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DOI: 10.1055/s-2005-921931
Indium(I) Bromide-Mediated Regioselective Markovnikov Hydroselenation, Diselenation and Hydration of Terminal Alkynes with Diphenyldiselenide in Aqueous Media
Publikationsverlauf
Publikationsdatum:
28. November 2005 (online)
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Abstract
The indium(III) selenolate obtained from indium(I) bromide and diphenyldiselenide promotes, alternatively, the Markovnikov hydroselenation, diselenation or hydration of terminal alkynes, depending on the experimental conditions.
Key words
indium(I) bromide - diphenyldiselenide - vinyl selenides - vinyl diselenides - hydration of alkynes - aqueous media
- 1
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12a For hydration of alkynes catalyzed by mercury salts, see:
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Lucey DW.Atwood JD. Organometallics 2002, 21: 2481 ; and references therein - 13
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References
[Br2InOH(bipy)]2·4THF was prepared by stirring equimolar quantities of InBr and PhSeBr (1 mmol) in 20 mL of dry THF (Na/benzophenone), in a three-neck round-bottom flask, equipped with an addition funnel charged with 1 mmol of 2,2′-dipyridyl (bipy) dissolved in 5 mL of THF. As soon as the solid InBr dissolved giving a pale yellow solution, the stirring was interrupted and the bipy solution added dropwise. After addition of the bipy, H2O (5 mmol) was added, and the flask opened to the lab atmosphere and monitored for precipitation of colorless crystals. As soon as these crystals start to deposit in the vessel, any solid impurities were filtered and the crystals allowed to grow. This treatment leaded to the deposition of [Br2InOH(bipy)]2·4THF (42 mg, 0.05 mmol, 10%) after 24 h at r.t. These crystals become an amorphous powder, upon drying. Analysis of the powder revealed loss of THF. Anal. Calcd for [Br2InOH(bipy)]2·2THF (%): Br, 30.8; In, 22.1. Found (%): Br, 30.7; In, 21.9. After removal of [Br2InOH(bipy)]2·4THF, the THF solution was transferred to a separation funnel and partitioned in H2O-CH2Cl2. The CH2Cl2 solution was pumped to dryness and the residue was purified by column chromatography in silica/hexane to give PhSeSePh (47 mg, 0.15 mmol, 30%) melting at 60 °C (lit. [17] 63 °C).
6Electronic Supplementary Information available: crystallographic data for the compound [Br2InOH(bipy)]2·4THF: CCDC No 279659.
7The Markovnikov hydroselenation of the alkynes involved the following steps: aqueous EtOH (95%, 2 mL) was deoxygenated by refluxing it, under N2 atmosphere, for 2 h in a Schlenk tube. After cooling to r.t., the tube was charged with PhSeSePh (314 mg, 1 mmol) and InBr (195 mg, 1 mmol). Continuous stirring led to the dissolution of the red solid InBr after 15-30 min. At this point, the alkyne (1 mmol) was added via syringe, and the reaction monitored by TLC. After 3 h, the reaction was quenched with H2O and the organics extracted with CH2Cl2 (2 × 10 mL). The extract was dried (Na2SO4) and evaporated to dryness under vacuo. The oily residue was purified by columnn chromatography (silica gel/hexane) to produce the vinylic selenides 2; yields are given in Scheme
[3]
. Spectroscopic Data for Compounds 2a-c are as follow:
2-Phenylselenohex-1-ene (2a) [63831-76-5]:
[9]
yield 70%; colorless oil. 1H NMR (CDCl3): δ = 7.50 (m, 2 H), 7.22 (m, 3 H), 5.43 (s, 1 H), 5.08 (s, 1 H), 2.25 (t, J = 7.4 Hz, 2 H), 1.47 (quint., J = 7.3 Hz, 2 H), 1.27 (sext., J = 7.4 Hz, 2 H), 0.85 (t, J = 7.3 Hz, 3 H). 13C NMR and DEPT-135 (CDCl3): δ = 143.44 (C
quat.
