Diisopropyl azodicarboxylate → HCID 117642877, compound

HRID 1507751Notes

Reaction equation

HRID 1507751 reaction equation
CC(OC(/N=N/C(OC(C)C)=O)=O)C.[P:15]([O-:32])([O:24][CH2:25][C:26]1[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=1)[O:16][CH2:17][C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1.[OH:33][CH2:34][CH2:35][CH2:36][O:37][CH2:38][C:39]([CH3:48])([CH3:47])[C:40]([O:42][C:43]([CH3:46])([CH3:45])[CH3:44])=[O:41].CC1C=CC(S(OCCCOCC2C=CC=CC=2)(=O)=O)=CC=1>C1COCC1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[CH2:17]([O:16][P:15]([O:33][CH2:34][CH2:35][CH2:36][O:37][CH2:38][C:39]([CH3:48])([CH3:47])[C:40]([O:42][C:43]([CH3:46])([CH3:45])[CH3:44])=[O:41])([O:24][CH2:25][C:26]1[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=1)=[O:32])[C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1

Participants

7

Reactant 4

HCID 5363146Diisopropyl azodicarboxylateHCID 11151365HCID 11151365, compoundHCID 21904359DibenzylphosphiteHCID 89625032HCID 89625032, compound

Product 1

HCID 117642877HCID 117642877, compoundYield 76.8%

Reagents, catalysts & solvents 2

HCID 11776TriphenylphosphineCatalystHCID 8028TetrahydrofuranSolvent

Procedure

DIAD (1.36 mL, 6.97 mmol) was added dropwise to a stirred solution of PPh3 (76 mg, 0.30 mmol), dibenzyl phosphite (1.94 g, 6.97 mmol) and tert-butyl 3-(3-hydroxypropoxy)-2,2-dimethylpropanoate (53) (1.08 g, 4.65 mmol) [prepared using the same procedure as Example F1 steps (ii)-(iii) using 3-(benzyloxy)propyl 4-methylbenzenesulfonate in step (ii)] in THF (100 mL) at 0° C. The reaction was allowed to warm to RT and stirred for 16 h, and the volatiles were removed in vacuo. The crude product was purified by silica gel chromatography (120 g, 0-60% EtOAc in isohexane) to afford tert-butyl 3-(3-((bis(benzyloxy)phosphoryl)oxy)propoxy)-2,2-dimethylpropanoate (54) (1.76 g, 54%) as a clear colourless oil: m/z 515 (M+Na)+ (ES+). 1H NMR (400 MHz, DMSO-d6) δ: 7.40-7.35 (m, 10H), 5.07-4.96 (m, 4H), 4.04-3.92 (m, 2H), 3.39 (t, J=6.2 Hz, 2H), 3.28 (s, 2H), 1.77 (quin, J=6.2 Hz, 2H), 1.35 (s, 9H), 1.02 (s, 6H).

Workup

  1. customprepared
  2. customat 0° C
  3. customthe volatiles were removed in vacuo
  4. customThe crude product was purified by silica gel chromatography (120 g, 0-60% EtOAc in isohexane)

Sources & evidence

ORD record
ord-3463205e96354303ac02d1412e37880e
Source dataset
uspto-grants-2015_12
Patent number
US09221756B2

Reaction notes

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