Peracetic Acid → HCID 58042462, compound

3-Chloro-2-(tetrahydro-2H-pyran-4-yloxy)pyridine (Preparation 25, 1.40 g, 6.55 mmol) and bis(pinacolato)diboron (6.65 g, 13.11 mmol) were dissolved in heptane (30 mL) and degassed five times with nitrogen. Di-tert-butyldipyridyl (0.017 mg, 0.066 mmol) was added, followed by (1,5-cyclooctadiene)(methoxy)lridium(I) dimer (0.022 mg, 0.033 mmol). The mixture was again degassed five times with nitrogen and stirred at room temperature for 18 hours. The reaction was quenched by slow addition of methanol (50 mL) and concentrated in vacuo to afford a red/orange oil, which was purified by silica gel chromatography eluting with 66% EtOAc in heptane to afford an impure product. The obtained crude product was dissolved in and a 1:1 mixture of acetic acid:water (30 mL) was added and cooled to 5° C. (ice bath). Peracetic acid was slowly added over 2 minutes. The reaction was stirred at 5° C. for 30 minutes, then a 1 M aqueous solution of sodium thiosulfate was added. The reaction was allowed to slowly warm to room temperature over 30 minutes, diluted with water (50 mL) and extracted with EtOAc (3×50 mL). The combined organics were then dried over magnesium sulfate, filtered, and concentrated in vacuo to afford a yellow oil, which was purified by silica gel chromatography eluting with EtOAc to afford an off-white solid. The solid was triturated in heptane to afford the title compound as a white solid (0.483 g, 43%):

1. customdegassed five times with nitrogen
2. additionDi-tert-butyldipyridyl (0.017 mg, 0.066 mmol) was added
3. customThe mixture was again degassed five times with nitrogen
4. customThe reaction was quenched by slow addition of methanol (50 mL)
5. concentrationconcentrated in vacuo
6. customto afford a red/orange oil, which
7. customwas purified by silica gel chromatography
8. washeluting with 66% EtOAc in heptane
9. customto afford an impure product
10. customThe obtained crude product
11. dissolutionwas dissolved in and
12. temperaturecooled to 5° C. (ice bath)
13. stirringThe reaction was stirred at 5° C. for 30 minutes
14. temperatureto slowly warm to room temperature over 30 minutes
15. extractionextracted with EtOAc (3×50 mL)
16. dry with materialThe combined organics were then dried over magnesium sulfate
17. filtrationfiltered
18. concentrationconcentrated in vacuo
19. customto afford a yellow oil, which
20. customwas purified by silica gel chromatography
21. washeluting with EtOAc
22. customto afford an off-white solid
23. customThe solid was triturated in heptane

ORD record

ord-ea7ccb99586449609a2478c5696a5ced

Source dataset

uspto-grants-2013_11

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US08592629B2