(3aS)-1-methyl-3,3-diphenyl-hexahydropyrrolo(1,2-c)(1,3,2)oxazaborole → HCID 131726528, compound

HRID 1991519Notes

Reaction equation

HRID 1991519 reaction equation
[C:1]([SiH2:5][O:6][C:7]([CH3:25])([CH3:24])[CH:8]1[CH2:17][CH2:16][C:15]2[C:10](=[CH:11][C:12]([CH2:18][C:19]([CH3:22])([CH3:21])[CH3:20])=[CH:13][CH:14]=2)[C:9]1=[O:23])([CH3:4])([CH3:3])[CH3:2].B1(C)OC(C2C=CC=CC=2)(C2C=CC=CC=2)[C@H]2N1CCC2.B.CSC>O1CCCC1>[C:1]([SiH2:5][O:6][C:7]([CH3:25])([CH3:24])[CH:8]1[CH2:17][CH2:16][C:15]2[C:10](=[CH:11][C:12]([CH2:18][C:19]([CH3:22])([CH3:21])[CH3:20])=[CH:13][CH:14]=2)[CH:9]1[OH:23])([CH3:4])([CH3:3])[CH3:2]

Participants

5

Reactant 3

HCID 2734713(3aS)-1-methyl-3,3-diphenyl-hexahydropyrrolo(1,2-c)(1,3,2)oxazaboroleHCID 12423031(Dimethyl sulfide)trihydroboronHCID 131726529HCID 131726529, compound

Product 1

HCID 131726528HCID 131726528, compoundYield 70%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-12.5 °C

Procedure

To a −30° C. cooled solution of 2-(tert-Butyl-dimethyl-silanyloxymethyl)-7-(2,2-dimethyl-propyl)-3,4-dihydro-2H-naphthalen-1-one (2.20 g, 6.09 mmol) in tetrahydrofuran (20 mL) was added (S)-2-methyl-Cbs-oxazaborolidine (1 M in toluene, 0.61 mL, 0.61 mmol) and a solution of borane-methyl sulfide complex (2 M in tetrahydrofuran, 2.15 mL, 4.3 mmol) in tetrahydrofuran (5 mL). The reaction mixture was heated at −20 to −5° C. for 5 h. The reaction mixture was quenched with methanol (8.3 mL) at −5° C. and then allowed to warm to room temperature and stirred overnight. The solvent was removed under reduced pressure. Flash column chromatography (silica gel, 0-5% ethyl acetate/hexanes) recovered 790 mg of ketone and provided chiral 2-(tert-Butyl-dimethyl-silanyloxymethyl)-7-(2,2-dimethyl-propyl)-1,2,3,4-tetrahydro-naphthalen-1-ol (980 mg, 70%): 1H NMR (300 MHz, CDCl3) δ 7.14 (s, 1H) , 7.03-6.96 (m, 2H), 4.84 (d, J=2.5 Hz, 1H), 3.92-3.82 (m, 2H), 3.04 (d, J=3.7 Hz, 1H), 2.92-2.67 (m, 2H), 2.46 (s, 2H), 2.04-1.86 (m, 2H), 1.75-1.63 (m, 1H), 0.91 (s, 9H), 0.90 (s, 9H), 0.10 (s, 3H), 0.09 (s, 3H).

Workup

  1. customThe reaction mixture was quenched with methanol (8.3 mL) at −5° C.
  2. temperatureto warm to room temperature
  3. customThe solvent was removed under reduced pressure
  4. customFlash column chromatography (silica gel, 0-5% ethyl acetate/hexanes) recovered 790 mg of ketone

Sources & evidence

ORD record
ord-0f0f49c7a3d84909aac740fde2edba35
Source dataset
uspto-grants-2010_01
Patent number
US07645780B2

Reaction notes

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