Methyl iodide → HCID 11207350, compound

Temperature

-100 °C

A solution of alcohol 29 (887 mg, 3.82 mmol) in THF (50 mL) was cooled to −78° C., and 3.20 mL of n-BuLi (2.5 M in hexanes, 8.00 mmol) was added dropwise. The mixture was slowly brought to −7° C. over 1 h, and stirred at this temperature for 10 min. It was then cooled to −100° C. in a THF-liquid N2 bath. To this cold dark orange solution was slowly added a solution of MeI (0.72 mL, 11.56 mmol) in THF (5 mL) over 30 min via syringe pump. The resulting light yellow solution was warmed to −60° C. prior to quenching with saturated aqueous NH4Cl. After warming to room temperature, the two layers were separated, and the aqueous layer was extracted with EtOAc (3×30 mL). The combined organic layers were washed with brine, and dried over Na2SO4. Flash column chromatography (EtOAc/hexanes; 1:4) afforded 660 mg (70% yield) of 31 as a white solid. mp 81.5-83.5° C.; [α]20D=+407.8 (c=0.55CH2Cl2); 1H NMR (CDCl3, 300 MHz) δ 7.20-7.35 (m, 5H), 6.27 (d, J=5.4 Hz, 1H), 5.98 (br d, J=10.8 Hz, 1H), 5.75 (dd, J=4.5 Hz, 10.8 Hz), 3.79 (dd, J=2.7 Hz, 6.0 Hz, 1H), 2.55 (m, 1H), 2.45 (m, 1H), 1.65 (br s, 1H), 1.25 (d, J=7.5 Hz, 3H), 1.20 (d, J=6.9 Hz, 3H); 13C NMR (CDCl3, 75 MHz) δ 140.9, 138.7, 136.1, 130.5, 130.2, 129.9, 129.2, 126.7, 84.7, 43.5, 38.1, 19.4, 17.6; Analytical. Calculated for C15H18OS: C, 73.13; H, 7.36. Found: C, 72.42; H, 7.22.

1. temperatureThe resulting light yellow solution was warmed to −60° C.
2. customto quenching with saturated aqueous NH4Cl
3. temperatureAfter warming to room temperature
4. customthe two layers were separated
5. extractionthe aqueous layer was extracted with EtOAc (3×30 mL)
6. washThe combined organic layers were washed with brine
7. dry with materialdried over Na2SO4

ORD record

ord-336aa01dbe29406f86a022344008d3f8

Source dataset

uspto-grants-2009_03

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US07501535B2