L-Serine → Ethyl 2-cyanomethyl-2-phenylmethylpropanoate

HRID 1108365Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1108365
[C:1]1([CH2:7][CH:8]([CH3:14])[C:9]([O:11][CH2:12][CH3:13])=[O:10])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.Br[CH2:16][C:17]#[N:18].C([N-]C(C)C)(C)C.[Li+].CN(P(N(C)C)(N(C)C)=O)C.N[C@H](C(O)=O)CO>C1COCC1>[C:1]1([CH2:7][CH:8]([CH3:14])[C:9]([O:11][CH2:12][CH3:13])=[O:10])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[C:17]([CH2:16][C:8]([CH2:7][C:1]1[CH:2]=[CH:3][CH:4]=[CH:5][CH:6]=1)([CH3:14])[C:9]([O:11][CH2:12][CH3:13])=[O:10])#[N:18]

Komponenten

8

Edukt 5

HCID 5951L-SerineHCID 11534BromoacetonitrileHCID 12679HexamethylphosphoramideHCID 562367Ethyl 2-methyl-3-phenylpropanoateHCID 2724682Lithium diisopropylamide

Produkt 2

HCID 562367Ethyl 2-methyl-3-phenylpropanoateHCID 10704694Ethyl 2-cyanomethyl-2-phenylmethylpropanoateAusbeute 135,9 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 8028TetrahydrofuranLösungsmittel

Versuchsvorschrift

The reaction of ethyl 2-phenylmethylpropanoate (9.60 g, 50 mmol) with bromoacetonitrile (9.0 g, 75 mmol) in the presence of lithium diisopropylamide (prepared by treating diisopropylamine (6.06 g, 60 mmol) with butyllithium in hexanes (2.5 M, 24 mL, 60 mmol)) in THF (150 mL) and HMPA (4.3 mL, 25 mmol), as described above in the preparation of Example 4, gave 11.95 g of the crude product as a pale yellow colored liquid. Ethyl 2-phenylmethylpropanoate was prepared as in Spencer R W, Tam T F, Thomas E, Robinson V J, Krantz A (1986) "Ynenol lactones: Synthesis and investigation of reactions relevant to their inactivation of serine proteases" J. Am. Chem. Soc., 108 5589-5597. Flash chromatography over silica gel (hexanes-CH2Cl2, 3:2) afforded 7.86 g (68%) of the nitrile as a colorless viscous liquid. Analytical sample was prepared by bulb-to-bulb distillation (pot temp. 110-115° C. (0.9 mmHg)).

Aufarbeitung

  1. customas described above in the preparation of Example 4
  2. customgave 11.95 g of the crude product as a pale yellow colored liquid

Quellen und Nachweise

ORD-Eintrag
ord-e72d74b513c34a1ea5a17edc4cc61807
Quelldatensatz
uspto-grants-2000_05
Patentnummer
US06066666

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