), 134.66 (C
ar
-H), 129.11 (C
ar
-H), 129.06 (C
quat.
), 127.63 (C
ar
-H), 116.05 (=CH2), 38.01 (CH2), 30.82 (CH2), 21.88 (CH2), 13.79 (CH3).
2-Phenylseleno-hept-1-ene (2b) [211189-33-2]:
[18]
yield 80%; colorless oil. 1H NMR (CDCl3): δ = 7.47 (m, 2 H), 7.22 (m, 3 H), 5.41 (s, 1 H), 5.03 (s, 1 H), 2.20 (t, J = 7.3 Hz, 2 H), 1.46 (quint., J = 7.3 Hz, 2 H), 1.20 (m, 4 H), 0.80 (t, J = 7.1 Hz, 3 H). 13C NMR (CDCl3): δ = 143.52, 134.68, 129.13, 129.09, 127.67, 116.13, 38.31, 31.01, 28.37, 22.39, 14.00.
2-Phenylselenodec-1-ene (2c): colorless oil. 1H NMR (CDCl3): δ = 7.48 (m, 2 H), 7.22 (m, 3 H), 5.43 (s, 1 H), 5.04 (s, 1 H), 2.21 (t, J = 7.3 Hz, 2 H), 1.47 (quint., J = 7.3 Hz, 2 H), 1.20 (s, 10 H), 0.82 (t, J = 6.8 Hz, 3 H). 13C NMR and DEPT-135 (CDCl3): δ = 143.50 (C
quat.
), 134.67 (C
ar
-H), 129.13 (C
ar
-H), 129.04 (C
quat.
), 127.65 (C
ar
-H), 116.07 (=CH2), 38.32 (CH2), 31.83 (CH2), 29.32 (CH2), 29.19 (CH2), 28.81 (CH2), 28.67 (CH2), 22.64 (CH2), 14.09 (CH3).
Compounds 2′a were prepared as a 2:3 mixture of stereoisomers (Z:E) following the same experimental conditions described above,
[7]
except the reaction time, which in this case was 48 h.
(Z,E)-2-Phenylselenohex-2-ene (2′a):
[9]
colorless oil. 1H NMR (CDCl3): δ = 7.40 (m, 2 H), 7.19 (m, 3 H), 5.91 (t, J = 7.4 Hz, 0.4 H), 5.74 (t, J = 7.0 Hz, 0.6 H), 2.19 (q, J = 7.3 Hz, 1.2 H), 2.04 (q, J = 7.3 Hz, 0.8 H), 1.95 (s, 3 H), 1.38 (sext, J = 7.4 Hz, 2 H), 0.88 (t, J = 7.3 Hz, 1.8 H), 0.87 (t, J = 7.3 Hz, 1.2 H). 13C NMR and DEPT-135 (CDCl3): δ = 137.46 (C-H), 134.67 (C-H), 133.08 (C-H), 132.55 (C-H), 130.56 (C
quat
), 129.75 (C
quat
), 128.99 (C-H), 128.91 (C-H), 127.43 (C
quat
), 126.80 (C-H), 126.77 (C-H), 125.69 (C
quat.
), 33.90 (CH2), 31.54 (CH2), 26.47 (CH3), 22.58 (CH2), 22.40 (CH2), 19.98 (CH2), 13.78 (CH3), 13.70 (CH3). MS (70 eV, EI, for 80Se): m/z (unassigned Z,E-isomers, %): 240 (24, 40) [M], 157 (17, 10), 130 (9, 64), 116 (100, 4), 55 (87, 100).
Heptan-2-one (3b) [110-43-0]:
[19]
colorless liquid. 1H NMR (CDCl3): δ = 2.39 (t, J = 7.5 Hz, 2 H), 2.10 (s, 3 H), 1.54 (quint., J = 7.3 Hz, 2 H), 1.26 (m, 4 H), 0.86 (t, J = 6.8 Hz, 3 H). 13C NMR (CDCl3): δ = 209.16, 43.66, 31.27, 29.71, 23.47, 22.34, 13.82.
