Potassium Carbonate → HCID 118294434, compound

HRID 1048840Notes

Reaction equation

HRID 1048840 reaction equation
[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]

Participants

10

Reactant 5

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

Product 1

HCID 118294434HCID 118294434, compoundYield 2,406.8%

Reagents, catalysts & solvents 4

HCID 16683746DiacetyloxymercuryCatalystHCID 887MethanolSolvent2×HCID 8028TetrahydrofuranSolvent2×HCID 21881883Oxolane--water (1/1)Solvent

Conditions

Temperature
0 °C

Procedure

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).

Workup

  1. customat room temperature

Sources & evidence

ORD record
ord-4a01eaa29ebc4f05bf3dd74ff65bd684
Source dataset
uspto-grants-2016_07
Patent number
US09382213B2

Reaction notes

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