2-Bromo-1,3,2-benzodioxaborole → HCID 86686475, compound

HRID 513255Notes

Reaction equation

HRID 513255 reaction equation
B1(Br)OC2C(=CC=CC=2)O1.[OH:11][C:12]1[C:13]2[C:14](=[O:45])[CH2:15][CH2:16][C@H:17]([O:35][CH2:36][C:37]3[CH:42]=[CH:41][C:40]([O:43][CH3:44])=[CH:39][CH:38]=3)[C:18]=2[C:19]([O:33][CH3:34])=[C:20]2[C:25]=1[C:24]([O:26]COC)=[C:23]([CH:30]=[O:31])[C:22]([CH3:32])=[CH:21]2>ClCCl.C(=O)(O)[O-].[Na+]>[OH:26][C:24]1[C:25]2[C:20](=[C:19]([O:33][CH3:34])[C:18]3[C@@H:17]([O:35][CH2:36][C:37]4[CH:42]=[CH:41][C:40]([O:43][CH3:44])=[CH:39][CH:38]=4)[CH2:16][CH2:15][C:14](=[O:45])[C:13]=3[C:12]=2[OH:11])[CH:21]=[C:22]([CH3:32])[C:23]=1[CH:30]=[O:31]

Participants

5

Reactant 2

HCID 35523842-Bromo-1,3,2-benzodioxaboroleHCID 86686473HCID 86686473, compound

Product 1

HCID 86686475HCID 86686475, compoundYield 82.9%

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolvent3×HCID 516892Sodium BicarbonateSolvent

Conditions

Temperature
23 °C

Procedure

A solution of B-bromocatecholborane (418 mg, 2.10 mmol, 2.0 equiv) in dichloromethane (15 mL) was added to a solution of (S)-9-hydroxy-10-methoxy-5-(4-methoxybenzyloxy)-1-(methoxymethoxy)-3-methyl-8-oxo-5,6,7,8-tetrahydroanthracene-2-carbaldehyde (490 mg, 1.05 mmol, 1 equiv) in dichloromethane (15 mL) at −78° C. After 50 min, the reaction mixture was diluted with saturated aqueous sodium bicarbonate solution (25 mL) and dichloromethane (100 mL). The cooling bath was removed, and the partially frozen mixture was allowed to warm to 23° C. The biphasic mixture was diluted with 0.2 M aqueous sodium hydroxide solution (100 mL). The layers were separated. The aqueous layer was extracted with dichloromethane (100 mL). The organic layers were combined. The combined solution was washed sequentially with 0.1 M aqueous hydrochloric acid solution (100 mL), water (2×100 mL), then saturated aqueous sodium chloride solution (100 mL) and the washed solution was dried over sodium sulfate. The dried solution was filtered and the filtrate was concentrated to provide 380 mg of the product, (S)-1,9-dihydroxy-10-methoxy-5-(4-methoxybenzyloxy)-3-methyl-8-oxo-5,6,7,8-tetrahydroanthracene-2-carbaldehyde, as a yellow foam (86%). 1H NMR (500 MHz, CDCl3): 15.89 (br s, 1H), 12.81 (br s, 1H), 10.51 (s, 1H), 7.27-7.26 (m, 3H), 6.86 (d, 2H, J=9.2 Hz), 5.14 (app s, 1H), 4.62 (d, 1H, J=11.0 Hz), 4.51 (d, 1H, J=11.0 Hz), 3.85 (s, 3H), 3.80 (s, 3H), 3.21 (m, 1H), 2.73 (s, 3H), 2.62 (m, 1H), 2.54 (m, 1H), 2.07 (m, 1H). 13C NMR (125 MHz, CDCl3): 204.4, 192.7, 166.6, 164.3, 159.3, 144.4, 142.7, 137.9, 130.4, 130.2, 129.4, 114.9, 114.2, 113.9, 113.8, 109.4, 70.4, 67.1, 62.8, 55.3, 31.8, 26.5. FTIR, cm−1 (thin film): 3316 (br w), 2938 (m), 1678 (m), 1610 (s), 1514 (m), 1393 (m), 1246 (s). HRMS (ESI): Calcd for (C25H24O7+Na)+ 459.1414; Found 459.1354. TLC (50% ethyl acetate-hexanes): Rf=0.30 (CAM).

Workup

  1. customThe cooling bath was removed
  2. additionThe biphasic mixture was diluted with 0.2 M aqueous sodium hydroxide solution (100 mL)
  3. customThe layers were separated
  4. extractionThe aqueous layer was extracted with dichloromethane (100 mL)
  5. washThe combined solution was washed sequentially with 0.1 M aqueous hydrochloric acid solution (100 mL), water (2×100 mL)
  6. dry with materialsaturated aqueous sodium chloride solution (100 mL) and the washed solution was dried over sodium sulfate
  7. filtrationThe dried solution was filtered
  8. concentrationthe filtrate was concentrated

Sources & evidence

ORD record
ord-3faaec0dcb2549c0b900909055f788c8
Source dataset
uspto-grants-2015_08
Patent number
US09102697B2

Reaction notes

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