Toluene → 2-Methyl-3b,4,6,7,7a,8-hexahydro-1-thia-5-aza-cyclopenta[alpha]indene-5-carboxylic acid ethyl ester

HRID 1013406Notes

Reaction equation

HRID 1013406 reaction equation
[CH2:1]([O:3][C:4]([N:6]1[CH2:14][CH:13]2[CH:9]([CH2:10][C:11]3[S:17][C:16](Br)=[CH:15][C:12]=32)[CH2:8][CH2:7]1)=[O:5])[CH3:2].[CH3:19][Zn]C.C1(C)C=CC=CC=1>O1CCOCC1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2]>[CH2:1]([O:3][C:4]([N:6]1[CH2:14][CH:13]2[CH:9]([CH2:10][C:11]3[S:17][C:16]([CH3:19])=[CH:15][C:12]=32)[CH2:8][CH2:7]1)=[O:5])[CH3:2]

Participants

6

Reactant 3

HCID 1140TolueneHCID 597894672-Bromo-3b,4,6,7,7a,8-hexahydro-1-thia-5-aza-cyclopenta[alpha]indene-5-carboxylic acid ethyl esterHCID 178477796HCID 178477796, compound

Product 1

HCID 1317270432-Methyl-3b,4,6,7,7a,8-hexahydro-1-thia-5-aza-cyclopenta[alpha]indene-5-carboxylic acid ethyl esterYield 59%

Reagents, catalysts & solvents 2

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 312751,4-DioxaneSolvent

Conditions

Temperature
22 °C

Procedure

A solution of the product from step b) (863 mg, 2.62 mmol) in dioxane (13.1 ml) was treated with Pd(dppf)2Cl2 (128 mg, 0.157 mmol) and a 2M solution of dimethylzinc in toluene (2.62 ml, 5.24 mmol) at 102° C. for 1 h. The reaction was cooled to 22° C. and carefully quenched with sat. NH4Cl (3 ml). After the effervescence subsided, the reaction was extracted with EtOAc (3×50 ml). The combined organic extracts were dried (MgSO4), concentrated and eluted through a plug of silica-gel using 50:50 hexanes:EtOAc to give 411 mg (59%) of the subtitle compound. MS calculated for C14H19NO2S +H 266, observed 266.

Workup

  1. customcarefully quenched with sat. NH4Cl (3 ml)
  2. extractionthe reaction was extracted with EtOAc (3×50 ml)
  3. dry with materialThe combined organic extracts were dried (MgSO4)
  4. concentrationconcentrated
  5. washeluted through a plug of silica-gel

Sources & evidence

ORD record
ord-e81fb452da624da183d09cc4dee48554
Source dataset
uspto-grants-2011_07
Patent number
US07981919B2

Reaction notes

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