Boron Trichloride → HCID 131736382, compound

HRID 1055508Notes

Reaction equation

HRID 1055508 reaction equation
C([O:8][C@H:9]1[C@H:15]([O:16]CC2C=CC=CC=2)[C@@H:14]([O:24]CC2C=CC=CC=2)[C@:13]2([C:33]3[CH:38]=[CH:37][C:36]([Cl:39])=[C:35]([CH2:40][C:41]4[CH:46]=[CH:45][C:44]([O:47][CH2:48][CH3:49])=[CH:43][CH:42]=4)[CH:34]=3)[O:32][C@:10]1([CH:50]([OH:57])[C:51]#[C:52][Si:53]([CH3:56])([CH3:55])[CH3:54])[CH2:11][O:12]2)C1C=CC=CC=1.B(Cl)(Cl)Cl>ClCCl>[Cl:39][C:36]1[CH:37]=[CH:38][C:33]([C@@:13]23[O:32][C@:10]([CH:50]([OH:57])[C:51]#[C:52][Si:53]([CH3:56])([CH3:54])[CH3:55])([CH2:11][O:12]2)[C@@H:9]([OH:8])[C@H:15]([OH:16])[C@H:14]3[OH:24])=[CH:34][C:35]=1[CH2:40][C:41]1[CH:42]=[CH:43][C:44]([O:47][CH2:48][CH3:49])=[CH:45][CH:46]=1

Participants

4

Reactant 2

HCID 25135Boron TrichlorideHCID 131736383HCID 131736383, compound

Product 1

HCID 131736382HCID 131736382, compoundYield 100%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Conditions

Temperature
-78 °C

Procedure

To a solution of 1-[(1S,2S,3S,4R,5S)-2,3,4-tribenzyloxy-5-[4-chloro-3[(4-ethoxyphenyl)methyl]phenyl]-6,8-dioxabicyclo[3.2.1]octan-1-yl]-3-trimethylsilyl-prop-2-yn-1-ol 4a (0.65 g, 0.81 mmol) in dichloromethane (30 mL) was added dropwise boron trichloride (8.89 mL, 8.89 mmol, 1 M in dichloromethane) at −78° C. The mixture was stirred at −78° C. for 2 hours. After the addition, the reaction mixture was quenched with 5 mL of water and adjusted to pH 6-7 with saturated aqueous sodium hydrogen carbonate. The resulting mixture was extracted with dichloromethane (30 mL×3). The combined organic layers were washed with water (20 mL×2) and then saturated aqueous sodium chloride (20 mL×2), dried over anhydrous sodium sulfate and concentrated in vacuo to give the title compound 4b as red oil (0.43 g, 100%). The crude product was used in next step without further purification. The compound was characterized by the following spectroscopic data: 1H NMR (400 MHz, CDCl3) δ(ppm): 7.40 (m, 1H), 7.29 (m, 1H), 7.10 (d, 2H), 6.82 (d, 2H), 4.69 (t, 1H), 4.23 (m, 1H), 4.12 (m, 1H), 4.10 (m, 1H), 4.02 (m, 2H), 3.99 (m, 1H), 3.75 (d, 1H), 3.71 (d, 1H), 2.71 (d, 1H), 2.65 (d, 1H), 1.42 (t, 3H), 0.21 (s, 9H).

Workup

  1. additionAfter the addition
  2. customthe reaction mixture was quenched with 5 mL of water
  3. extractionThe resulting mixture was extracted with dichloromethane (30 mL×3)
  4. washThe combined organic layers were washed with water (20 mL×2)
  5. dry with materialsaturated aqueous sodium chloride (20 mL×2), dried over anhydrous sodium sulfate
  6. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-5c158dbba19e4c7cbdc7a3318bae6d03
Source dataset
uspto-grants-2016_07
Patent number
US09394329B2

Reaction notes

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