Regio- and Stereospecific Synthesis of Functionalized Divinyl Selenides

Abstract

Symmetrical Z,Z-bis(1-hydroxymethyl-2-chlorovinyl) selenides have been obtained in high yields by regio- and stereo­specific addition of selenium dichloride to propargylic alcohols. Presumably, the hydroxyl group plays an important role in the ­regio- and stereospecific addition.

selenium - alkynes - divinyl selenides - divinyl di­selenides - electrophilic addition - regioselectivity - stereoselectivity

References and Notes

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<A NAME="RG27107ST-12">12</A>

Representative Procedure for the Preparation of (3 Z )-4-Chloro-3-{[( Z )-2-chloro-1-(1-hydroxy-1-methyl-ethyl)vinyl]selanyl}-2-methylbut-3-en-2-ol (1e) The THF solution of selenium dichloride (1 mmol) prepared by the known procedure³ was added dropwise to a solution of 2-methylbut-3-yn-2-ol (172 mg, 2 mmol) in dry THF (2 mL) at 0 °C. Then the reaction mixture was stirred at r.t. for 35 min. After completion of the reaction (TLC), the reaction mixture was extracted with EtOAc (20 mL) and washed with H₂O (5 mL) and brine (2 × 5 mL). The organic layer was dried over Mg₂SO₄. After evaporation of the solvent the crude product, containing 92% of selenide 1e and 8% of diselenide 2e, was obtained. After column chromatography with silica gel (hexanes-EtOAc, 4:1) pure 1e was obtained (264 mg, 82% yield).

