Scope of the allylation reaction with [RuCp(PP)]+ catalysts
thiophenol, hexanethiol, aniline, diethylmalonate and 2,3,4,6-
tetra-O-benzyl-D-glucose were commercially available and used
as received.
( CH2), 68.2 (OCCH2), 41.4 (CH2), 36.3 (CH2), 30.4 (CH). MS (ESI)
m/z = 193.37 [M + H]+.
[RuCpCl(PPh3)2],[23]
[RuCpCl(dppe)][24]
and [RuCpCl(o-
Allyl 2-adamantyl ether
EtOdppe)][8] were synthesized as reported. Mass spectrometry
was performed on a Finnigan MAT 900 equipped with an electro-
1H-NMR (CDCl3): δ 6.02–5.91 (m, 1H, H-allyl), 5.29 (dd, 1H, J = 3
and 18 Hz, H-allyl), 5.13 (dd, 1H, J = 3 and 9 Hz, H-allyl), 4.00 (d,
2H, J = 3 Hz, OCH2-allyl), 3.49–3.46 (m, 2H, OCH2), 2.17–2.08 (m,
3H, H-Ada), 1.86–1.78 (m, 6H, H-Ada), 1.76–1.63 (m, 6H, H-Ada).
13C-NMR (CDCl3): δ 136.6 (CH ), 116.6 ( CH2), 81.8 (CHO), 69.1
(CH2O), 38.4 (CH2), 32.7 (CH), 28.3 (CH2). MS (ESI) m/z = 193.10 [M
+ H]+.
1
spray interface. H NMR spectra (300 MHz), 13C-NMR (75.5 MHz)
1
and 31P{ H}NMR spectra (121.4 MHz) were measured on a Bruker
DPX-300. Chemical shifts are reported in ppm. The spectra were
taken at room temperature.
General Procedure for Catalytic Reactions
A 2.5 mmol aliquot of alcohol, 0.0025 mmol of the ruthenium
complex and 0.005 mmol of AgOTs were charged into the reaction
vessel and flushed with argon. Degassed and dried toluene was
added (2.5 ml) and the mixture was stirred for five minutes. Allyl
alcohol or diallyl ether was added (2.5–5 mmol) and the reaction
mixture was stirred at the indicated temperature. Samples were
takenatcertaintimeintervalswithanairtightsyringeandanalyzed
by gas chromatography. The products were isolated by means
of fractional distillation and characterized by 1H-NMR, 13C-NMR
and mass spectrometry. The spectroscopic data of the products
allyl octyl ether,[25] allyl butyl ether,[26] allyl ethyl ether,[27] allyl
cyclohexyl ether,[25] 3-allylindole,[28] allyl phenyl sulfide[29] and
allyl n-hexyl sulfide[30] were in agreement with the data found in
literature. Spectra of the new pure compounds are supplied as
Supporting Information.
General Procedure for Reactions with Alkyl-substituted Allyl
Alcohols
A 0.0025 mmol aliquot of the ruthenium complex [RuCpCl(PPh3)2],
0.005 mmol of AgOTs and 0.05 mmol of HOTs were charged
into the reaction vessel and flushed with argon. Degassed and
dried toluene was added (2.5 ml) and the mixture was stirred
for 5 min. Allylic alcohols 6–8 were added (2.5 mmol) and the
reaction mixture was stirred at 60 ◦C. Samples were taken at
certain time intervals with an airtight syringe and analyzed by gas
chromatography. The products (product mixtures) were isolated
by means of extraction with n-hexane from 10% aqueous NaOH
and subsequent distillation and were characterized by 1H-NMR
spectroscopy and mass spectrometry.
Dihex-1-en-3-yl ether (mixture of diastereoisomers 9 and 10)
Formation of acetals 4 and 5 (mixture of products)
1H-NMR (CDCl3): δ 5.87–5.81 (m, 2H, CHCH ), 5.19 (dd, 2H, J = 2
and 17 Hz, CH2), 5.11 (dd, 2H, J = 2 and 10 Hz, CH2), 4.11-4.07
(m, 2H, OCH), 1.54–1.47 (m, 4H, CH2), 1.44–1.36 (m, 4H, CH2), 0.92
(t, 6H, J = 7 Hz, CH3). MS (ESI) m/z = 183.2 [M + H]+.
