Potassium Carbonate → HCID 118294434, Verbindung

HRID 1048840Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1048840
[Cl-].COC[P+](C1C=CC=CC=1)(C1C=CC=CC=1)[C:6]1C=CC=C[CH:7]=1.CC([O-])(C)C.[Na+].[C:30]([C:33]1[CH:38]=[CH:37][C:36]([C:39]2[CH:44]=[CH:43]C(C#N)=C[CH:40]=2)=[CH:35][C:34]=1[O:47][CH3:48])(=O)[CH3:31].[CH3:49]/[C:50](/[O-])=[C:51](/P(OC)(OC)=O)\[N+:52]#N.C([O-])([O-])=O.[K+].[K+]>C1COCC1.C1COCC1.O.CO.[Hg](OC(C)=O)OC(C)=O>[CH3:48][O:47][C:34]1[CH:35]=[C:36]([C:39]2[CH:40]=[CH:49][C:50]([C:51]#[N:52])=[CH:43][CH:44]=2)[CH:37]=[CH:38][C:33]=1[CH:30]([CH3:31])[C:6]#[CH:7]

Komponenten

10

Edukt 5

HCID 11430Potassium CarbonateHCID 2723798Methoxymethyl-triphenylphosphonium chlorideHCID 23676156Sodium t-butoxideHCID 118294417HCID 118294417, VerbindungHCID 178502985HCID 178502985, Verbindung

Produkt 1

HCID 118294434HCID 118294434, VerbindungAusbeute 2.406,8 %

Reagenzien, Katalysatoren, Lösungsmittel 4

HCID 16683746DiacetyloxymercuryKatalysatorHCID 887MethanolLösungsmittel2×HCID 8028TetrahydrofuranLösungsmittel2×HCID 21881883Oxolane--water (1/1)Lösungsmittel

Reaktionsbedingungen

Temperatur
0 °C

Versuchsvorschrift

According to the general procedure for homologation, methoxymethyl triphenylphosphonium chloride (1.09 g, 3.18 mmol) in dry THF (4 mL), NaOtBu (0.382 g, 3.9 mmol), ketone 13 (0.400 g, 1.59 mmol) in THF (3 mL) were stirred at 0° C. Following the general workup, the mixture of enol ethers (0.330 g, 1.18 mmol) in THF/H2O (9:1, 5 mL) were hydrolyzed using Hg(OAc)2 (1.13 g, 3.5 mmol) at room temperature. After the general extraction procedure, aldehyde (0.285 g, 1.1 mmol) in MeOH (3 mL), Ohira-Bestmann reagent (0.442 g, 2.15 mmol) dissolved in MeOH (1 mL), powdered K2CO3 (0.370 g, 2.68 mmol) were stirred at 0° C. Following the general workup and flash chromatography (SiO2, 10 g, 5% EtOAc/hexanes) alkyne 22 was obtained as a white solid (0.200 g, 47% yield over 3 steps); TLC Rf=0.2 (5% EtOAc/hexanes); mp 103.7-104° C.; 1H NMR (500 MHz, CDCl3) δ 7.72 (m, 2H), 7.67 (m, 3H), 7.19 (d, J=7.9 Hz, 1H), 7.03 (s, 1H), 4.23 (q, J=7.0, 1H), 3.92 (s, 3H), 2.25 (d, J=2.4 Hz, 1H), 1.48 (d, J=7.0 Hz, 3H); 13C NMR (125 MHz, CDCl3) δ 156.7, 145.8, 139.3, 132.7, 131.9. 128.6, 127.9, 119.9, 119.9, 119.1, 111.1, 109.5, 87.3, 69.9, 55.8, 25.4, 22.8; IR (neat cm−1) 3285, 3069, 2935, 2221, 1604, 1488, 1393, 1225, 1024, 807, 657; HRMS (DART, M++H) m/z 262.1253 (calculated for C18H16NO, 262.1232).

Aufarbeitung

  1. customat room temperature

Quellen und Nachweise

ORD-Eintrag
ord-4a01eaa29ebc4f05bf3dd74ff65bd684
Quelldatensatz
uspto-grants-2016_07
Patentnummer
US09382213B2

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