Stereoselective Preparation of Homo- and Hetero-1,1-Dihalo-1-alkenes

Patrick Le Ménez; Jean-Daniel Brion; Jean-François Betzer; Ange Pancrazi; Janick Ardisson

doi:10.1055/s-2003-39296

LETTER

Stereoselective Preparation of Homo- and Hetero-1,1-Dihalo-1-alkenes

Patrick Le Ménez^a, Jean-Daniel Brion*^a, Jean-François Betzer^b, Ange Pancrazi^b, Janick Ardisson*^b
^a CNRS-BIOCIS, Faculté de Pharmacie, Université de Châtenay-Malabry, 92296 Châtenay-Malabry, France
Fax: +33(146)835398;
^b ‘Laboratoire de Synthèse Organique Sélective et Chimie Organométallique’, CNRS-UCP-ESCOM, UMR 8123, 13 Bd de l’Hautil, 95092 Cergy-Pontoise Cedex, France
Fax: +33(130)756015; e-Mail: janick.ardisson@chim.u-cergy.fr;

Abstract

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Abstract

Metallate rearrangements performed on 5-lithio-2,3-dihydrofuran 1 gave access to several homo- and hetero-1,1-bimetallated (or pseudo) alkenes 3 upon exposure to a cyanocuprate and quench with an electrophilic reagent Ε X. After metal/halogen exchange, several homo- or hetero-1,1-dihalo-1-alkenes were prepared stereospecifically and in good yields.

Key words

metallate rearrangement - Kocienski reaction - cuprate reagent - halogen exchange - 1,1-dihalo-1-alkene

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References

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Preparation of Z -7: A solution of the 5-lithio-2,3-dihydro-furan derivative 1 (2.5 mmol) [9] in THF (4 mL) was added, via cannula, to the solution of the bis-(trimethylsilyl) dilithio-cyanocuprate [15] at -30 °C (2.75 mmol, 1.1 equiv) in THF-Et₂O (6 mL/12 mL). The mixture was stirred at -5 °C to 0 °C for 1.5 h. The mixture was then cooled at -40 °C and Bu₃SnCl (4 equiv) was added. The temperature was allowed to rise to 0 °C over 1 h, stirring was maintained for 4 h, while the temperature rose to 20 °C. The reaction mixture was poured into a solution of saturated aqueous NH₄Cl/concentrated ammonia (4:1) at 0 °C and stirred for 30 min before extraction with diethyl ether. After purification by chromatography on silica gel compound Z -7 was obtained in 86% yield. IR (Neat): 3298, 2954, 2923, 2871, 1571, 1463, 1244, 1180, 1046, 960, 871, 830, 743, 685, 620, 591 cm^-1. ¹H NMR (200 MHz, CDCl₃) δ 0.0 (s, 9 H), 0.88 (m, 15 H), 1.32 (m, 6 H + OH), 1.45 (m, 6 H), 2.45 (q, J = 6.5 Hz, 2 H), 3.69 (t, J = 6.5 Hz, 2 H), 6.72 (t, J = 6.5 Hz, 1 H, J _H- ¹¹⁹ _Sn = J _H- ¹¹⁷ _Sn = 170.0 Hz). ¹³C NMR (50 MHz, CDCl₃) δ -0.3 (3 CH₃), 11.3 (3 CH₂, J _C- ¹¹⁹ _Sn = 318.0 Hz, J _C- ¹¹⁷ _Sn = 304.0 Hz), 13.6 (3 CH₃), 27.4 (3 CH₂, J _C- ¹¹⁹ _Sn = J _C- ¹¹⁷ _Sn = 58.0 Hz), 29.2 (3 CH₂, J _C- ¹¹⁹ _Sn = J _C- ¹¹⁷ _Sn = 19.0 Hz), 42.4 (CH₂, J _C- ¹¹⁹ _Sn = J _C- ¹¹⁷ _Sn = 57.5 Hz), 62.1 (CH₂), 147.6 (C), 150.7 (CH, J _C- ¹¹⁹ _Sn = J _C- ¹¹⁷ _Sn = 20.0 Hz). MS (CI, CH₄): for major ¹²⁰Sn isotope, m/z 377, 311, 308, 306, 304, 252, 250, 248, 102.

<A NAME="RG02803ST-11">11</A> To a solution of the vinyltin derivative Z -7 in CH₂Cl₂ (or CH₃CN) at 0 °C (or below) was slowly added a CH₂Cl₂ solution of iodine (1.05 equiv) until persistence of an orange-red color (1 h at 0 °C). The solution was then washed with an aqueous KF and a saturated aqueous Na₂SO₃ solution before evaporation of the solvent and chromato-graphy on silica gel. Compound Z -8 was obtained in 91% yield. ¹H NMR (200 MHz, CDCl₃) δ 0.18 (s, 9 H), 2.45 (q, J = 6.5 Hz, 2 H), 2.5 (s, 1 H), 3.72 (t, J = 6.5 Hz, 2 H), 6.57 (t, J = 6.5 Hz, 1 H). ¹³C NMR (50 MHz, CDCl₃) δ 1.5 (3 CH₃), 42.1 (CH₂), 60.6 (CH₂), 116.0 (C), 143.5 (CH). MS (CI, CH₄): m/z 181, 143, 103, 91, 73. Anal. calcd for C₇H₁₅IOSi: C, 31.12; H, 5.60; I, 46.97; O, 5.92; Si, 10.40; Found: C, 31.32; H, 5.48.

