Lithium Chloride → HCID 67124283, compound

HRID 406140Notes

Reaction equation

HRID 406140 reaction equation
O[C:2]1[C:7]2[C@@:8]3(O)[C@@:21]([O:25][CH3:26])([C@H:22](O)[CH2:23][C:6]=2[CH:5]=[C:4]([CH3:46])[C:3]=1[C:47]([O:49]C)=[O:48])[C:20](=[O:27])[C:19]1[C:10](=[CH:11][C:12]2[C:13](=[O:43])[C:14](NC4C(OC)C(O)C(OC)C(C)O4)=[CH:15][C:16](=[O:29])[C:17]=2[C:18]=1O)[C:9]3=[O:44].[Cl-].[Li+]>CS(C)=O>[CH3:26][O:25][C:21]12[C:20](=[O:27])[C:19]3[C:10](=[CH:11][C:12]4[C:13](=[O:43])[CH:14]=[CH:15][C:16](=[O:29])[C:17]=4[CH:18]=3)[C:9](=[O:44])[CH:8]1[C:7]1[CH:2]=[C:3]([C:47]([OH:49])=[O:48])[C:4]([CH3:46])=[CH:5][C:6]=1[CH2:23][CH2:22]2

Participants

4

Reactant 2

HCID 433294Lithium ChlorideHCID 67121455HCID 67121455, compound

Product 1

HCID 67124283HCID 67124283, compoundYield 19.9%

Reagents, catalysts & solvents 1

HCID 679Dimethyl SulfoxideSolvent

Procedure

To a solution of (6R,6aS,14aR)-methyl 1,6,8,14a-tetrahydroxy-11-(4-hydroxy-3,5-dimethoxy-6-methyltetrahydro-2H-pyran-2-ylamino)-6a-methoxy-3-methyl-7,9,12,14-tetraoxo-5,6,6a,7,9,12,14,14a-octahydrobenzo[a]tetracene-2-carboxylate (100 mg, 0.14 mmol) in DMSO (1 mL) was added lithium chloride (121 mg, 2.87 mmol). The reaction mixture was irradiated with microwaves at 120° C. for 21 min. The crude material was purified by preparative HPLC (10:90 acetonitrile/water to 100% acetonitrile with 0.05% TFA over 50 min) to afford (6R,6aS,14aR)-1,6,8,14a-tetrahydroxy-11-(2S,3R,4R,5R,6S)-4-hydroxy-3,5-dimethoxy-6-methyltetrahydro-2H-pyran-2-ylamino)-6a-methoxy-3-methyl-7,9,12,14-tetraoxo-5,6,6a,7,9,12,14,14a-octahydrobenzo[a]tetracene-2-carboxylic acid (12.0 mg, 12.5%) as a dark orange-red solid: 1H NMR (500 MHz, acetone-d6) δ 14.27 (s, 1H), 8.06 (s, 1H), 6.91 (d, J=8.0 Hz, 1H), 6.62 (s, 1H), 6.00 (s, 2H), 5.09-5.05 (m, 1H), 4.90-4.83 (m, 1H), 4.78-4.71 (m, 1H), 4.55-4.43 (m, 1H), 3.86-3.82 (m, 1H), 3.74 (s, 3H), 3.73-3.70 (m, 1H), 3.54 (s, 3H), 3.53-3.45 (m, 2H), 3.32 (s, 3H), 3.30-3.20 (m, 2H), 3.06 (t, J=9.1 Hz, 2H), 2.43 (s, 3H), 1.19 (d, J=6.0 Hz, 3H); MS (ESI+) m/z 684 (M+H); HPLC 93.4% (AUC), tR 11.84 min.

Workup

  1. customThe reaction mixture was irradiated with microwaves at 120° C. for 21 min
  2. customThe crude material was purified by preparative HPLC (10:90 acetonitrile/water to 100% acetonitrile with 0.05% TFA over 50 min)

Sources & evidence

ORD record
ord-ee9caacf30f7406eb3775eca993875f6
Source dataset
uspto-grants-2014_06
Patent number
US08754054B2

Reaction notes

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