Sodium Carbonate → ethyl (E)-4-[3-(1-adamantyl)-4-benzyloxyphenyl]-3-chlorocinnamate

HRID 1826609Notes

Reaction equation

HRID 1826609 reaction equation
C([O-])([O-])=O.[Na+].[Na+].FC(F)(F)S(O[C:13](=[CH:19][C:20]1[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=1)[C:14]([O:16][CH2:17][CH3:18])=[O:15])(=O)=O.[C:28]12([C:38]3[CH:39]=[C:40](B(O)O)[CH:41]=[CH:42][C:43]=3[O:44][CH2:45][C:46]3[CH:51]=[CH:50][CH:49]=[CH:48][CH:47]=3)[CH2:37][CH:32]3[CH2:33][CH:34]([CH2:36][CH:30]([CH2:31]3)[CH2:29]1)[CH2:35]2.[Cl-:55].[Li+]>C(COC)OC.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[C:28]12([C:38]3[CH:39]=[C:40]([C:23]4[CH:24]=[CH:25][C:20](/[CH:19]=[CH:13]/[C:14]([O:16][CH2:17][CH3:18])=[O:15])=[CH:21][C:22]=4[Cl:55])[CH:41]=[CH:42][C:43]=3[O:44][CH2:45][C:46]3[CH:51]=[CH:50][CH:49]=[CH:48][CH:47]=3)[CH2:37][CH:32]3[CH2:33][CH:34]([CH2:36][CH:30]([CH2:31]3)[CH2:29]1)[CH2:35]2

Participants

7

Reactant 4

HCID 10340Sodium CarbonateHCID 433294Lithium ChlorideHCID 12134904[3-(Adamantan-1-yl)-4-(benzyloxy)phenyl]boronic acidHCID 86589621Ethyl (trifluoro-methane-sulfonyloxy)cinnamate

Product 1

HCID 67390349ethyl (E)-4-[3-(1-adamantyl)-4-benzyloxyphenyl]-3-chlorocinnamateYield 79.7%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 80711,2-DimethoxyethaneSolvent

Procedure

Aqueous Na2CO3 (1.4 mL, 2.0 M) was added to the ethyl (trifluoro-methane-sulfonyloxy)cinnamate (0.55 g, 1.53 mmol), 3-(1-adamantyl)-4-benzyloxyphenylboronic acid (0.50 g, 1.38 mmol) [1H NMR spectrum (300 MHz, CDCl3) δ 1.77, 2.26 (2 s, 12, AdCH2), 2.07 (s, 3, AdCH), 5.21 (s, 2, CH2), 7.06 (d, J=8.2 Hz, 1, ArH), 7.3–7.5 (mn, 5, ArH), 8.03 (d, J=7.8 Hz, 1, ArH), 8.19 ppm (s, 1, ArH)], tetrakis(triphenylphosphine)palladium (0.16 g, 0.14 mmol), and lithium chloride (0.13 g, 3.1 mmol) in dimethoxyethane (12 mL) under argon. The mixture was heated at reflux (80–85° C.) overnight to achieve the biaryl coupling, then worked-up, and chromatographed (10% ethyl acetate/hexane) to give ethyl (E)-4-[3-(1-adamantyl)-4-benzyloxyphenyl]-3-chlorocinnamate as a white solid (0.58 g, 79%): m.p. 148–150° C.; Rf0.61 (20% ethyl acetate/hexane); 1H NMR spectrum (300 MHz, CDCl3) δ 1.73, 2.17 (2 s, 12, AdCH2), 2.04 (s, 3, AdCH), 1.33 (t, J=7.1 Hz, 3 CH3), 4.26 (q, J=7.1 Hz, 2, CH2), 5.17 (s, 2, CH2), 6.46 (d, J=15.9 Hz, 1, HC═CCO), 7.00 (d, J=8.2 Hz, 1, ArH), 7.3–7.5 (m, 8, ArH), 7.52 (d, J=7.1 Hz, 1, ArH), 7.62 (s, 1, ArH), 7.65 ppm (d, J=15.4 Hz, 1, C═CHCO).

Workup

  1. temperatureThe mixture was heated
  2. temperatureat reflux (80–85° C.) overnight
  3. customchromatographed (10% ethyl acetate/hexane)

Sources & evidence

ORD record
ord-d5f299eb2c704089b14074b260f782c0
Source dataset
uspto-grants-2006_05
Patent number
US07053071B2

Reaction notes

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