Triphenylphosphine → 4-(2-[4-Carbomethoxymethyloxyphenyl]ethynyl)-4-(3-cyclopentyloxy-4-methoxyphenyl)-1,1-(ethylenedioxy)cyclohexane

HRID 343571Notes

Reaction equation

HRID 343571 reaction equation
[CH:1]1([O:6][C:7]2[CH:8]=[C:9]([C:15]3([C:25]#[CH:26])[CH2:20][CH2:19][C:18]4([O:24][CH2:23][CH2:22][O:21]4)[CH2:17][CH2:16]3)[CH:10]=[CH:11][C:12]=2[O:13][CH3:14])[CH2:5][CH2:4][CH2:3][CH2:2]1.[CH3:27][O:28][C:29](=[O:39])[CH2:30][O:31][C:32]1[CH:37]=[CH:36][C:35](I)=[CH:34][CH:33]=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>C(N(CC)CC)C.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:29]([CH2:30][O:31][C:32]1[CH:37]=[CH:36][C:35]([C:26]#[C:25][C:15]2([C:9]3[CH:10]=[CH:11][C:12]([O:13][CH3:14])=[C:7]([O:6][CH:1]4[CH2:2][CH2:3][CH2:4][CH2:5]4)[CH:8]=3)[CH2:20][CH2:19][C:18]3([O:21][CH2:22][CH2:23][O:24]3)[CH2:17][CH2:16]2)=[CH:34][CH:33]=1)([O:28][CH3:27])=[O:39]

Participants

6

Reactant 3

HCID 11776TriphenylphosphineHCID 6457537Methyl 2-(4-iodophenoxy)acetateHCID 110895964-(3-Cyclopentyloxy-4-methoxyphenyl)-1,1-(ethylenedioxy)-4-ethynylcyclohexane

Product 1

HCID 542626814-(2-[4-Carbomethoxymethyloxyphenyl]ethynyl)-4-(3-cyclopentyloxy-4-methoxyphenyl)-1,1-(ethylenedioxy)cyclohexaneYield 73.2%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 8471TriethylamineSolvent

Procedure

A stirred mixture of 4-(3-cyclopentyloxy-4-methoxyphenyl)-1,1-(ethylenedioxy)-4-ethynylcyclohexane (0.075 g, 0.21 mmol) and 4-iodophenoxyacetic acid methyl ester (0.060 g, 0.21 mmol, prepared as described in Example 35a) in dry triethylamine (2 mL) was treated at 80° C. for 1.5 hr by the procedure of Example 11 with a mixture of tetrakis(triphenylphosphine)palladium (0.018 g, 0.016 mmol), cuprous iodide (0.004 g, 0.021 mmol), and triphenylphosphine (crystal). The crude product was chromatographed (silica 40 to 50% ethyl acetate in hexanes) and stripped in vacuo to afford the tided intermediate as a dark red oil (0.080 g, 73%). 1H-NMR (400 MHz, CDCl3) δ 7.98 (d, 9.4 Hz, 2H), 7.50 (d, J=9.4 Hz, 2H), 7.20 (d, J=1.9 Hz, 1H), 7.12 (d-d, J=1.9 Hz, J=8.6 Hz, 1H), 6.84 (d, J=8.6, 1H), 4.80 (p, J=3.8 Hz, 1H), 4.00 (s, br, 4H), 3.92 (s, 3H), 3.85 (s, 3H), 2.3 to 1.5 (m, 17H with H2O).

Workup

  1. customThe crude product was chromatographed (silica 40 to 50% ethyl acetate in hexanes)

Sources & evidence

ORD record
ord-140d2630397d47c48d76d32391812729
Source dataset
uspto-grants-1999_01
Patent number
US05861421

Reaction notes

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