Hydrochloric Acid → HCID 59013465, compound

HRID 1716978Notes

Reaction equation

HRID 1716978 reaction equation
Cl[C:2]([O:4][CH3:5])=[O:3].[Cl:6][C:7]1[CH:8]=[C:9]2[C:23](=[CH:24][C:25]=1[CH2:26][C:27]1[CH:32]=[CH:31][C:30]([CH2:33][CH3:34])=[CH:29][CH:28]=1)[C@:12]1([C@H:17]([OH:18])[C@@H:16]([OH:19])[C@H:15]([OH:20])[C@@H:14]([CH2:21][OH:22])[O:13]1)[CH2:11][CH2:10]2.Cl>C(Cl)Cl.N1C(C)=CC(C)=CC=1C>[C:2](=[O:3])([O:4][CH3:5])[O:22][CH2:21][C@H:14]1[O:13][C@@:12]2([C:23]3[C:9](=[CH:8][C:7]([Cl:6])=[C:25]([CH2:26][C:27]4[CH:28]=[CH:29][C:30]([CH2:33][CH3:34])=[CH:31][CH:32]=4)[CH:24]=3)[CH2:10][CH2:11]2)[C@H:17]([OH:18])[C@@H:16]([OH:19])[C@@H:15]1[OH:20]

Participants

6

Reactant 3

HCID 313Hydrochloric AcidHCID 6586Methyl chloroformateHCID 46871672HCID 46871672, compound

Product 1

HCID 59013465HCID 59013465, compound

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolventHCID 79532,4,6-TrimethylpyridineSolvent

Conditions

Temperature
-40 °C

Procedure

A solution of methyl chloroformate (114 mg, 1.20 mmol) in CH2Cl2 (0.5 mL) was added dropwise to a solution of (1S,3′R,4′S,5′S,6′R)-5-chloro-6-(4-ethylbenzyl)-6′-(hydroxymethyl)-2,3,3′,4′,5′,6′-hexahydrospiro[indene-1,2′-pyran]-3′,4′,5′-triol (compound AV) (418 mg, 1.00 mmol) in 2,4,6-collidine (5 mL) at −40° C. The whole was stirred at −40° C. for 1 h and at room temperature for 1.5 h. The reaction mixture was poured into ice-cooled 10% HCl and extracted with AcOEt. The organic layer was washed with saturated NaHCO3 and brine, dried over MgSO4, and evaporated. The residue was chromatographed on silica gel to give the acylated product BH (420 mg, 87%). 1H NMR (CD3OD, 300 MHz) δ 7.25 (s, 1H), 7.23 (s, 1H), 7.09 (m, 4H), 4.05 (s, 2H), 3.80 (m, 1H), 3.65 (s, 3H), 3.62-3.34 (m, 5H), 2.91 (dd, J=6.6, 7.8 Hz, 2H), 2.60 (q, J=7.8 Hz, 2H), 2.55 (dt, J=7.5, 13.2 Hz, 1H), 2.10 (dt, J=7.5, 13.2 Hz, 1H), 1.20 (t, J=7.8 Hz, 3H); MS ESI m/e 477 (M+1).

Workup

  1. additionThe reaction mixture was poured into ice-
  2. extractionextracted with AcOEt
  3. washThe organic layer was washed with saturated NaHCO3 and brine
  4. dry with materialdried over MgSO4
  5. customevaporated
  6. customThe residue was chromatographed on silica gel
  7. customto give the acylated product BH (420 mg, 87%)

Sources & evidence

ORD record
ord-cf04d557193d4c7d900058bda5f26e07
Source dataset
uspto-grants-2010_09
Patent number
US07803778B2

Reaction notes

Loading…