Dimethyl Sulfoxide → Boc-Tyr(Bzl)-aldehyde

HRID 1585300Notes

Reaction equation

HRID 1585300 reaction equation
C(Cl)(=O)C(Cl)=O.CS(C)=O.[C:11]([NH:18][C@H:19]([CH2:35][OH:36])[CH2:20][C:21]1[CH:26]=[CH:25][C:24]([O:27][CH2:28][C:29]2[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=2)=[CH:23][CH:22]=1)([O:13][C:14]([CH3:17])([CH3:16])[CH3:15])=[O:12].C(N(CC)CC)C.OS([O-])(=O)=O.[K+]>C(Cl)Cl.CCCCCC>[C:11]([NH:18][C@H:19]([CH:35]=[O:36])[CH2:20][C:21]1[CH:22]=[CH:23][C:24]([O:27][CH2:28][C:29]2[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=2)=[CH:25][CH:26]=1)([O:13][C:14]([CH3:16])([CH3:15])[CH3:17])=[O:12]

Participants

8

Reactant 5

HCID 679Dimethyl SulfoxideHCID 8471TriethylamineHCID 65578Oxalyl chlorideHCID 516920Potassium bisulfateHCID 7019534Boc-tyr(bzl)-OL

Product 1

HCID 7015729Boc-Tyr(Bzl)-aldehyde

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolvent4×HCID 8058HexaneSolvent

Conditions

Temperature
0 °C

Procedure

4.76 g (37.5 mmol) of oxalyl chloride in 33.6 ml of methylene chloride are treated dropwise, at -60° C. and under a N2 atmosphere, with a solution of 3.5 ml (49 mmol) of DMSO in 60 ml of methylene chloride. After the mixture has been stirred for 15 min, 8.94 g (25 mmol) of (S)-N-Boc-(p-benzyloxyphenylalaninol) in 150 ml of methylene chloride are added, and this mixture is subsequently stirred for about 25 min. 14 ml (100 mmol) of triethylamine in 30 ml of methylene chloride are then added and the mixture is stirred for 30 min. 222 ml of a 20% of a KHSO4 solution and 187 ml of hexane are added, and the mixture is warmed to 0° C. The aqueous phase is separated off and extracted 2× with ethyl acetate. The organic phases are washed with saturated NaHCO3 solution and saline, dried with Na2SO4 and evaporated to give the title compound: TLC Rf (C)0.71; 1H-NMR (200 MHz, CDCl3): 1.44 (s, 9H), 3.06 (d, J=6 Hz, 2H), 4.39 (m, 1H), 5.03 (s +sb, H2C--O+HN), 6.86-6.98 and 7.03-7.15 (2m, each 2H), 7.30-7.48 (m, 5H), 9.62 (s, 1H).

Workup

  1. stirringthis mixture is subsequently stirred for about 25 min
  2. stirringthe mixture is stirred for 30 min
  3. customThe aqueous phase is separated off
  4. extractionextracted 2× with ethyl acetate
  5. washThe organic phases are washed with saturated NaHCO3 solution and saline
  6. dry with materialdried with Na2SO4
  7. customevaporated

Sources & evidence

ORD record
ord-feb59d0469844bfeb29c4f9c8b9bff8c
Source dataset
uspto-grants-1999_08
Patent number
US05935976

Reaction notes

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