Potassium Carbonate → HCID 118294434、化合物

HRID 1048840ノート

反応式

HRID 1048840 の反応式
[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]

参加物

10

反応物 5

HCID 11430Potassium CarbonateHCID 2723798Methoxymethyl-triphenylphosphonium chlorideHCID 23676156Sodium t-butoxideHCID 118294417HCID 118294417、化合物HCID 178502985HCID 178502985、化合物

生成物 1

HCID 118294434HCID 118294434、化合物収率 2,406.8%

試薬・触媒・溶媒 4

HCID 16683746Diacetyloxymercury触媒HCID 887Methanol溶媒2 回HCID 8028Tetrahydrofuran溶媒2 回HCID 21881883Oxolane--water (1/1)溶媒

反応条件

温度
0 °C

実験手順

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).

後処理

  1. customat room temperature

出典と根拠

ORDレコード
ord-4a01eaa29ebc4f05bf3dd74ff65bd684
出典データセット
uspto-grants-2016_07
特許番号
US09382213B2

反応ノート

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