References and Notes
1
Braverman S.
Segev D.
J. Am. Chem. Soc.
1974,
96:
1245
2
Braverman S.
Pechenick T.
Gottlieb HE.
Sprecher M.
J. Am. Chem. Soc.
2003,
125:
14290
3
Maaninen A.
Chivers T.
Parvez M.
Pietikaeinen J.
Laitinen RS.
Inorg. Chem.
1999,
38:
4093
4
Comasseto JV.
Ling LW.
Petragnani N.
Stefani HA.
Synthesis
1997,
373
5 For review, see: Gavrilova GM.
Amosova SV.
Heteroat. Chem.
2006,
17:
491
6
Trofimov BA.
Amosova SV.
Gusarova NK.
Musorin GK.
Tetrahedron
1982,
38:
713
7a
Testaferri L.
Tiecco M.
Tingoli M.
Chianelli D.
Tetrahedron
1986,
42:
4577
7b
Testaferri L.
Tiecco M.
Tingoli M.
Chianelli D.
Tetrahedron
1986,
42:
63
8a
Murai T.
Kondo T.
Kato S.
Heteroat. Chem.
2004,
15:
187
8b
Murai T.
Takada H.
Kanda T.
Kato S.
Tetrahedron Lett.
1994,
35:
8817
9
Kato S.
Komuro T.
Takahiro K.
Ishihara H.
Murai T.
J. Am. Chem. Soc.
1993,
115:
3000
10
Comasseto JV.
Petragnani N.
J. Organomet. Chem.
1978,
152:
295
11
Silveira CC.
Santos PCS.
Braga AL.
Tetrahedron Lett.
2002,
43:
7517
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.
14
Duddeck H.
Prog. Nucl. Magn. Reson. Spectrosc.
1995,
27:
1
15
Liotta D.
Zima G.
Saindane M.
J. Org. Chem.
1982,
47:
1258
16
Usuki Y.
Iwaoka M.
Tomoda S.
Chem. Lett.
1992,
1507
17a
Filer CN.
Ahern D.
Fazio R.
Shelton EJ.
J. Org. Chem.
1980,
45:
1313
17b
Schmid GH.
Garratt DG.
Tetrahedron Lett.
1975,
3991
18
Zade SS.
Panda S.
Singh HB.
Wolmershaeuser G.
Tetrahedron Lett.
2005,
46:
665
For recent reviews, see:
19a
Tiecco M.
Organoselenium Chemistry. Modern Developments in Organic Synthesis, In Topics in Current Chemistry
Vol. 208:
Wirth T.
Springer;
Berlin:
2000.
p.7
19b
Browne DM.
Wirth T.
Curr. Org. Chem.
2006,
10:
1893
19c
Beaulieu PL.
Deziel R. In Organoselenium Chemistry
Back TG.
Oxford University Press;
Oxford UK:
1999.
p.35
20a
Comasseto JV.
J. Organomet. Chem.
1983,
253:
131
20b
Gerard J.
Hevesi L.
Tetrahedron
2001,
57:
9109
20c
Amosova SV.
Martynov AV.
Mahaeva NA.
Belozerova OV.
Penzic MV.
Albanov AI.
Yarosh OG.
Voronkov MG.
J. Organomet. Chem.
2007,
692:
946
21a
Martynov AV.
Potapov VA.
Amosova SV.
Makhaeva NA.
Beletskaya IP.
Hevesi L.
J. Organomet. Chem.
2003,
674:
101
21b
Silveira CC.
Braga AL.
Vieira AS.
Zeni G.
J. Org. Chem.
2003,
68:
662
21c
Tingoli M.
Tiecco M.
Testaferri L.
Temperini A.
Pelizzi G.
Bacchi A.
Tetrahedron
1995,
51:
4691
22
Augustyns B.
Maulide N.
Marko IE.
Tetrahedron Lett.
2005,
46:
3895
23a
Sheng S.-R.
Liu X.-L.
Xu Q.
Song C.-S.
Synthesis
2003,
2763
23b
Pearson WH.
Szura DP.
Postich MJ.
J. Am. Chem. Soc.
1992,
114:
1329
23c
Hamaguchi M.
Nagai T.
J. Org. Chem.
1989,
54:
3957
24
Reich HJ.
Willis WW.
J. Am. Chem. Soc.
1980,
102:
5967
