Lithium diisopropylamide → 2-[(E)-2-(2-chloro-4-methoxyphenyl)ethenyl]-5-methoxy-1H-indole

HRID 11085Notes

Reaction equation

HRID 11085 reaction equation
[OH:1][C:2]1[CH:14]=[CH:13][C:12]2[NH:11][C:10]3[CH:9]=C(I)C4C(=O)NC(=O)C=4[C:5]=3[C:4]=2[CH:3]=1.[Br-].[Cl:22][C:23]1[CH:48]=[C:47]([O:49][CH3:50])[CH:46]=[CH:45][C:24]=1[CH2:25][P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.[Li+].[CH3:52]C([N-]C(C)C)C>>[Cl:22][C:23]1[CH:48]=[C:47]([O:49][CH3:50])[CH:46]=[CH:45][C:24]=1/[CH:25]=[CH:9]/[C:10]1[NH:11][C:12]2[C:4]([CH:5]=1)=[CH:3][C:2]([O:1][CH3:52])=[CH:14][CH:13]=2

Participants

4

Reactant 3

HCID 2724682Lithium diisopropylamide2×HCID 118428349-hydroxy-4-iodopyrrolo[3,4-c]carbazole-1,3(2H,6H)-dioneHCID 87899044(2-Chloro-4-methoxybenzyl)(triphenyl)phosphonium bromide

Product 1

HCID 219806922-[(E)-2-(2-chloro-4-methoxyphenyl)ethenyl]-5-methoxy-1H-indole

Procedure

The 5-methoxy-1H-indole-2-carbaldehyde (1) was reacted with (2-chloro-4-methoxybenzyl)(triphenyl)phosphonium bromide (574) prepared as described in example 162 using the procedure described in example 37, except that the LDA and aldehyde were sequentially added at 0° C., the ratio of LDA:aldehyde was 1.5:1 and the reaction time was 5 h, to give (after crystallisation from CH2Cl2/pentane) the diene (575) as a pale yellow solid (the pure E isomer) (64%), mp 129–132° C. 1H NMR (CDCl3) δ 8.17 (br s, 1H), 7.60 (d, J=8.8 Hz, 1H), 7.25 (d, J=8.3 Hz, 1H), 7.19 (d, J=16.5 Hz, 1H), 7.03 (d, J=2.4 Hz, 1H), 6.96 (d, J=17.3 Hz, 1H), 6.94 (d, J=2.4 Hz, 1H), 6.86 (dd, J=8.7, 2.6 Hz, 1H), 6.85 (dd, J=8.7, 2.8 Hz, 1H), 6.54 (d, J=1.7 Hz, 1H), 3.85 (s, 3H), 3.83 (s, 3H). Found: C, 69.05; H, 5.41; N, 4.68. C18H16ClNO2 requires C, 68.90; H, 5.14; N, 4.46.

Workup

  1. customprepared
  2. additionwere sequentially added at 0° C.
  3. customto give
  4. custom(after crystallisation from CH2Cl2/pentane) the diene (575) as a pale yellow solid (the pure E isomer) (64%), mp 129–132° C

Sources & evidence

ORD record
ord-7ccdd8dbcf034a15acfdf0ca50cc01a9
Source dataset
uspto-grants-2006_08
Patent number
US07094798B1

Reaction notes

Loading…