Dimethyldioxirane → HCID 6478909, compound

HRID 562503Notes

Reaction equation

HRID 562503 reaction equation
[Cl:1][C:2]1[C:7]2[CH2:8][C:9](=[O:22])[CH:10]=[CH:11][CH2:12][CH2:13][CH:14]=[CH:15][CH2:16][CH:17]([CH3:21])[O:18][C:19](=[O:20])[C:6]=2[C:5]([O:23]COCC)=[CH:4][C:3]=1[O:28]COCC.CC1(C)O[O:35]1>CC#N>[CH3:21][C@@H:17]1[O:18][C:19](=[O:20])[C:6]2[C:5]([OH:23])=[CH:4][C:3]([OH:28])=[C:2]([Cl:1])[C:7]=2[CH2:8][C:9](=[O:22])[CH:10]=[CH:11][CH2:12][CH2:13][C@H:14]2[O:35][C@@H:15]2[CH2:16]1

Participants

4

Reactant 2

HCID 115197DimethyldioxiraneHCID 66823681HCID 66823681, compound

Product 1

HCID 6478909HCID 6478909, compoundYield 101.6%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Procedure

To a solution of compound 2-112 (50 mg, 0.11 mmol) in CH3CN (5 mL) at 0° C. was added freshly made DMDO (275 μL, 0.11 mmol, 0.04 M in acetone) and the mixture was stirred for 1.5 h. After evaporation of the solvents under reduced pressure, purification by flash chromatography (silica gel, 0-70% Et2O/hexane gradient) afforded compound 2-122 (41 mg, 79%) as a 1:1 mixture of two diastereoisomers. 1H NMR (400 MHz, CDCl3, 25° C.): δ=7.12 (s, 1H), 7.11 (s, 1H), 6.90-6.76 (m, 2H), 6.11 (d, J=15.6 Hz, 1H), 6.05 (d, J=15.8 Hz, 1H), 5.37-5.27 (m, 6H), 5.26-5.21 (m, 4H), 4.14 (d, J=16.9 Hz, 1H), 4.12 (d, J=17.4 Hz, 1H), 4.04 (d, J=17.2 Hz, 1H), 3.82-3.70 (m, 9H), 2.81-2.78 (m, 1H), 2.74-2.72 (m, 1H), 2.67-2.62 (m, 2H), 2.38-2.11 (m, 8H), 2.05-2.03 (m, 1H), 2.03-2.00 (m, 1H), 1.74-1.60 (m, 2H), 1.41 (d, J=7.2 Hz, 3H), 1.39 (d, J=6.2 Hz, 3H), 1.27-1.22 (m, 12H); 13C NMR (100 MHz, CDCl3, 25° C.): δ=195.1 (×2), 166.7, 166.3, 154.9, 154.8, 154.0, 153.5, 147.8, 147.4, 132.9, 132.4, 129.1, 129.0, 119.7 (×2), 118.0, 117.9, 102.9, 102.8, 93.9 (×2), 93.6 (×2), 71.1, 70.4, 64.8 (×2), 64.6 (×2), 58.4, 57.6, 56.9, 55.1, 43.4 (×2), 39.0, 37.9, 29.9, 29.7, 27.9 (×2), 18.4, 18.0, 15.0 (×4); HRMS (ESI-TOF): m/z: calculated for C24H32ClO8: 483.1780, found 483.1814 [M+H+].

Workup

  1. customAfter evaporation of the solvents
  2. customunder reduced pressure, purification by flash chromatography (silica gel, 0-70% Et2O/hexane gradient)

Sources & evidence

ORD record
ord-1459e2493ae04637a94f724363a0cf6f
Source dataset
uspto-grants-2011_11
Patent number
US08067412B2

Reaction notes

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