1,1-Dibromoethane → HCID 68310141, compound

HRID 2405742Notes

Reaction equation

HRID 2405742 reaction equation
ClC([SiH3])(Cl)Cl.BrC(Br)C.[C:10]([N:17]1[CH2:20][CH:19](I)[CH2:18]1)([O:12][C:13]([CH3:16])([CH3:15])[CH3:14])=[O:11].Br[C:23]1[CH:41]=[CH:40][C:26]([CH2:27][C@@H:28]2[C:33]([CH3:35])([CH3:34])[O:32][C:31]([O:36][CH3:37])=[N:30][S:29]2(=[O:39])=[O:38])=[C:25]([F:42])[CH:24]=1>CC(N(C)C)=O.[Zn].[Cu]I.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]>[C:13]([O:12][C:10]([N:17]1[CH2:20][CH:19]([C:23]2[CH:41]=[CH:40][C:26]([CH2:27][C@@H:28]3[C:33]([CH3:35])([CH3:34])[O:32][C:31]([O:36][CH3:37])=[N:30][S:29]3(=[O:39])=[O:38])=[C:25]([F:42])[CH:24]=2)[CH2:18]1)=[O:11])([CH3:16])([CH3:15])[CH3:14]

Participants

9

Reactant 4

HCID 112011,1-DibromoethaneHCID 11000522Tert-butyl 3-iodoazetidine-1-carboxylateHCID 71317501CID 71317501HCID 86706566HCID 86706566, compound

Product 1

HCID 68310141HCID 68310141, compoundYield 30.3%

Reagents, catalysts & solvents 4

HCID 23994ZincCatalystHCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 31374DimethylacetamideSolvent2×

Conditions

Temperature
65 °C

Procedure

Zinc dust (252 mg) was suspended in DMA (0.5 ml) and heated to 65° C. Subsequently, trichloromethylsilane (27 mg) and dibromoethane (34 mg) were added and the mixture was stirred at 65° C. for 30 min. Then 1-BOC-3-iodoazetidine (465 mg) in 0.5 ml of DMA was added dropwise and the mixture was stirred for a further 30 min. (R)-5-(4-bromo-2-fluorobenzyl)-2-methoxy-6,6-dimethyl-5,6-dihydro-[1,4,3]oxathiazine 4,4-dioxide (250 mg) was dissolved in 1 ml and added dropwise to the warm solution, and the mixture was stirred at 65° C. for a further 30 min. Copper(I) iodide (25 mg) and 1,1′-bis(diphenylphosphino)ferrocenepalladium(II) chloride (53 mg) were added and the suspension was heated to 85° C. for 1 hour. After cooling, the mixture was filtered through a membrane. The solution was purified by means of preparative HPLC. This gave the product (91 mg) with a molecular weight of 456.5 g/mol (C21H29FN2O6S), MS (ESI): (M-butene+H+) 401.5 g/mol.

Workup

  1. dissolutionwas dissolved in 1 ml
  2. additionadded dropwise to the warm solution
  3. stirringthe mixture was stirred at 65° C. for a further 30 min
  4. temperaturethe suspension was heated to 85° C. for 1 hour
  5. temperatureAfter cooling
  6. filtrationthe mixture was filtered through a membrane
  7. customThe solution was purified by means of preparative HPLC

Sources & evidence

ORD record
ord-e8bbfd22f9c74ecdac8705e5ebe6f040
Source dataset
uspto-grants-2014_08
Patent number
US08809325B2

Reaction notes

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