Decan-2-one (3c) [693-54-9]:
[20]
colorless liquid. 1H NMR (CDCl3): δ = 2.35 (t, J = 7.4 Hz, 2 H), 2.06 (s, 3 H), 1.50 (quint., J = 7.2 Hz, 2 H), 1.21 (br s, 10 H), 0.81 (t, J = 7.2 Hz, 3 H). 13C NMR and DEPT-135 (CDCl3): δ = 208.94 (C=O), 43.62 (CH2), 31.68 (CH2), 29.60 (CH3), 29.22 (CH2), 29.04 (CH2), 28.99 (CH2), 23.73 (CH2), 22.49 (CH2), 13.89 (CH3). MS (70 eV, EI): m/z (%) = 156 (2) [M], 138 (10), 113 (10), 99 (82), 71 (100).
5-Phenylselenopentan-2-one (6) [66241-86-9]:
[2a]
[21]
1H NMR (CDCl3): δ = 7.41 (m, 2 H), 7.18 (m, 3 H), 2.83 (t, J = 7.1 Hz, 2 H), 2.49 (t, J = 7.1 Hz, 2 H), 2.01 (s, 3 H), 1.87 (quint., J = 7.0 Hz, 2 H). 13C NMR (CDCl3): δ = 207.74, 132.44, 129.84, 128.94, 126.73, 42.82, 29.80, 27.00, 23.84.
Nonan-2,8-dione (5a) [30502-73-9]:
[22]
yield 70%; colorless liquid. 1H NMR (CDCl3): δ = 2.36 (t, J = 7.3 Hz, 4 H), 2.06 (s, 6 H), 1.51 (quint., J = 7.5 Hz, 4 H), 1.21 (quint., J = 6.8 Hz, 2 H). 13C NMR (CDCl3): δ = 208.97, 43.34, 29.85, 28.49, 23.37. MS (70 eV, EI): m/z (%) = 138 (10), 99 (61), 71 (100).
Decan-2,9-dione (5b) [16538-91-3]:
[23]
yield 92%; colorless solid; mp 52-53 °C. 1H NMR (CDCl3): δ = 2.35 (t, J = 7.4 Hz, 4 H), 2.06 (s, 6 H), 1.50 (quint., J = 6.8 Hz, 4 H), 1.20 (t, J = 7.3 Hz, 4 H). 13C NMR (CDCl3): δ = 209.01, 43.57, 29.78, 28.86, 23.56. MS (70 eV, EI): m/z (%) = 170 (1) [M], 152 (19), 128 (13), 113 (47), 58 (100).
Tetradecan-2,13-dione (5c) [7029-11-0]:
[22]
yield 90%; colorless solid; mp 74 °C. 1H NMR (CDCl3): δ = 2.34 (t, J = 7.5 Hz, 4 H), 2.07 (s, 6 H), 1.49 (quint., J = 7.3 Hz, 4 H), 1.19 (br s, 12 H). 13C NMR (CDCl3): δ = 209.25, 43.79, 29.80, 29.36, 29.33, 29.14, 23.86. MS (70 eV, EI):
m/z (%) = 211 (2), 169 (8), 58 (100).
(E)-1-Phenyl-1,2-phenylselenoethene [132330-37-1]: [13] 1H NMR (CDCl3): δ = 7.09-7.52 (m, 15 H), 7.02 (s, 1 H). 13C NMR and DEPT-135 (CDCl3): δ = 139.51 (C quat. ), 133.01 (CH), 132.08 (CH), 131.13 (C quat. ), 130.62 (C quat. ), 130.44 (C quat. ), 129.24 (CH), 129.15 (CH), 128.59 (CH), 128.28 (CH), 128.24 (CH), 127.43 (CH), 127.40 (CH), 126.04 (CH). MS (70 eV, EI for 80Se): m/z (%) = 416 (42) [M], 259 (56), 178 (100), 157 (71). We were not able to obtain a pure sample of the minoritary Z-isomer for NMR studies; nevertheless GC-MS analysis, 416 [M], is consistent with the proposed structure.