Methane → O-benzyl-L-tyrosine

HRID 874084Notes

Reaction equation

HRID 874084 reaction equation
O[NH:2][C@H:3]([C:19](N)=[O:20])[CH2:4][C:5]1[CH:10]=[CH:9][C:8]([O:11][CH2:12][C:13]2[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=2)=[CH:7][CH:6]=1.C(Cl)(Cl)=[O:23].C>C1COCC1>[NH2:2][C@H:3]([C:19]([OH:20])=[O:23])[CH2:4][C:5]1[CH:10]=[CH:9][C:8]([O:11][CH2:12][C:13]2[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=2)=[CH:7][CH:6]=1

Participants

5

Reactant 3

HCID 297MethaneHCID 6371PhosgeneHCID 131732573HCID 131732573, compound

Product 1

HCID 725701O-benzyl-L-tyrosineYield 65%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
50 °C

Procedure

HO-Tyr(Bzl)-NH2 (20.0 g, 105.7 mmol) was suspended in 300 mL of anhydrous THF and heated to 50° C. Phosgene (20% in toluene) (73.7 mL, 147.4 mmol) was added the amino acid suspension. The amino acid dissolved over the course of approx. 1 hr, forming a pale yellow solution. The solution was concentrated on the rotovap, transferred to a beaker, and hexane was added to precipitate the product. The off-white solid was isolated by filtration and dissolved in anhydrous THF. The solution was stirred over carbon black and subsequently filtered over a bed of Celite. An excess of hexane was added to the filtrate to precipitate the product. The NCA was isolated by filtration and dried in vacuo. 14.3 g (65% yield) of Tyr(Bzl) NCA was isolated as a off-white, solid. 1H NMR (d6-DMSO) δ 9.07 (1H), 7.49-7.29 (5H), 7.12-7.07 (2H), 6.98-6.94 (2H), 5.06 (2H), 4.74 (1H), 3.05-2.88 (2H) ppm.

Workup

  1. customforming a pale yellow solution
  2. concentrationThe solution was concentrated on the rotovap
  3. additionwas added
  4. customto precipitate the product
  5. customThe off-white solid was isolated by filtration
  6. filtrationsubsequently filtered over a bed of Celite
  7. additionAn excess of hexane was added to the filtrate
  8. customto precipitate the product
  9. customThe NCA was isolated by filtration
  10. customdried in vacuo

Sources & evidence

ORD record
ord-fa13eed48fe6426694c8991f7c7d7035
Source dataset
uspto-grants-2015_03
Patent number
US08980326B2

Reaction notes

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