2-Chloropyridine → HCID 59846446, Verbindung

HRID 1363173Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1363173
[Si:1]([O:8][CH2:9][CH2:10][CH:11]=[O:12])([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2].[Cl:13][C:14]1[C:19]([Li])=[CH:18][CH:17]=[CH:16][N:15]=1.[Li+].CC([N-]C(C)C)C.ClC1C=CC=CN=1>C1COCC1>[Si:1]([O:8][CH2:9][CH2:10][CH:11]([C:19]1[C:14]([Cl:13])=[N:15][CH:16]=[CH:17][CH:18]=1)[OH:12])([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2]

Komponenten

6

Edukt 4

HCID 79772-ChloropyridineHCID 2724682Lithium diisopropylamideHCID 36623923-((Tert-butyldimethylsilyl)oxy)propanalHCID 178506730HCID 178506730, Verbindung

Produkt 1

HCID 59846446HCID 59846446, Verbindung

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 8028TetrahydrofuranLösungsmittel2×

Versuchsvorschrift

(Prepared similarly to literature procedure, Murtiashaw, C. W., et. al. J. Org. Chem., 1992, 57, 1930-1933). A solution of 3-(tert-butyldimethylsilyloxy)propanal (2.3 g, prepared from 3-(tert-butyldimethylsilyloxy)propan-1-ol via Swern oxidation as per Li, X.; Lantrip, D.; Fuchs, P. L. J. Am. Chem. Soc., 2003, 125, 14262-14263, Supporting information) in THF (10 mL) was slowly added via double ended needle to a solution of 2-chloro-3-lithiopyridine (prepared in turn from freshly prepared LDA (11.4 mM) and 2-chloropyridine (11.4 mM) (as per Gribble, G. W.; Saulnier, M. G. Tet. Lett. 1980, 21, 4137-4140) in THF (25 mL) at −78° C. The resulting mixture was allowed to slowly warm to RT over 15 hr, quenched via the addition of sat. NH4Cl (2 mL) and solvents reduced in vacuo. The resultant slurry was taken up in EtOAc, washed with brine, and purified via column chromatography (eluted with 15, 20 and 25% EtOAc/Hex) to yield the titled product (1.0 g), NMR CDCl3 1H δ 8.3 (dd, 1H), 8.0 (dd, 1H), 7.3 (dd, 1H), 5.2 (d, 1H), 4.5 (m, 1H), 4.0-3.8 (m, 2H), 2.1 (m, 1H), 1.8 (m, 1H) 0.9 (s, 9H), 0.1 (s, 6H); MH+=302/304.

Aufarbeitung

  1. custom(Prepared similarly to literature procedure, Murtiashaw, C
  2. customquenched via the addition of sat. NH4Cl (2 mL) and solvents
  3. washwashed with brine
  4. custompurified via column chromatography (eluted with 15, 20 and 25% EtOAc/Hex)

Quellen und Nachweise

ORD-Eintrag
ord-9b926f4c566f4dcf84a7f6f0992cf982
Quelldatensatz
uspto-grants-2011_02
Patentnummer
US07884109B2

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