<A NAME="RG27107ST-13">13</A>

Analytical and Spectroscopic Data for Representative Compounds
(2 Z )-3-Chloro-2-{[( Z )-2-chloro-1-(hydroxymethyl)vin-yl]selanyl}prop-2-en-1-ol (1a) Viscous liquid. IR (neat): 3453 (br), 2972, 1571, 1368, 1169, 1129, 980 cm^-1. ¹H NMR (600 MHz, CDCl₃): δ = 3.62 (br s, 2 H, OH), 4.46 (d, 4 H, J = 1.1 Hz), 6.55 (t, 2 H, J = 1.1 Hz). ¹³C NMR (150 MHz): δ = 60.9 (CH₂), 122.2 (CH, ² J _C,Se = 22.6 Hz), 132.8 (C, ¹ J _C,Se = 112.6 Hz). HRMS: m/z calcd for C₆H₈Cl₂O₂ ⁷⁸Se: 259.9074; found: 259. 9058.
(2 Z )-3-Chloro-2-{[(1 Z )-2-chloro-1-(hydroxy-methyl)prop-1-enyl]selanyl}but-2-en-1-ol (1b) Solid, mp 56-58 °C. IR (KBr): 3324 (br), 2976, 1606, 1455, 1015 cm^-1. ¹H NMR (600 MHz, CDCl₃): δ = 2.40 (t, 6 H, J = 0.9 Hz), 3.67 (br s, 2 H), 4.41 (q, 4 H, J = 0.9 Hz). ¹³C NMR (150 MHz): δ = 26.6 (CH₃), 63.5 (CH₂), 126.5 (=CCH₂, ¹ J _C,Se = 112.3 Hz), 134.0 (=CCl, ² J _C,Se = 15.9 Hz). HRMS: m/z calcd for C₈H₁₂Cl₂O₂ ⁸⁰Se: 289.9380; found: 289.9358. Anal. Calcd: C, 33.13; H, 4.17. Found: C, 33.25; H, 4.20. (2 Z )-3-Chloro-2-{[(1 Z )-2-chloro-1-(hydroxymethyl)but-1-enyl]selanyl}pent-2-en-1-ol (1c) Yellowish, viscous liquid. IR (neat): 3323 (br), 2974, 1604, 1455, 1015 cm^-1. ¹H NMR (300 MHz, CDCl₃): δ = 1.11 (t, J = 7.5 Hz, 6 H), 2.73 (q, J = 9.0 Hz, 4 H), 4.05 (br s, 2 H), 4.36 (s, 4 H). ¹³C NMR (75 MHz): δ = 12.2 (2 C), 32.9 (2 C), 63.6 (2 C), 125.8 (2 C), 140.2 (2 C). HRMS: m/z calcd for C₁₀H₁₆Cl₂O₂ ⁷⁸Se: 315.9706; found: 315.9700.
(2 Z )-3-Chloro-2-{[( Z )-2-chloro-1-(hydroxymethyl)-2-phenylvinyl]selanyl}-3-phenylprop-2-en-1-ol (1d) Yellowish, viscous liquid. IR (neat): 3438 (br), 2953, 1605, 1456, 1011 cm^-1. ¹H NMR (600 MHz, CDCl₃): δ = 2.75 (br s, 2 H), 4.51 (s, 4 H), 7.17-7.19 (m, 4 H), 7.30-7.35 (m, 6 H). ¹³C NMR (150 MHz): δ = 64.1 (CH₂), 128.2 (o-CH_arom), 128.8 (m-CH_arom), 129.1 (CCH₂), 129.2 (p-CH_arom), 134.2 (ipso-C_arom), 138.6 (CCl). HRMS: m/z calcd for C₁₈H₁₆Cl₂O₂ ⁷⁸Se: 411.9700; found: 411.9697. (3 Z )-4-Chloro-3-{[( Z )-2-chloro-1-(1-hydroxy-1-methyl-ethyl)vinyl]selanyl}-2-methylbut-3-en-2-ol (1e) Brownish solid, mp 83 °C. IR (KBr): 3454 (br), 2972, 1567, 1368, 1169, 1129, 980 cm^-1. ¹H NMR (600 MHz, CDCl₃): δ = 1.61 (s, 12 H), 2.92 (br s, 2 H), 6.28 (s, 2 H). ¹³C NMR (150 MHz): δ = 28.4 (CH₃), 74.3 (C), 116.4 (CH, ² J _C,Se = 15.9 Hz), 143.0 (C=, ¹ J _C,Se = 116.6 Hz). HRMS: m/z calcd for C₁₀H₁₆Cl₂O₂ ⁸⁰Se: 317.9693; found: 317.9677. Anal. Calcd: C, 37.76; H, 5.07. Found: C, 37.58; H, 5.08.
(3 Z )-4-Chloro-3-{[( Z )-2-chloro-1-(1-hydroxy-1-methyl-ethyl)vinyl]diselanyl}-2-methylbut-3-en-2-ol (2e) Yellowish solid, mp 88-89 °C. ¹H NMR (600 MHz, CDCl₃): δ = 1.64 (s, 12 H), 2.70 (br s, 2 H), 6.17 (s, 2 H). ¹³C NMR (150 MHz): δ = 28.22 (CH₃), 74.9 (C), 113.0 (CH), 139.5 (C=, ¹ J _C,Se = 132.4 Hz). HRMS: m/z calcd for C₁₀H₁₆ ³⁷Cl₂O₂ ⁷⁸Se₂ [M⁺]: 397.8814; found: 397.8816. Anal. Calcd: C, 30.25; H, 4.06. Found: C, 30.29; H, 3.88.
(1 Z )-1-Chloro-2-{[( Z )-2-chloro-1-(1-hydroxy-1-methyl propyl)vinyl]selanyl}-3-methylpent-1-en-3-ol (1f) Deep-brown liquid; was obtained as an inseparable mixture of two diastereomers in the ratio 3:2. IR (neat): 3446 (br), 2972, 1568, 1456, 1158 cm^-1. First diastereomer: ¹H NMR (600 MHz, CDCl₃): δ = 0.94 (t, J = 7.5 Hz, 6 H), 1.59 (s, 6 H), 1.81-2.09 (m, 2 H) 2.73 (br s, 2 H), 6.33 (s, 2 H). ¹³C NMR (150 MHz): δ = 8.1 (CH₃), 26.5 (CH₃), 33.2 (CH₂), 76.8 (C), 116.41 (CH, ² J _C,Se = 15.9 Hz), 142.4 (C, ¹ J _C,Se = 116.3 Hz). Second diastereomer: ¹H NMR (600 MHz, CDCl₃): δ = 0.94 (t, J = 7.5 Hz, 6 H), 1.58 (s, 6 H), 1.81-2.09 (m, 2 H) 2.73 (br s, 2 H), 6.32 (s, 2 H). ¹³C NMR (150 MHz): δ 8.1 (CH₃), 26.4 (CH₃), 33.2 (CH₂), 76.8 (C), 116.39 (CH, ² J _C,Se = 15.9 Hz), 142.3 (C, ¹ J _C,Se = 116.6 Hz). HRMS: m/z calcd for C₁₂H₂₀Cl₂O₂ ⁸⁰Se: 346.0006; found: 346.0012.
(2 Z )-3-Chloro-2-({( Z )-2-chloro-1-[hydroxy(phen-yl)methyl]vinyl}selanyl)-1-phenylprop-2-en-1-ol (1h) Colorless solid, mp 122-124 °C. IR (KBr): 3453 (br), 3075, 1568, 1169, 1128, 924 cm^-1. ¹H NMR (300 MHz, CDCl₃): δ = 3.37 (br s, 2 H), 6.05 (s, 2 H), 6.54 (s, 2 H), 7.24-7.43 (m, 10 H). ¹³C NMR (75 MHz): δ = 71.3 (CH), 123.6 (CH), 125.9 (CH), 128.2 (CH), 128.6 (CH), 137.4 (C), 140.6 (C). HRMS: m/z calcd for C₁₈H₁₆Cl₂O₂ ⁸⁰Se: 413.9693; found: 413.9715. Anal Calcd: C, 52.20; H, 3.89. Found: C, 51.91; H, 3.79.

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