HCID 86675581, compound → HCID 71183845, compound

HRID 1422598Notes

Reaction equation

HRID 1422598 reaction equation
[N+](=[C:3]([C:10]1[CH:15]=[CH:14][CH:13]=[C:12]([N+:16]([O-:18])=[O:17])[CH:11]=1)[C:4]([O:6][CH2:7][CH:8]=[CH2:9])=[O:5])=[N-]>ClCCl.CCCCCCCC([O-])=O.CCCCCCCC([O-])=O.CCCCCCCC([O-])=O.CCCCCCCC([O-])=O.[Rh+2].[Rh+2]>[N+:16]([C:12]1[CH:11]=[C:10]([C:3]23[CH2:9][CH:8]2[CH2:7][O:6][C:4]3=[O:5])[CH:15]=[CH:14][CH:13]=1)([O-:18])=[O:17]

Participants

4

Reactant 1

HCID 86675581HCID 86675581, compound

Product 1

HCID 71183845HCID 71183845, compoundYield 91.1%

Reagents, catalysts & solvents 2

HCID 1162193473482-96-9CatalystHCID 6344DichloromethaneSolvent2×

Procedure

To a solution of commercially available rhodium(II) octanoate dimer (Rh2(C7H16CO2)4) CAS-no. [73482-96-9] (440 mg, 565 μmol, Eq: 0.00941) in dichloromethane (180 ml) at 50° C. was added a solution of allyl 2-diazo-2-(3-nitrophenyl)acetate (intermediate B4a) (14.85 g, 60.1 mmol, Eq: 1.00) in dichloromethane (38 ml) via syringe pump within 18 h. Refluxing was continued for 30 min, the solvent was evaporated and the crude material was purified by flash chromatography (silica gel, 70 g, 0% to 100% EtOAc in heptane) to give (1SR,5RS)-1-(3-nitrophenyl)-3-oxabicyclo[3.1.0]hexan-2-one (12 g, 54.7 mmol, 91.1% yield) as a light brown solid. [cf. Adv. Synth. Catal. 2001, 343, 299 for an enantioselective version of this reaction]. MS (ISP): m/z=237.1 [(M+NH4)+].

Workup

  1. temperatureRefluxing
  2. customthe solvent was evaporated
  3. customthe crude material was purified by flash chromatography (silica gel, 70 g, 0% to 100% EtOAc in heptane)

Sources & evidence

ORD record
ord-1e705b2ec02c4285bdc0f39540511412
Source dataset
uspto-grants-2015_01
Patent number
US08927535B2

Reaction notes

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