Toluene → 3,3,5-Trimethylcyclohexanone

HRID 600173Notes

Reaction equation

C1OC2C(C3C4OCOC=4C=CC=3P(C3C=CC=CC=3)C3C=CC=CC=3)=C(P(C3C=CC=CC=3)C3C=CC=CC=3)C=CC=2O1.O(C(C)(C)C)[Na].C1(C)C=CC=CC=1.[O:58]=[C:59]1[CH2:66][C:63]([CH3:65])([CH3:64])[CH2:62][C:61]([CH3:67])=[CH:60]1>CC(O)(C)C>[CH3:64][C:63]1([CH3:65])[CH2:62][CH:61]([CH3:67])[CH2:60][C:59](=[O:58])[CH2:66]1

Participants

Conditions

Temperature: 50 °C

Procedure

Into a 100-mL stainless-steel autoclave was put 22.6 mmol (0.03 mmol; Cu reduced) of the chiral copper complex [CuBr ((S)-SEGPHOS)]n obtained in the same manner as described in Example 1, 18.3 mg (0.03 mmol) of (S)-SEGPHOS and 28.8 mg (0.30 mmol) of NaO-t-Bu, followed by replacing with nitrogen in the autoclave, and then 2 mL of a mixed solvent of toluene and t-BuOH in a ratio of 3:1, and isophorone 1 (0.15 mL, 1 mmol) were added. The reaction was carried out with stirring under a hydrogen pressure of 5.0 MPa at 50° C. for 17 hours. The reaction mixture was analyzed by using GC. The results indicated that the products shown in the scheme A, that is, 3,3,5-trimethylcyclohexanone 2 was obtained in a yield of 18% (optical purity 93% ee), 3,3,5-trimethylcyclohexanol 3 was obtained in a yield of 61% (dr: 93/7, optical purity of main diastereomer: 95% ee), and 3,3,5-trimethyl-2-cyclohexenol 4 was obtained in a trace amount, respectively.

Workup

customobtained in the same manner

Sources & evidence

ORD record: ord-a725c47cc9c54e3fb32e2be660ed47fa
Source dataset: uspto-grants-2011_03
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07902110B2

Reaction notes

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