tert-Butylsulfinamide, (R)-(+)- → (R)-(-)-N-[(4-allyldimethylsilylphenyl)methylene]-tert-butanesulfinamide

HRID 2228383Notes

Reaction equation

HRID 2228383 reaction equation
[C:1]([S@:5]([NH2:7])=[O:6])([CH3:4])([CH3:3])[CH3:2].[CH2:8]([C:11]1[CH:18]=[CH:17][C:14]([CH:15]=O)=[C:13]([SiH:19]([CH3:21])[CH3:20])[CH:12]=1)[CH:9]=[CH2:10]>C1COCC1.[Cl-].[Na+].O.[O-]CCC.[Ti+4].[O-]CCC.[O-]CCC.[O-]CCC>[CH2:8]([C:11]1[CH:18]=[CH:17][C:14]([CH:15]=[N:7][S@@:5]([C:1]([CH3:4])([CH3:3])[CH3:2])=[O:6])=[C:13]([SiH:19]([CH3:21])[CH3:20])[CH:12]=1)[CH:9]=[CH2:10]

Participants

6

Reactant 2

HCID 10964479tert-Butylsulfinamide, (R)-(+)-HCID 1317233714-Allyldimethylsilylbenzaldehyde

Product 1

HCID 131723380(R)-(-)-N-[(4-allyldimethylsilylphenyl)methylene]-tert-butanesulfinamideYield 68.3%

Reagents, catalysts & solvents 3

HCID 9903917Titanium tetrapropoxideCatalystHCID 8028TetrahydrofuranSolventHCID 57417360Sodium chloride; waterSolvent

Procedure

To a solution of (R)-(−)-tert-butanesulfinamide (3.7 g, 30 mmol) and 4-allyldimethylsilylbenzaldehyde (2 Scheme 1, 6.2 g, 30 mmol) in dry THF (15 mL) was added titanium(IV) propoxide (17 mL, 60 mmol). The mixture was refluxed for 1 h under a N2 atmosphere. The mixture was cooled immediately upon reaction completion, and poured into a brine (30 mL) with rapid stirring. The resulting white suspension was filtered through a pad of celite, which was then washed with ethyl acetate (100 mL). The filtrate was transferred to a separatory funnel where the organic layer was washed with brine (20 mL). The organic layer was dried (Na2SO4), concentrated. The crude oil was purified by column chromatography (1:5 ethyl acetate/hexanes) to afford a colorless oil (6.3 g, 68%); 1H NMR (300 MHz, CDCl3) δ 0.30 (s, 6 H), 1.26 (s, 9 H), 1.76 (d, J=7.92 Hz, 2 H), 4.83 (s, 1 H), 4.88 (d, J=4.41 Hz, 1 H), 5.74 (ddt, J=15.84, 9.27, 8.28 Hz, 1 H), 7.62 (d, J=7.92 Hz, 2 H), 7.82 (d, J=7.92 Hz, 2 H), 8.59 (s, 1 H); 13C NMR (75 MHz, CDCl3) −3.5 (2C), 22.6 (3C), 23.4, 57.8, 113.9, 128.4 (2C),134.0, 134.2 (2C), 134.4, 144.6, 162.8; HRMS (M+1) calcd for C16H26NOSSi 308.1505, found 308.1415.

Workup

  1. temperatureThe mixture was refluxed for 1 h under a N2 atmosphere
  2. temperatureThe mixture was cooled immediately upon reaction completion
  3. filtrationThe resulting white suspension was filtered through a pad of celite, which
  4. washwas then washed with ethyl acetate (100 mL)
  5. customThe filtrate was transferred to a separatory funnel
  6. washwhere the organic layer was washed with brine (20 mL)
  7. dry with materialThe organic layer was dried (Na2SO4)
  8. concentrationconcentrated
  9. customThe crude oil was purified by column chromatography (1:5 ethyl acetate/hexanes)

Sources & evidence

ORD record
ord-8f38a4b09f80424d80ac91c0796844e4
Source dataset
uspto-grants-2002_07
Patent number
US06416861B1

Reaction notes

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