Dichloromethane → HCID 58208606, compound

HRID 2168172Notes

Reaction equation

HRID 2168172 reaction equation
[Br-:1].[Li+].[OH:3][C@@H:4]1[C@H:8]2[N:9]([C:23]([O:25][C:26]([CH3:29])([CH3:28])[CH3:27])=[O:24])[CH2:10][C@@H:11](OS(C3C=CC(C)=CC=3)(=O)=O)[C@H:7]2[O:6][CH2:5]1.C(Cl)Cl>CN(C=O)C>[Br:1][C@H:11]1[CH2:10][N:9]([C:23]([O:25][C:26]([CH3:29])([CH3:28])[CH3:27])=[O:24])[C@@H:8]2[C@@H:4]([OH:3])[CH2:5][O:6][C@H:7]12

Participants

5

Reactant 3

HCID 6344DichloromethaneHCID 82050Lithium BromideHCID 59343397(3R,3aR,6R,6aS)-tert-Butyl 3-hydroxy-6-(tosyloxy)tetrahydro-2H-furo[3,2-b]pyrrole-4(5H)-carboxylate

Product 1

HCID 58208606HCID 58208606, compoundYield 52.6%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
130 °C

Procedure

Lithium bromide (11.51 g, 132 mmol) was added to a stirred solution of tosylate (35b) (5.28 g, 13.2 mmol) in anhydrous DMF (75 mL) and the mixture heated at 130° C. for 4 hours. The black solution was left to cool to ambient temperature then reduced in vacuo. The residue was taken into DCM (100 mL) and washed with H2O (100 mL). The organic layer was dried (Na2SO4), filtered and reduced in vacuo to leave a black tar (Yield 3.3 g). Flash chromatography over silica, eluting with ethyl acetate:heptane mixtures 5:95 to 30:70 gave bromide (111) (2.14 g, 52.6%) as a pale green solid. TLC (Rf=0.4, EtOAc:heptane 3:1), analytical HPLC main peak, Rt=9.34 min., HPLC-MS 252.1/254.1 [M+H−56]+, 308.1/310.1 [M+H]+; 330.0/332.0 [M+Na]+; [α]D22−90.2° (c=2.33, CHCl3); δC (125 MHz, CDCl3) 28.35/28.44 ((CH3)3C), 48.26/48.75 (BrCHCH), 53.48/54.14 (BocNCH2), 67.78/68.29 (BocNCH), 75.48/75.63 (OCH2CHOH), 75.24/76.08 (OCH2CHOH), 80.78/81.07 ((CH3)3C quarternary), 87.01/87.85 (BrCHCH), 153.83/154.61 (Boc C═O).

Workup

  1. waitThe black solution was left
  2. temperatureto cool to ambient temperature
  3. washwashed with H2O (100 mL)
  4. dry with materialThe organic layer was dried (Na2SO4)
  5. filtrationfiltered
  6. customto leave a black tar (Yield 3.3 g)
  7. washFlash chromatography over silica, eluting with ethyl acetate

Sources & evidence

ORD record
ord-5628a3cdb8624f4baa6a40b1b975be53
Source dataset
uspto-grants-2015_06
Patent number
US09045492B2

Reaction notes

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