Diethyl azodicarboxylate → HCID 23317256, compound

HRID 1982107Notes

Reaction equation

HRID 1982107 reaction equation
N[C@H](C(NC(C([O-])=O)C([O-])=O)=O)CO.CCOC(/N=N/C(OCC)=O)=O.[CH2:27]([O:29][C:30]([CH:32]([NH-:38])[C:33]([O:35][CH2:36][CH3:37])=[O:34])=[O:31])[CH3:28].[C:39]([N:49]1[CH2:51][CH:50]1[C:52](O)=[O:53])([O:41][CH2:42][C:43]1[CH:48]=[CH:47][CH:46]=[CH:45][CH:44]=1)=[O:40]>C1COCC1>[CH2:27]([O:29][C:30]([CH:32]([C:33]([O:35][CH2:36][CH3:37])=[O:34])[N:38]1[CH2:51][CH:50]([NH:49][C:39]([O:41][CH2:42][C:43]2[CH:48]=[CH:47][CH:46]=[CH:45][CH:44]=2)=[O:40])[C:52]1=[O:53])=[O:31])[CH3:28]

Participants

5

Reactant 3

HCID 5462977Diethyl azodicarboxylateHCID 86740843HCID 86740843, compoundHCID 86740844HCID 86740844, compound

Product 1

HCID 23317256HCID 23317256, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

The Cbz protected serylaminomalonate (0.5 g, 1.2 mmoles) and 0.33 g (1.2 mmoles) of TPP in 30 mL of THF were treated with 0.2 mL (1.29 mmoles) of DEAD for 1 hour at R.T. The mixture was chromatographed as above, yielding 0.29 g (63% mass recovery) of the mixture of the title compound and 1-Cbz-2-carboxyaziridine diethoxycarbonylmethylamide. 105 mg of the mixture was prep TLC'd (silica, 2 mm, ether/hexanes, 4 times). The title compound eluted first, and after evaporation, 64.1 mg (0.18 mmoles, 15%) was isolated as an oil. IR (neat) 1770, 1750, 1715. NMR 1.13-1.33 (6H, m), 3.56-3.7 (2H, m), 4.0-4.4 (4H, m), 4.6-4.8 (1H, m), 5.1 (3H, 2 overlapping singlets), 5.8-6 (1H, m), 7.4 (5H, s). The aziridine side product: 39.5 mg (0.1 mmoles, 8.7%) IR (neat) 1760, 1730. NMR 1.16-1.33 (6H, t), 2.4-2.6 (2H, dd), 3.06-3.16 (1H, dd), 4.1-4.4 (4H, dq), 4.5-4.8 (1H, b), 5.06-5.1 (1H, d), 5.13 (2H, s), 7.4 (5H, s).

Workup

  1. customThe mixture was chromatographed as above,
  2. customyielding

Sources & evidence

ORD record
ord-d9bbdd6d40b4487a8b06e74e07ede3ae
Source dataset
uspto-grants-1986_06
Patent number
US04595532

Reaction notes

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