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Synlett 2004(5): 0807-0810  
DOI: 10.1055/s-2004-820017
LETTER
© Georg Thieme Verlag Stuttgart · New York

Facile Synthesis of Cross-Conjugated gem-Disubstituted Trienes via ­Palladium-Catalyzed Cross-Coupling Protocol of 1,1-Disubstituted 2,4-Diiodo-But-1-ene With Alkenes

Min Shi*, Li-Xiong Shao
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 354 Fenglin Lu, Shanghai 200032, P. R. China
Fax: +86(21)64166128; e-Mail: mshi@pub.sioc.ac.cn.;
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Publication History

Received 4 February 2004
Publication Date:
24 February 2004 (online)

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Abstract

Cross-conjugated coupling products described in the title are obtained in moderate to high yields by the reactions of the corresponding 1,1-disubstituted 2,4-diiodo-but-1-enes, which are derived from the ring-opening reaction of methylenecyclopropanes with iodine, with substituted alkenes in the presence of palladium(II) catalyst under simple Heck-type reaction conditions.

Key words

methylenecyclopropanes - cross-conjugated trienes - cross-coupling reaction - palladium catalyst - alkenes - diiodides

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13

Typical Procedure for the Ring-Opening of MCPs 1 by I 2 in 1,2-Dichloroethane (DCE): Under an ambient atmosphere, MCP 1a (10 mmol), I2 (10 mmol) and 1,2-dichloroethane (2.5 mL) were added into a Schlenk tube. The mixture was stirred at r.t. for 8 h. The solvent was removed under reduced pressure and the residue was then purified by a flash column chromatography to give product 2a as a yellow solid; mp 112-114 °C. 1H NMR (300 MHz, CDCl3) δ = 3.08 (t, J = 7.2 Hz, 2 H), 3.37 (t, J = 7.2 Hz, 2 H), 3.80 (s, 3 H, CH3O), 3.84 (s, 3 H, CH3O), 6.84 (d, J = 9.0 Hz, 4 H, Ar), 7.07 (d, J = 6.9 Hz, 2 H, Ar), 7.16 (d, J = 6.9 Hz, 2 H, Ar). 13C NMR (75 MHz, CDCl3): δ = 6.58, 44.53, 55.13, 55.19, 105.46, 113.31, 113.75, 129.91, 130.11, 132.54, 138.99, 149.71, 158.73, 158.79. IR (CH2Cl2): 3046, 2954, 2833, 2676, 2299, 2050, 1605, 1508, 1265, 1247, 741, 705 cm-1. MS: m/z (%) = 520 (84.92) [M+], 393 (28.23), 266 (100). HRMS: m/z calcd for C18H18I2O2: 519.9396; found: 519.9406.

14

Typical Procedure for the Heck-Type Reaction: Under an ambient atmosphere, 2a (0.25 mmol), 3a (0.30 mmol), Pd(OAc)2 (0.05 mmol), tetrabutylammonium chloride (TBAC) (0.25 mmol), NaHCO3 (0.5 mmol) and N,N-dimethylformamide (DMF) (1.0 mL) were added into a Schlenk tube. The reaction mixture was stirred at 100 °C for about 24 h. The reaction solution was washed with saturated brine, dried over anhyd MgSO4, and then purified by a flash column chromatography to give 5a as a pale yellow solid. Mp: 85-88 °C. 1H NMR (300 MHz, CDCl3) δ = 3.72 (s, 3 H), 5.36 (dd, J = 1.2, 11.4 Hz, 1 H), 5.39 (dd, J = 1.2, 17.7 Hz, 1 H), 6.21 (d, J = 15.9 Hz, 1 H), 6.39 (dd, J = 11.4, 17.7 Hz, 1 H), 7.09-7.18 (m, 5 H, Ar), 7.27-7.33 (m, 5 H, Ar), 7.47 (d, J = 15.9 Hz, 1 H). 13C NMR (75 MHz, CDCl3): δ = 51.49, 119.71, 121.65, 127.73, 127.81, 127.89, 128.13, 131.06, 131.11, 132.61, 135.14, 141.10, 141.48, 144.32, 147.80, 167.82. IR (CH2Cl2): 3067, 2978, 2304, 115, 1605, 1265, 739 cm-1. MS m/z (%) = 290 (35.94) [M+], 258 (32.98), 215 (100). HRMS: m/z calcd for C20H18O2: 290.1301; found: 290.1290.

15

To clarify the selectivity of the reaction, an experimental run was carried out on a larger scale of 2d (2.0 mmol) and 3a (2.4 mmol) as the substrates. We found that no other isomer was obtained based on the 1H NMR spectroscopic data of the reaction mixtures. At present stage, we are not sure of the reason on the selectivity of the reaction of 2c and 3c yet. We have determined the relative configuration of 5g by 1H NMR as the corresponding coupling constant of the former is 16.5 Hz and 8.7 Hz for the latter (Supporting Information).