4-(Hydroxymethyl)benzeneboronic acid → HCID 89519193, compound

HRID 2283170Notes

Reaction equation

HRID 2283170 reaction equation
[OH:1][CH2:2][C:3]1[CH:8]=[CH:7][C:6](B(O)O)=[CH:5][CH:4]=1.[Cl:12][CH:13]([Cl:32])[C:14]([N:16]1[C@H:20]([CH2:21][F:22])[C@@H:19]([C:23]2[CH:28]=[CH:27][C:26](I)=[CH:25][CH:24]=2)[O:18][C:17]1([CH3:31])[CH3:30])=[O:15]>C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.O>[Cl:12][CH:13]([Cl:32])[C:14]([N:16]1[C@H:20]([CH2:21][F:22])[C@@H:19]([C:23]2[CH:28]=[CH:27][C:26]([C:6]3[CH:7]=[CH:8][C:3]([CH2:2][OH:1])=[CH:4][CH:5]=3)=[CH:25][CH:24]=2)[O:18][C:17]1([CH3:31])[CH3:30])=[O:15]

Participants

5

Reactant 2

HCID 27347064-(Hydroxymethyl)benzeneboronic acidHCID 86695394(4S,5R)-3-(dichloroacetyl)-4-(fluoromethyl)-5-(4-iodophenyl)-2,2-dimethyl-1,3-oxazolidine

Product 1

HCID 89519193HCID 89519193, compoundYield 67%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 962WaterSolvent

Conditions

Temperature
80 °C

Procedure

A mixture of (4-(hydroxymethyl)phenyl)boronic acid (2.5 g, 16.8 mmol), 2,2-dichloro-1-((4S,5R)-4-(fluoromethyl)-5-(4-iodophenyl)-2,2-dimethyloxazolidin-3-yl)ethanone (5.0 g, 11.21 mmol) Cs2CO3 (7.3 g, 22.4 mmol) and Pd(PPh3)4 (1.3 g, 1.12 mmol) dioxane (100 mL) and water (30 mL) is heated at 80° C. for 4 hours under nitrogen. Reaction is cooled, washed with water (30 mL), dried over Na2SO4, and concentrated to a syrup. Crude compound adsorbed on celite and purified on silica gel column eluting from 10% to 50% EtOAC/heptane to get the title compound (3.2 g): 1H NMR (400 MHz, CDCl3) δ: (1H NMR) 1.68 (bs, 3H), 1.75 (bs, 3H), 4.50-4.75 (m, 2H), 4.78 (d, 2H, J=6.0 Hz) 4.80-4.87 (m, 0.5H) 5.0-5.13 (br, 1H), 5.14-5.3 (m, 0.5H), 6.2-6.41 (br, 1H), 7.48 (d, 1H, J−8 Hz), 7.53 (d, 1H, J=8.0 Hz), 7.62 (d, 1H, J=8.0 Hz), 7.65 (d, 1H, J=8.0 Hz), (m/z (Cl) 368 [M-(CH3)2CO].

Workup

  1. customReaction
  2. temperatureis cooled
  3. washwashed with water (30 mL)
  4. dry with materialdried over Na2SO4
  5. concentrationconcentrated to a syrup
  6. custompurified on silica gel column
  7. washeluting from 10% to 50% EtOAC/heptane

Sources & evidence

ORD record
ord-f5964d1a53894b249381ba01291128be
Source dataset
uspto-grants-2015_09
Patent number
US09145355B2

Reaction notes

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