Download PDF
Synlett 2007(17): 2663-2666  
DOI: 10.1055/s-2007-991051
LETTER
© Georg Thieme Verlag Stuttgart · New York

Regio- and Stereospecific Synthesis of Functionalized Divinyl Selenides

Samuel Braverman*, Ranjan Jana, Marina Cherkinsky, Hugo E. Gottlieb, Milon Sprecher
Department of Chemistry, Bar-Ilan University, Ramat-Gan 52900, Israel
Fax: +972(3)7384053; e-Mail: bravers@mail.biu.ac.il;
Further Information

Publication History

Received 12 August 2007
Publication Date:
25 September 2007 (online)

    Permissions and Reprints All articles of this category

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.

Key words

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

12

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).

13

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-CHarom), 128.8 (m-CHarom), 129.1 (CCH2), 129.2 (p-CHarom), 134.2 (ipso-Carom), 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.