2,6-Lutidine → (3S,6R,7S,8S)-(S,E)-2-Methyl-1-(2-methylthiazol-4-yl)hexa-1,5-dien-3-yl 3,7-bis((tert-butyldimethylsilyl)oxy)-4,4,6,8-tetramethyl-5-oxotridec-12-enoate

HRID 1518917Notes

Reaction equation

HRID 1518917 reaction equation
[Si:1]([O:8][C@H:9]([C:27]([CH3:42])([CH3:41])[C:28](=[O:40])[C@H:29]([CH3:39])[C@@H:30]([OH:38])[C@@H:31]([CH3:37])[CH2:32][CH2:33][CH2:34][CH:35]=[CH2:36])[CH2:10][C:11]([O:13][C@@H:14]([CH2:24][CH:25]=[CH2:26])/[C:15](/[CH3:23])=[CH:16]/[C:17]1[N:18]=[C:19]([CH3:22])[S:20][CH:21]=1)=[O:12])([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2].N1C(C)=CC=CC=1C.[Si:51](OS(C(F)(F)F)(=O)=O)([C:54]([CH3:57])([CH3:56])[CH3:55])([CH3:53])[CH3:52]>C(Cl)Cl>[Si:1]([O:8][C@H:9]([C:27]([CH3:41])([CH3:42])[C:28](=[O:40])[C@H:29]([CH3:39])[C@@H:30]([O:38][Si:51]([C:54]([CH3:57])([CH3:56])[CH3:55])([CH3:53])[CH3:52])[C@@H:31]([CH3:37])[CH2:32][CH2:33][CH2:34][CH:35]=[CH2:36])[CH2:10][C:11]([O:13][C@@H:14]([CH2:24][CH:25]=[CH2:26])/[C:15](/[CH3:23])=[CH:16]/[C:17]1[N:18]=[C:19]([CH3:22])[S:20][CH:21]=1)=[O:12])([C:4]([CH3:5])([CH3:7])[CH3:6])([CH3:3])[CH3:2]

Participants

5

Reactant 3

HCID 79372,6-LutidineHCID 123564tert-Butyldimethylsilyl trifluoromethanesulphonateHCID 11028520HCID 11028520, compound

Product 1

HCID 11125479(3S,6R,7S,8S)-(S,E)-2-Methyl-1-(2-methylthiazol-4-yl)hexa-1,5-dien-3-yl 3,7-bis((tert-butyldimethylsilyl)oxy)-4,4,6,8-tetramethyl-5-oxotridec-12-enoateYield 73%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

A solution of (3S,6R,7S,8S)—(S,E)-2-methyl-1-(2-methylthiazol-4-yl)hexa-1,5-dien-3-yl 3-((tert-butyldimethylsilyl)oxy)-7-hydroxy-4,4,6,8-tetramethyl-5-oxotridec-12-enoate (Nicolaou, K. C.; He, Y.; Vourloumis, D.; Vallberg, H.; Roschangar, F.; Sarabia, F.; Ninkovic, S.; Yang, Z.; Trujillo, J. I. J. Am. Chem. Soc. 1997, 119, 7960-7973) in DCM at −50° C. was treated with 2,6-lutidine (1.82 mL, 15.7 mmol) followed by TBSOTf (3.60 mL, 15.7 mmol). The reaction mixture was stirred at the same temperature for 0.5 h, quenched by NH4Cl (sat.) and extracted with DCM (3×). The combined organic layers were dried (MgSO4), filtered and concentrated under reduced pressure. Purification by chromatography on SiO2 (hexanes:ethyl ether=100:2 to 10:1) followed by the second chromatography (hexanes: diethyl ether=100:4 to 100:6 to 10:1) afforded 0.281 g (73%) of the title compound as a colorless oil.

Workup

  1. customquenched by NH4Cl (sat.)
  2. extractionextracted with DCM (3×)
  3. dry with materialThe combined organic layers were dried (MgSO4)
  4. filtrationfiltered
  5. concentrationconcentrated under reduced pressure
  6. customPurification by chromatography on SiO2 (hexanes:ethyl ether=100:2 to 10:1)

Sources & evidence

ORD record
ord-9320a12ac5ef489ab2b46dd17ffad9f6
Source dataset
uspto-grants-2015_07
Patent number
US09073801B2

Reaction notes

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