Benzenepropanal → HCID 89800244, compound

HRID 2170127Notes

Reaction equation

HRID 2170127 reaction equation
[CH:1](=[O:10])[CH2:2][CH2:3][C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][CH:5]=1.[CH3:11][CH2:12][CH2:13][CH2:14][CH2:15][CH3:16].C[CH:18]([OH:20])C.C[CH2:22][O:23][C:24]([CH3:26])=[O:25]>>[O:20]=[C:18]1[C:12]2[C:13](=[CH:14][CH:15]=[CH:16][CH:11]=2)[CH:26]([C:24]([O:23][CH3:22])=[O:25])[CH:1]([CH2:2][CH2:3][C:4]2[CH:9]=[CH:8][CH:7]=[CH:6][CH:5]=2)[O:10]1

Participants

4

Reactant 3

HCID 7707BenzenepropanalHCID 8857Ethyl AcetateHCID 21585144Isopropanol hexane

Product 1

HCID 89800244HCID 89800244, compound

Procedure

Prepared according to general procedure A using freshly distilled hydrocinnamaldehyde (32.4 mL, 0.246 mmol). The reaction was stirred for 22 h to give a diastereomeric mixture of carboxylic acids in a 75:25 ratio. After esterification, both diastereomers (anti-20 and syn-20) were purified by column chromatography to give a pale yellow oil (71.7 mg, 94%, combined yield for both diastereoisomers). The diastereomeric ratio of the esters was found to be 79:21 (anti-20:syn-20) by 1H-NMR spectroscopic analysis. CSP-HPLC analysis. Chiralpak OJ-H (4.6 mm×25 cm), hexane/IPA: 80/20, 0.5 mL min-1, RT, UV detection at 254 nm, retention times: anti-20 52.6 min. (major enantiomer) and 76.2 min. (minor enantiomer); syn-20 66.5 min. (major enantiomer) and 106.6 min. (minor enantiomer). TLC (hexanes:EtOAc, 8:2 v/v): Rf=0.35; anti-20: 1H NMR (600 MHz, CDCl3): δ=8.15 (d, J=7.8 Hz, 1H), 7.59 (app. t, 1H), 7.47 (app. t, 1H), 7.35-7.25 (m, 3H), 7.25-7.15 (m, 3H), 4.91-4.84 (m, 1H), 3.92 (d, J=6.8 Hz, 1H), 3.76 (s, 3H), 2.92-3.02 (m, 1H), 2.83-2.75 (m, 1H), 2.13-2.03 (m, 1H), 1.97-1.87 (m, 1H); 13C NMR (100 MHz, CDCl3): δ=170.6, 164.0, 140.6, 136.0, 134.3, 130.7, 128.9, 128.7, 128.6, 127.3, 126.40, 124.7, 78.3, 52.9, 48.7, 35.7, 31.3; syn-20: 1H NMR (600 MHz, CDCl3): δ=8.15 (d, J=7.9 Hz, 1H), 7.56 (app. t, 1H), 7.48 (app. t, 1H), 7.35-7.25 (m, 2H), 7.25-7.15 (m, 4H), 4.60-4.53 (m, 1H), 3.83 (d, J=3.2, 1H), 3.68 (s, 3H), 3.02-2.92 (m, 1H), 2.90-2.83 (m, 1H), 2.30-2.21 (m, 1H), 2.14-2.02 (m, 1H); 13C NMR (100 MHz, CDCl3): δ=169.4, 164.8, 140.5, 136.8, 133.9, 130.9, 129.2, 128.8, 128.7, 127.4, 126.42, 125.5, 77.3, 52.8, 48.1, 34.5, 31.4; IR (neat): 3062, 3027, 2952, 2927, 2860, 1723, 1603, 1457, 1244, 1159, 1120, 1086, 700 cm−1; HRMS (ESI): calcd. for [M+Na]+O19H18O4Na requires 333.1103. found 333.1103.

Workup

  1. customPrepared
  2. customto give
  3. customAfter esterification, both diastereomers (anti-20 and syn-20) were purified by column chromatography
  4. customto give a pale yellow oil (71.7 mg, 94%
  5. customcombined yield for both diastereoisomers)
  6. custom80/20, 0.5 mL min-1, RT, UV detection
  7. custom52.6 min. (major enantiomer) and 76.2 min. (minor enantiomer)
  8. customsyn-20 66.5 min. (major enantiomer) and 106.6 min. (minor enantiomer)

Sources & evidence

ORD record
ord-2b3ea846bad64af680021f331a0316e9
Source dataset
uspto-grants-2015_06
Patent number
US09050586B2

Reaction notes

Loading…