A 2.5 aliquot mmol of 1-octanol, 2.5 mmol of allyl alcohol, 2.5 µmol
ofRuCp(dppe)Cland5 µmolofAgOTswerechargedintoareaction
vesselandflushedwithargon.A2.5 mlaliquotofdegassedtoluene
was added and the mixture was stirred at 100 ◦C. 1H-NMR (CDCl3):
δ 5.94–5.86 (m, H-allyl), 5.21 (dd, J = 4 and 9 Hz, H-allyl), 4.15–3.97
(m, CH2 allyl), 3.54 (m, CH2), 3.38 (m, CH2), 1.63–1.26 (m, CH2), 0.93-
0.88 (m, CH3). 13C-NMR (CDCl3): δ 134.8 (CH-allyl), 116.4 ( CH2),
104.2 (OCHO), 66.0 (CH2), 65.1 (CH2), 31.9 (CH2), 30.5 (CH2), 29.6
(CH2), 27.5 (CH2), 26.4 (CH2), 19.3 (CH2), 13.8 (CH3), 8.9 (CH3). MS
(ESI) m/z (compound 4) = 301.4 [M + H]+, 271.5 [M − C2H5]+. MS
(ESI) m/z (compound 5) = 229.3 [M + H]+, 199.8 [M − C2H5]+.
Dihex-2-en-1-yl ether (11) and hex-2-en-1-yl hex-1-en-3-yl ether (12)
(mixture of products)
1H-NMR major component 11 (CDCl3): δ 5.58–5.55 (m, 2H, CH),
4.03 (d, 2H, J = 5 Hz, OCH2), 2.06–2.04 (m, 2H, CH2); 1.43–1.36
(m, 4H, CH2), 0.91 (t, 3H, J = 7 Hz). MS (ESI) m/z = 183.1 [M + H]+.
Hex-1-en-3-yl n-octyl ether (13)
1-Allyl-2,3,4,6-tetra-O-benzyl-α-D-glucopyranoside and 1-allyl-2,3,4,
6-tetra-O-benzyl-β-D-glucopyranoside (mixture of products)
1HNMR(CDCl3):δ 5.60(m,1H,H-allyl),5.09(dd,1H, J = 2and16 Hz,
H2C ), 5.07 (dd, 1H, J = 2 and 10 Hz, H2C ), 3.57–3.53 (m, 1H,
OCH); 3.42–3.39 (m, 1H, OCH), 3.18–3.15 (m, 1H, OCH), 1.51–1.22
(m, 16H, CH2), 0.86–0.78 (m, 6H, CH3). MS (ESI) m/z = 213.1 [M +
H]+.
The general procedure for catalytic reaction was followed,
with the difference that purification of the product was not
performed by means of distillation, but after evaporation of the
reaction mixture to dryness, n-hexane was added. This caused
precipitation of the starting material, which was removed by
filtration; the resulting filtrate was concentrated to yield a mixture
of the products. The 1H-NMR spectroscopic data of 1-allyl-2,3,4,6-
tetra-O-benzyl-α-D-glucopyranoside[31] and 1-allyl-2,3,4,6-tetra-O-
benzyl-β-D-glucopyranoside[32] were in agreement with the data
found in literature.
Hex-2-en-1-yl n-octyl ether (14)
1H NMR (CDCl3): δ 5.61–5.56 (m, 2H, CH), 4.00 (d, 2H, J = 5 Hz,
OCH2), 3.43–3.38 (m, 2H, OCH2); 2.10–2.06 (m, 2H, CH2),
1.56–1.22 (m, 12H, CH2), 0.90–0.71 (m, 6H, CH3). MS (ESI)
m/z = 213.5 [M + H]+.
Phosphonium Salt Formation
Allyl 1-adamantyl ether
1H-NMR (CDCl3): δ 5.97–5.86 (m, 1H, H-allyl), 5.26 (dd, 1H, J = 3
and 17 Hz, H-allyl), 5.11 (dd, 1H, J = 3 and 9 Hz, H-allyl), 3.97 (d, 2H,
J = 5 Hz, OCH2), 2.15–2.13 (m, 3H, CH), 1.78–1.76 (m, 6H, CH2),
1.61–1.56 (m, 6H, CH2CO). 13C-NMR (CDCl3): δ 136.4 ( CH), 115.2
A2.5 µmolaliquotof[RuCpCl(PPh3)2],5 µmolofAgOTs,0.05 mmol
of triphenylphosphine and 0.05 mmol of HOTs were charged into
the reaction vessel and flushed with argon. Degassed and dried
toluene was added (2.5 ml) and the mixture was stirred for 5 min.
c
Appl. Organometal. Chem. 2011, 25, 212–219
Copyright ꢀ 2010 John Wiley & Sons, Ltd.
wileyonlinelibrary.com/journal/aoc