Triphenylphosphine → Methyl (R)-4-Chloro-3-hydroxybutyrate

HRID 1855231Notes

Reaction equation

HRID 1855231 reaction equation
[OH:1][C@@H:2]([CH2:8]O)[CH2:3][C:4]([O:6][CH3:7])=[O:5].C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C(=O)N([Cl:36])C(=O)C1>C(Cl)Cl>[Cl:36][CH2:8][C@H:2]([OH:1])[CH2:3][C:4]([O:6][CH3:7])=[O:5]

Participants

5

Reactant 3

HCID 11776TriphenylphosphineHCID 31398ChlorosuccinimideHCID 9877378methyl (3R)-3,4-dihydroxybutanoate

Product 1

HCID 10920707Methyl (R)-4-Chloro-3-hydroxybutyrateYield 26%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Conditions

Temperature
5 °C

Procedure

To a solution of (R)-methyl 3,4-dihydroxybutanoate (125.1 g, 0.93 mol) in CH2Cl2 (1.8 L) was added PPh3 (244.5 g, 0.93 mol) and slowly added NCS (124.2 g, 0.93 mol) under ice water cooling. The mixture was stirred at 5° C. for 20 min and then stirred for 18 h at room temperature. After evaporating the solvent, the residue was purified by column chromatography (P.E\E.A 20:1-5:1, gradient) to give (R)-methyl 4-chloro-3-hydroxybutanoate (33 g, 26% over 3 steps). 1H NMR (300 MHz, CDCl3) δ 4.18-4.25 (m, 1H), 3.68 (s, 3H), 3.55-3.60 (m, 2H), 3.32-3.33 (d, J=4.2 Hz, 1H), 2.52-2.68 (m, 2H).

Workup

  1. stirringstirred for 18 h at room temperature
  2. customAfter evaporating the solvent
  3. customthe residue was purified by column chromatography (P.E\E.A 20:1-5:1, gradient)

Sources & evidence

ORD record
ord-90a1c93a6b8e4932b8519de00d09528a
Source dataset
uspto-grants-2015_02
Patent number
US08962856B2

Reaction notes

Loading…