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Preparation of Z -9, E -10 and E -11 derivatives:
A solution of the 5-lithio-2,3-dihydrofuran derivative 1 (2.5 mmol) in THF (4 mL) was added, via cannula, to the solution of the bis-[(tributyl)stannyl] dilithiocyanocuprate [9] at -30 °C (2.75 mmol, 1.1 equiv) in THF-Et₂O (6 mL/12 mL). The mixture was stirred at -5°C to 0 °C for 1.5 h 30. The mixture was then cooled at -40 °C and a THF solution (1-2 mL) of the quenching agent, NIS, NBS or NCS (4.0 equiv), was added. The temperature was allowed to rise to 0 °C for 1 h, stirring was maintained for 4 h, with temperature going up to 20 °C. The reaction mixture was poured into a solution of saturated aqueous NH₄Cl/concentrated ammonia (4:1) at 0 °C and stirred for 30 min before extraction with diethyl ether. The Z -9 compound was obtained in 75% yield. IR (Neat): 3324, 2950, 2920, 2870, 2850, 1594, 1461, 1376, 1180, 1044, 907, 733, 690, 664, 597 cm^-1. ¹H NMR (200 MHz, CDCl₃) δ 0.85 (t, J = 8.0 Hz, 6 H), 0.96 (t, J = 8.0 Hz, 9 H), 1.30 (m, 6 H), 1.48 (m, 1 H, OH), 2.45 (q, J = 6.5 Hz, 2 H), 3.69 (t, J = 6.5 Hz, 2 H), 6.14 (t, J = 6.5 Hz, 1 H, J _H- ¹¹⁹ _Sn = J _H- ¹¹⁷ _Sn = 42.0 Hz). ¹³C NMR (50 MHz, CDCl₃) δ 11.1 (3 CH₂, J _C- ¹¹⁹ _Sn = 348.0 Hz, J _C- ¹¹⁷ _Sn = 332.0 Hz), 13.6 (3 CH₃), 27.2 (3 CH₂, J _C- ¹¹⁹ _Sn = J _C- ¹¹⁷ _Sn = 60.0 Hz), 28.6 (3 CH₂, J _C- ¹¹⁹ _Sn = J _C- ¹¹⁷ _Sn = 20.0 Hz), 42.6 (CH₂, J _C- ¹¹⁹ _Sn = J _C- ¹¹⁷ _Sn = 32.0 Hz), 60.9 (CH₂), 110.0 (C), 145.2 (CH, J _C- ¹¹⁹ _Sn = J _C- ¹¹⁷ _Sn = 20.0 Hz). MS (CI, CH₄): for major ¹²⁰Sn isotope, m/z 377, 322, 307, 252. Anal. calcd for C₁₆H₃₃IOSn: C, 39.46; H, 6.83; I, 26.06; O, 3.29; Sn 24.37; Found: C, 39.88; H, 7.09.

Selected NMR spectroscopic data
Z -12: ¹H NMR (200 MHz, CDCl₃) δ 2.22 (q, J = 6.5 Hz, 2 H), 3.63 (t, J = 6.5 Hz, 2 H), 6.51 (t, J = 6.5 Hz, 1 H). ¹³C NMR (50 MHz, CDCl₃) δ 40.4 (CH₂), 55.5 (C), 59.9 (CH₂), 143.5 (CH). E -13: ¹H NMR (200 MHz, CDCl₃) δ 2.37 (q, J = 7.0 Hz, 2 H), 3.72 (t, J = 7.0 Hz, 2 H), 6.90 (t, J = 7.0 Hz, 1 H). ¹³C NMR (50 MHz, CDCl₃) δ 37.8 (CH₂), 51.0 (C), 60.3 (CH₂), 143.7 (CH).
14 : ¹H NMR (200 MHz, CDCl₃) δ 1.8 (s, 1 H), 2.44 (q, J = 6.5 Hz, 2 H), 3.76 (t, J = 6.5 Hz, 2 H), 6.48 (t, J = 6.5 Hz, 1 H). ¹³C NMR (50 MHz, CDCl₃) δ 36.2 (CH₂), 60.3 (CH₂), 90.5 (C), 135.1 (CH).
E -15: ¹H NMR (200 MHz, CDCl₃) δ 2.43 (q, J = 7.0 Hz, 2 H), 3.69 (t, J = 7.0 Hz, 2 H), 6.51 (t, J = 7.0 Hz, 1 H). ¹³C NMR (50 MHz, CDCl₃) δ 34.9 (CH₂), 60.5 (CH₂), 68.5 (C), 140.3 (CH).
Z -16: ¹H NMR (200 MHz, CDCl₃) δ 2.34 (q, J = 7.0 Hz, 2 H), 3.73 (t, J = 7.0 Hz, 2 H), 6.18 (t, J = 7.0 Hz, 1 H). ¹³C NMR (50 MHz, CDCl₃) δ 39.2 (CH₂), 60.4 (CH₂), 75.7 (C), 137.3 (CH).

(Me₃Si)₂CuCNLi₂ was prepared by reaction of 2 equivalents of MeLi with 2.2 equivalents of (Me₃Si)₂ in THF/HMPA (5 mL:1 mL), and 1 equivalent of CuCN at 0 °C. For preparation of Me₃SiLi see:

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