Benzyl Alcohol → Phenylmethyl 4-nitrobenzoate
Reaction equation
[CH3:1][C:2]1[CH:3]=[C:4](P2(=O)CCCC2)[CH:5]=[CH:6][CH:7]=1.[PH3]=O.[N+:16]([C:19]1[CH:27]=[CH:26][C:22]([C:23]([OH:25])=[O:24])=[CH:21][CH:20]=1)([O-:18])=[O:17].N(C(OC(C)C)=O)=NC(OC(C)C)=O.C1([SiH3])C=CC=CC=1.C(O)C1C=CC=CC=1>>[N+:16]([C:19]1[CH:20]=[CH:21][C:22]([C:23]([O:25][CH2:1][C:2]2[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=2)=[O:24])=[CH:26][CH:27]=1)([O-:18])=[O:17]Participants
Conditions
- Temperature
- 80 °C
Procedure
The reaction is illustrated in FIG. 9. In air, a 1-dram vial equipped with a stir-bar was charged with phosphine oxide 1 (9.7 mg, 10 mol %), 4-nitrobenzoic acid (51.7 μL, 0.5 mmol), and diisopropyl azodicarboxylate (DIAD, 147.5 μL, 0.75 mmol). The vial was then sealed with a septum, and purged with argon. Distilled Toluene (1.5 mL) was added. Reaction was allowed to stir. Phenylsilane (67.8 μL, 0.55 mmol), and benzyl alcohol (51.7 μL, 0.5 mmol) was added. The septum was replaced with a PTFE-lined screw cap under an inert atmosphere, and the reaction was heated at 80° C. for 24 hours. The crude reaction mixture was filtered through a plug of celite, concentrated in vacuo, and purified via flash chromatography yielding the title compound 63%, 81.0 mg. To the best of our knowledge this is the first example of a Mitsunobu reaction catalytic in phosphine.
Workup
- customIn air, a 1-dram vial equipped with a stir-bar
- customThe vial was then sealed with a septum
- custompurged with argon
- additionDistilled Toluene (1.5 mL) was added
- customReaction
- customcap under an inert atmosphere
- customThe crude reaction mixture
- filtrationwas filtered through a plug of celite
- concentrationconcentrated in vacuo
- custompurified via flash chromatography
Sources & evidence
- ORD record
- ord-454aa69af3a449a89183fd6b6538ff53
- Source dataset
- uspto-grants-2014_12
- Patent number
- US08901365B2
Reaction notes
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