Methanol → HCID 10256786, compound

HRID 1784163Notes

Reaction equation

HRID 1784163 reaction equation
[C:1]1([S:7]([C:10]2[C@@H:11]([OH:28])[C@@H:12]([OH:27])[C@H:13]([CH3:26])[C@H:14]([O:18][Si:19]([C:22]([CH3:25])([CH3:24])[CH3:23])([CH3:21])[CH3:20])[C@@H:15]([CH3:17])[CH:16]=2)(=[O:9])=[O:8])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.N1C(C)=CC=CC=1C.[Si:37](OS(C(F)(F)F)(=O)=O)([C:40]([CH3:43])([CH3:42])[CH3:41])([CH3:39])[CH3:38].CO>C(Cl)Cl>[C:1]1([S:7]([C:10]2[C@@H:11]([OH:28])[C@@H:12]([O:27][Si:37]([C:40]([CH3:43])([CH3:42])[CH3:41])([CH3:39])[CH3:38])[C@H:13]([CH3:26])[C@H:14]([O:18][Si:19]([C:22]([CH3:23])([CH3:25])[CH3:24])([CH3:20])[CH3:21])[C@@H:15]([CH3:17])[CH:16]=2)(=[O:9])=[O:8])[CH:2]=[CH:3][CH:4]=[CH:5][CH:6]=1

Participants

6

Reactant 4

HCID 887MethanolHCID 79372,6-LutidineHCID 123564tert-Butyldimethylsilyl trifluoromethanesulphonateHCID 10025508HCID 10025508, compound

Product 1

HCID 10256786HCID 10256786, compoundYield 99.6%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Conditions

Temperature
-78 °C

Procedure

Compound 39 (77 mg, 0.18 mmol) was dissolved in dry methylene chloride (2.0 mL), and cooled to −78° C. To this cold solution were added 2,6-lutidine (32 μL, 0.27 mmol), followed by TBSOTf (50 μL, 0.22 mmol) under nitrogen. After stirring for 2 h at −78° C. (the reaction was monitored by TLC until completionusing a mixture of 1:1 EA/hexanes), 0.2 mL of methyl alcohol was then added to quench the excess of TBSOTf. The resulting solution was concentrated via rotary evaporation and the residue was purified by flash column chromatography (ethyl acetate/hexane, 1:5) to afford 97 mg (99% yield) of 52 as a white solid. mp 81.0-83.0° C.; [α]20D=+38.8 (c=1.3, CHCl3); 1H NMR (CDCl3, 300 MHz) δ 7.83-7.86 (m, 2H), 7.50-7.71 (m, 3H), 7.37 (d, J=7.8 Hz, 1H), 4.29 (br s, 1H), 3.81 (d, J=4.5 Hz, 1H), 3.56 (dd, J=2.1 Hz, 8.7 Hz, 1H), 2.79 (m, 1H), 2.53 (br s, 1H), 2.45 (m, 1H), 1.22 (d, J=7.2 Hz, 3H), 0.99 (d, J=7.2 Hz, 3H), 0.88 (s, 9H), 0.81 (s, 9H), 0.077 (s, 3H), 0.052 (s, 3H), −0.14 (s, 3H), −0.35 (s, 3H). 13C NMR (CDCl3, 75 MHz) δ 148.8, 139.6, 139.5, 133.5, 129.4, 128.1, 77.7, 73.3, 70.6, 40.3, 36.3, 26.1, 18.3, 18.1, 17.6, 17.5, −4.11, −4.54, −4.61, −4.90. LRMS (CI): m/z 541 [M+H]+; HRMS (CI) calculated for C27H48O5SSi2, 541.2839; found, 541.2834.

Workup

  1. additionwas then added
  2. customto quench the excess of TBSOTf
  3. concentrationThe resulting solution was concentrated via rotary evaporation
  4. customthe residue was purified by flash column chromatography (ethyl acetate/hexane, 1:5)

Sources & evidence

ORD record
ord-72bc74af69114b41ab0a74cdf3541e4c
Source dataset
uspto-grants-2009_03
Patent number
US07501535B2

Reaction notes

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