Methanol → N-(tert-Butoxycarbonyl)-2(S)-phenylglycinbromide

HRID 1275484Notes

Reaction equation

HRID 1275484 reaction equation
[C:1]([O:5][C:6]([NH:8][C@@H:9]([C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1)[CH2:10][OH:11])=[O:7])([CH3:4])([CH3:3])[CH3:2].C(Br)(Br)(Br)[Br:19].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.CO>CCOCC.CCCCCC.C(Cl)Cl.CCN(CC)CC>[C:1]([O:5][C:6]([NH:8][C@@H:9]([C:12]1[CH:13]=[CH:14][CH:15]=[CH:16][CH:17]=1)[C:10]([Br:19])=[O:11])=[O:7])([CH3:4])([CH3:2])[CH3:3]

Participants

9

Reactant 4

HCID 887MethanolHCID 11205Carbon tetrabromideHCID 11776TriphenylphosphineHCID 7016462(S)-2-((N-tert-Butoxycarbonyl)amino)-2-phenylethanol

Product 1

HCID 20638624N-(tert-Butoxycarbonyl)-2(S)-phenylglycinbromideYield 80%

Reagents, catalysts & solvents 4

HCID 3283Diethyl EtherSolvent2×HCID 6344DichloromethaneSolventHCID 8058HexaneSolventHCID 8471TriethylamineSolvent

Procedure

To a stirred solution of N-(tert-butoxycarbonyl)-2(S)-phenylglycinol (1.67 g, 7.0 mmol) and carbon tetrabromide (5.0 g, 15 mmol) in 35 mL of anhydrous ether was added a solution of triphenylphosphine (4.09 g, 15.4 mmol) in 25 mL of anhydrous ether at 0° C. The reaction mixture was stirred at room temperature for 12 h. The ether suspension was filtered with a sintered glass funnel containing a bed of celite. The ether filtrate was concentrated under reduced pressure to give a crude product. Flash chromatography (silica gel, 0.2% MeOH, 0.004% Et3N, 40% methylene chloride in hexane) afforded 1.68 g of product (80% yield) as a white solid, mp 108-109° C. 1H NMR (CDCl3) δ 1.431 (s, 9H, tert-Bu) 3.664 (s, 2H, BrCH2), 5.001 (s, 1H, NH), 5.272 (d, 1H, J=7.8 Hz, benzyl), 7.25-7.38 (m, 5H, aryl); 13C NMR (CDCl3) δ 28.24 (CH3) 37.00 (BrCH2), 54.80 (CMe3), 79.98 (NCH), 126.35 (aromatic), 127.88, 128.59, 139.40, 154.91.

Workup

  1. filtrationThe ether suspension was filtered with a sintered glass funnel
  2. additioncontaining a bed of celite
  3. concentrationThe ether filtrate was concentrated under reduced pressure
  4. customto give a crude product

Sources & evidence

ORD record
ord-017cf2a04eef4c3eb8963e5886689110
Source dataset
uspto-grants-2000_12
Patent number
US06162417

Reaction notes

Loading…