Trimethylsilyldiazomethane → (1R,10R,11S,16S)-5-methoxy-1,11,15,15-tetramethyl-8-thiatetracyclo[8.8.0.02,7.011,16]octadeca-2,4,6-trien-3-ol

HRID 422139Notes

Reaction equation

HRID 422139 reaction equation
[CH3:1][C@@:2]12[CH2:19][CH2:18][C@@H:17]3[C@:12]([CH3:22])([CH2:13][CH2:14][CH2:15][C:16]3([CH3:21])[CH3:20])[C@H:11]1[CH2:10][S:9][C:8]1[C:3]2=[C:4]([OH:24])[CH:5]=[C:6]([OH:23])[CH:7]=1.[CH3:25][Si](C=[N+]=[N-])(C)C>CO.C(Cl)Cl>[CH3:25][O:23][C:6]1[CH:7]=[C:8]2[C:3]([C@@:2]3([CH3:1])[C@H:11]([CH2:10][S:9]2)[C@:12]2([CH3:22])[C@H:17]([C:16]([CH3:20])([CH3:21])[CH2:15][CH2:14][CH2:13]2)[CH2:18][CH2:19]3)=[C:4]([OH:24])[CH:5]=1

Participants

5

Reactant 2

HCID 167693TrimethylsilyldiazomethaneHCID 53241885(1R,10R,11S,16S)-1,11,15,15-tetramethyl-8-thiatetracyclo[8.8.0.02,7.011,16]octadeca-2,4,6-triene-3,5-diol

Product 1

HCID 53241982(1R,10R,11S,16S)-5-methoxy-1,11,15,15-tetramethyl-8-thiatetracyclo[8.8.0.02,7.011,16]octadeca-2,4,6-trien-3-ol

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 6344DichloromethaneSolvent

Procedure

(1R,10R,11S,16S)-1,11,15,15-Tetramethyl-8-thiatetracyclo[8.8.0.02,7.011,16]octadeca-2,4,6-triene-3,5-diol (Compound No. 26) (346 mg, 1.0 mmol) was dissolved in MeOH (4 mL) and CH2Cl2 (12 mL). Trimethylsilyl diazomethane (0.80 mL, 2.0 M in ether, 1.6 mmol) was added portionwise over 29 h at room temperature, monitoring the reaction by 1H NMR. The mixture was then concentrated and purified by chromatography on silica gel (Hexanes/EtOAc, 4:1) followed by recrystallization from MeOH/water to give (1R,10R,11S,16S)-5-methoxy-1,11,15,15-tetramethyl-8-thiatetracyclo[8.8.0.02,7.011,16]octadeca-2,4,6-trien-3-ol (Compound No. 29) (142 mg, 39%) as a white solid. 1H NMR (CDCl3): δ 6.21 (d, 1H), 5.95 (d, 1H), 4.72 (s, 1H), 3.69 (s, 3H), 3.30 (m, 1H), 2.91 (m, 1H), 2.78 (m, 1H), 1.85-1.40 (m, 8H), 1.39 (s, 3H), 1.20-1.00 (m, 2H), 0.96 (s, 3H), 0.95 (m, 1H), 0.85 (s, 3H), 0.84 (s, 3H). MS m/z 359 (C22H32O2S−H+).

Workup

  1. customthe reaction by 1H NMR
  2. concentrationThe mixture was then concentrated
  3. custompurified by chromatography on silica gel (Hexanes/EtOAc, 4:1)
  4. customfollowed by recrystallization from MeOH/water

Sources & evidence

ORD record
ord-d68c2aac036d44e78dfa51d3b35f9d3d
Source dataset
uspto-grants-2012_01
Patent number
US08101605B2

Reaction notes

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