Sodium Carbonate → HCID 15454920, compound

HRID 2287530Notes

Reaction equation

HRID 2287530 reaction equation
[NH2:1][C@H:2]1[CH2:7][C@H:6]([C:8]([O:10][CH3:11])=[O:9])[CH2:5][N:4]([C:12]([O:14][CH2:15][C:16]2[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=2)=[O:13])[C@H:3]1[C:22]1[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=1.[CH3:28][O:29][C:30]1[CH:37]=[CH:36][C:35]([O:38][C:39]([F:42])([F:41])[F:40])=[CH:34][C:31]=1[CH:32]=O.[BH-](OC(C)=O)(OC(C)=O)OC(C)=O.[Na+].C([O-])([O-])=O.[Na+].[Na+]>C(Cl)Cl>[CH2:15]([O:14][C:12]([N:4]1[CH2:5][C@@H:6]([C:8]([O:10][CH3:11])=[O:9])[CH2:7][C@H:2]([NH:1][CH2:32][C:31]2[CH:34]=[C:35]([O:38][C:39]([F:40])([F:41])[F:42])[CH:36]=[CH:37][C:30]=2[O:29][CH3:28])[C@@H:3]1[C:22]1[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=1)=[O:13])[C:16]1[CH:17]=[CH:18][CH:19]=[CH:20][CH:21]=1

Participants

6

Reactant 4

HCID 10340Sodium CarbonateHCID 27833642-Methoxy-5-(trifluoromethoxy)benzaldehydeHCID 5049666Sodium triacetoxyborohydride2×HCID 15454918HCID 15454918, compound

Product 1

HCID 15454920HCID 15454920, compoundYield 125.3%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a stirred solution of (2S*,3S*,5S*)-3-amino-1-benzyloxycarbonyl-5-methoxycarbonyl-2-phenylpiperidine (0.79 g, 2.16 mmol) and 2-methoxy-5-trifluoromethoxybenzaldehyde (0.59 g, 2.70 mmol) in CH2Cl2 (25.0 ml) was added NaB(OAc)3H (0.69 g, 3.24 mmol) potionwise at room temperature. The turbid reaction mixture was stirred at room temperature for 3 hours; the NaB(OAc)3H added dissolved gradually with stirring, and the turbidity of the reaction mixture decreased. sat. Na2CO3 aq. solution was added, and from the mixture was separated the CH2C2 layer. The aqueous layer was extracted with CH2Cl2. The combined CH2Cl2 layer and extracts were dried (Na2SO4), and concentrated in vacuo to give a pale yellow oil (1.55 g). This was flash chromatographed over SiO2 (Merck Kieselgel 60, 32.0 g). Elution with CH2Cl2 --MeOH (300:1/200:1) gave title compound (1.15 g, 93.1%) as a colorless syrup, which crystallized spontaneously on standing in a refrigerator. This was recrystallized from (i-Pr)2O to give analytically pure title compound (1.058 g, 85.3%). mp 93.5-95.0 C. (fine colorless needles); IRmax (nujol): 1730(s), 1700(s), 1610(w), 1498(s), 1220(s), 1147(s), 1110(s), 1080(s), 1055(s), 1028(s), 742(s), 730(s), 703(s), 695(s) cm-1 ; 1H-NMR δ: 7.43-7.23(m, 9H), 7.21(br.s, 1H), 7.09-7.00(m, 2H), 6.73(d, J=9.2 Hz, 1H), 5.39(br.d, J=5.3 Hz, 1H), 5.16(d, J=12.5 Hz, 1H), 5.02(d, J=12.5 Hz, 1H), 4.50(dd, J=13.7, 1.8 Hz, 1H), 3.79(d, J=13.9 Hz, 1H), 3.68(d, J=13.9 Hz, 1H), 3.63(s, 3H), 3.54(dd, J=13.7, 5.5 Hz, 1H), 3.28(ddd, J=10.2, 5.5 4.8 Hz, 1H), 2.89-2.28(m, 1H), 2.24-2.01(m, 1H), 1.54(br.s, 2H) ppm.

Workup

  1. customThe turbid reaction mixture
  2. dissolutiondissolved gradually
  3. stirringwith stirring
  4. customfrom the mixture was separated the CH2C2 layer
  5. extractionThe aqueous layer was extracted with CH2Cl2
  6. dry with materialThe combined CH2Cl2 layer and extracts were dried (Na2SO4)
  7. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-7fba011e550643fab3886e1fb065af9f
Source dataset
uspto-grants-2000_07
Patent number
US06083943

Reaction notes

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