Sodium Carbonate → tert-butyl(6bR,10aS)-5-(2,3-dichlorophenyl)-1,2,6b,9,10,10a-hexahydropyrido[4,3-b][1,4]thiazino[2,3,4-hi]indole carboxylate

HRID 51029Notes

Reaction equation

HRID 51029 reaction equation
Br[C:2]1[CH:3]=[C:4]2[C:8]3=[C:9]([S:11][CH2:12][CH2:13][N:7]3[C@H:6]3[CH2:14][CH2:15][N:16](C(OC(C)(C)C)=O)[CH2:17][C@@H:5]23)[CH:10]=1.[Cl:25][C:26]1[C:31]([Cl:32])=[CH:30][CH:29]=[CH:28][C:27]=1B(O)O.[C:36]([O-:39])([O-])=[O:37].[Na+].[Na+]>C1C=CC=CC=1.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[Cl:25][C:26]1[C:31]([Cl:32])=[CH:30][CH:29]=[CH:28][C:27]=1[C:2]1[CH:3]=[C:4]2[C:8]3=[C:9]([S:11][CH2:12][CH:13]([C:36]([O:39][C:4]([CH3:8])([CH3:5])[CH3:3])=[O:37])[N:7]3[C@H:6]3[CH2:14][CH2:15][N:16]=[CH:17][C@H:5]23)[CH:10]=1

Participants

6

Reactant 3

HCID 10340Sodium CarbonateHCID 27346612,3-Dichlorobenzeneboronic acidHCID 21302667tert-butyl(6bR,10aS)-5-bromo-1,2,6b,9,10,10a-hexahydropyrido[4,3-b][1,4]thiazino[2,3,4-hi]indole-8(7H)-carboxylate

Product 1

HCID 86759404tert-butyl(6bR,10aS)-5-(2,3-dichlorophenyl)-1,2,6b,9,10,10a-hexahydropyrido[4,3-b][1,4]thiazino[2,3,4-hi]indole carboxylateYield 159.2%

Reagents, catalysts & solvents 2

HCID 178418476HCID 178418476, compoundCatalystHCID 241BenzeneSolvent

Conditions

Temperature
20 °C

Procedure

A solution of tert-butyl(6bR,10aS)-5-bromo-1,2,6b,9,10,10a-hexahydropyrido[4,3-b][1,4]thiazino[2,3,4-hi]indole-8(7H)-carboxylate (150 mg, 0.37 mmol) and 2,3-dichlorophenylboronic acid (143 mg, 0.75 mmol) in benzene (10 mL) and 2M Na2CO3 aqueous solution (0.74 mL, 1.48 mmol) was degassed at 20° C. Pd(PPh3)2Cl2 (7.8 mg, 0.01 mmol) was added, and the reaction mixture was degassed one more time. The reaction mixture was refluxed for 15 h then cooled to 20° C. The reaction mixture was diluted with EtOAc and washed with saturated NaHCO3 and brine. The combined organic layer was dried over MgSO4, filtered and concentrated in vacuo. The residue was chromatographed (silica gel; Hexane:EtOAc 3:1) to give tert-butyl(6bR,10aS)-5-(2,3-dichlorophenyl)-1,2,6b,9,10,10a-hexahydropyrido[4,3-b][1,4]thiazino[2,3,4-hi]indole carboxylate as a light yellow solid (140 mg, 81%).

Workup

  1. customthe reaction mixture was degassed one more time
  2. temperatureThe reaction mixture was refluxed for 15 h
  3. additionThe reaction mixture was diluted with EtOAc
  4. washwashed with saturated NaHCO3 and brine
  5. dry with materialThe combined organic layer was dried over MgSO4
  6. filtrationfiltered
  7. concentrationconcentrated in vacuo
  8. customThe residue was chromatographed (silica gel; Hexane:EtOAc 3:1)

Sources & evidence

ORD record
ord-7f90b6bb0bb34dd9969f9edfddb20b5a
Source dataset
uspto-grants-2004_03
Patent number
US06713471B1

Reaction notes

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