Reaction #609363

Reaction equation

Hg(OAc)2

KCl

(2R,3R,4R,5S)-1,3,4-tris(benzyloxy)hept-6-ene-2,5-diol

→

(((2S,3R,4R,5R,6R)-4,5-bis(benzyloxy)-6-((benzyloxy)methyl)-3-hydroxytetrahydro-2H-pyran-2-yl)methyl)mercury(II) chloride

Yield 85.2%

Solvents

EtOAc

THF

water

THF

Conditions

Workup

1. 1
   workup.WAITAfter 30 minutes
2. 2
   Washwashed with water (2×100 mL)
3. 3
   DryingThe organic phase was then dried over anhydrous sodium sulfate
4. 4
   Filtrationfiltered
5. 5
   Concentrationconcentrated in vacuo
6. 6
   Otherto give an oil
7. 7
   OtherThis oil was purified by silica gel chromatography
8. 8
   Washeluting with 20% EtOAc in hexane

Procedure

To a suspension of Hg(OAc)2 (12.4 g, 38.8 mmol, 1.0 equiv) in dry THF (174 mL), under nitrogen, was added a solution of (2R,3R,4R,5S)-1,3,4-tris(benzyloxy)hept-6-ene-2,5-diol (17.4 g, 38.8 mmol, 1.0 equiv) in dry THF (87 mL). The reaction mixture was stirred at room temperature for 16 hours and then a solution of KCl (4.3 g, 58.2 mmol, 1.5 equiv) in water (20 mL) was added. After 30 minutes, the reaction mixture was diluted with EtOAc (150 mL) and then washed with water (2×100 mL). The organic phase was then dried over anhydrous sodium sulfate, filtered, and concentrated in vacuo to give an oil. This oil was purified by silica gel chromatography, eluting with 20% EtOAc in hexane, to give (((2S,3R,4R,5R,6R)-4,5-bis(benzyloxy)-6-((benzyloxy)methyl)-3-hydroxytetrahydro-2H-pyran-2-yl)methyl)mercury(II) chloride as a pale yellow oil (22.6 g, 85%). 1H NMR (400 MHz, CDCl3) δ 7.37-7.29 (m, 11H), 7.27-7.24 (m, 2H), 7.23-7.19 (m, 2H), 4.62-4.48 (m, 6H), 4.37 (dd, J=7.1, 3.7 Hz, 1H), 4.15 (dt, J=6.3, 4.1 Hz, 1H), 3.82 (dd, J=10.1, 6.7 Hz, 1H), 3.72 (q, J=2.8, 1.9 Hz, 1H), 3.65-3.59 (m, 2H), 3.53-3.47 (m, 2H), 2.06-2.00 (m, 1H), 1.77 (dd, J=12.1, 3.8 Hz, 1H). ESI (M+1-Cl) 647.1; calc for C28H31ClHgO5 684.2.

Source