH:12]=[CH:13][CH:14]=1

Participants

5

Reactant 2

HCID 79724-MethylmorpholineHCID 15443826HCID 15443826, compound

Product 1

HCID 15444416HCID 15444416, compoundYield 81%

Reagents, catalysts & solvents 2

HCID 178419074HCID 178419074, compoundCatalystHCID 6344DichloromethaneSolvent

Procedure

A solution of 4-methylmorpholine (17.33 g, 148 mmol) in CH2Cl2 (400 mL) was dried over Mg2SO4 for 15 min and filtered into a round bottom flask containing ((1R,3S)-3-((tert-butyldiphenylsilyloxy)methyl)-1,2,2-trimethylcyclopentyl)methanol (40.5 g, 99 mmol). To the resulting clear solution was added 4 A° powdered molecular sieves (20 g), tetrapropylammonium perruthenate (TPAP) (0.693 g, 1.972 mmol) and stirred for 4 h at room temperature. The reaction was concentrated to ˜100 mL, diluted with hexane/Et2O (9:1, 500 mL) and filtered through a plug of silica gel. The plug was washed with 500 mL of hexane/Et2O (9:1). The filtrate was concentrated to afford (1R,3S)-3-((tert-butyldiphenylsilyloxy)methyl)-1,2,2-trimethylcyclopentanecarbaldehyde (32.61 g, 80 mmol, 81% yield) as a viscous pale yellow oil. 1H NMR (500 MHz, CDCl3) δ: 9.63 (1 H, s), 7.66 (4 H, dd, J=7.9, 1.5 Hz), 7.35-7.45 (6 H, m), 3.66-3.71 (1 H, dd, J=10.2, 6.9 Hz), 3.56 (1 H, dd, J=10.4, 7.0 Hz), 2.29 (1 H, ddd, J=13.7, 11.4, 6.0 Hz), 2.09-2.18 (1 H, m), 1.87-1.96 (1 H, m), 1.28-1.44 (2 H, m), 1.06 (3 H, s), 1.02-1.05 (12 H, s), 0.81 (3 H, s). LCMS (M+Na) calcd for C26H36NaO2Si: 431.25; found: 431.52.

Workup

  1. filtrationfiltered into a round bottom flask
  2. concentrationThe reaction was concentrated to ˜100 mL
  3. additiondiluted with hexane/Et2O (9:1, 500 mL)
  4. filtrationfiltered through a plug of silica gel
  5. washThe plug was washed with 500 mL of hexane/Et2O (9:1)
  6. concentrationThe filtrate was concentrated

Sources & evidence

ORD record
ord-483d611335b840c2a5d33e0874208935
Source dataset
uspto-grants-2012_03
Patent number
US08129398B2

Reaction notes

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