Self-metathesis of polyol allyl ethers towards carbohydrate-based oligohydroxy derivatives

Article abstract of DOI:10.1002/ejoc.201201083

Various allyl ethers of 1,4-anhydro-D-sorbitol and pentaerythritol were synthesised as starting materials for self-metathesis reactions. Thus, dimeric compounds having six free hydroxy groups became accessible and should be used as potential analogues of

Full text of DOI:10.1002/ejoc.201201083

FULL PAPER
DOI: 10.1002/ejoc.201201083
Self-Metathesis of Polyol Allyl Ethers towards Carbohydrate-Based
Oligohydroxy Derivatives
Maike Tober[a] and Joachim Thiem*[a]
Keywords: Carbohydrates / Metathesis / Renewable resources / Alditols / Homogeneous catalysis
Various allyl ethers of 1,4-anhydro-
D-sorbitol and pentae-
hydroxy groups became accessible and should be used as
rythritol were synthesised as starting materials for self-me- potential analogues of dipentaerythritol for alkyd resin for-
tathesis reactions. Thus, dimeric compounds having six free
mation.
interest.[13] Sorbitol, with six hydroxy groups, is known to
undergo intramolecular ring-closing reactions under acidic
conditions leading to mono- or dianhydro derivatives.[14]
Therefore, some kind of modification would be needed to
prevent this loss of availability of the hydroxy groups.
Introduction
Dipentaerythritol
[2,2,6,6-tetrakis(hydroxymethyl)-4-
oxaheptane-1,7-diol] is an important chemical commodity
used, for example, in lubricants, cosmetics, fire-resistant
coatings, and as stabilising agent. Dipentaerythritol is one
of the higher ether by-products of pentaerythritol pro-
duction,[1,2] and it is used as the polyol component in alkyd
resins.[3] The formation of pentaerythritol was observed in
1891 by reaction of acetaldehyde and formaldehyde with
lime milk.[4] Its production is still carried out in the same
way, with some improvements,[5–8] some of which allow the
formation of up to 35–40% yields of dipentaerythritol.[3,6,9]
As for any other material, the use of petrochemically de-
rived dipentaerythritol is ultimately problematic, due to the
anticipated peak in crude oil production first predicted by
Hubbert.[10,11] According to that theory, we must keep in
mind that raw oil is a finite resource, and therefore pro-
duction rates cannot be increased endlessly; they have to
peak someday. Another fact to consider is that the increase
in scientific effort that is needed to find and investigate new
oil fields, and the transport of the crude oil from, for exam-
ple, deep-sea oil-producing facilities, are becoming very ex-
pensive.[12] This will lead in the future to rising crude oil
prices, or prices stable at a high level, which will result in
high costs for the chemical industries.
Results and Discussion
Synthesis of Starting Materials for Self-Metathesis
Various allyl ethers of 1,4-anhydro-d-sorbitol were syn-
thesised as starting materials for self-metathesis reactions.
1,4-Anhydro-d-sorbitol (1) obtained from d-sorbitol[14] was
used in the synthesis of compounds 4, 10, 11, and 12 using
standard protecting-group chemistry as shown in Scheme 1.
Orthoester 3 served as the key intermediate in the syntheses
of compounds 4, 10, and 11. Allyl ether 4 was obtained in
two steps in 74% overall yield. Cleavage of the orthoester
in 4 and subsequent acetylation led to 10 in 59% overall
yield in four steps.
Protection of 3 as a 4-methoxybenzoyl ester (PMB) fol-
lowed by deblocking of the orthoester and subsequent pro-
tection of the vicinal free hydroxy groups 5-OH and 6-OH
as an isopropylidene acetal led to compound 7. Etherifi-
cation with allyl bromide followed by cleavage of the iso-
propylidene acetal and the 4-methoxybenzoyl ester and sub-
sequent acetylation led to 11 in eight steps and in 29% over-
all yield. Furthermore, compound 1 was transformed into
12 in 63% overall yield in four steps.
Thus, the search for alternative sources of raw materials
is of interest, and carbohydrates, natural polyols derived
from renewable resources, should be considered as alterna-
tives. Since pentitols and hexitols (e.g., xylitol and sorbitol)
are considered to be potential bulk chemicals, a closer look
in search of a useful analogue of dipentaerythritol was of
[a] Department of Chemistry, Faculty of Science, University of
Hamburg,
Self-Metathesis Reactions
Martin-Luther-King-Platz 6, 20146 Hamburg, Germany
Fax: +49-40-42838-4352
Compounds 4 and 10 were tested in self-metathesis reac-
tions to give dimerised products. In the first attempts to
synthesise the expected self-metathesis products (i.e., 17 and
18), an isomerisation of the double bond was observed.
E-mail: thiem@chemie.uni-hamburg.de
Homepage: http://www.chemie.uni-hamburg.de/oc/thiem/
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejoc.201201083.
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Self-Metathesis of Polyol Allyl Ethers
Scheme 1. Synthesis of starting materials for self-metathesis. (a) TrtCl, DMAP, Pyr, r.t., 10 h, 86%; (b) triethyl orthoacetate, p-TSA, DMF,
2 h, quant.; (c) NaH, BnBr, nBu4NI, DMF, 0 °C to r.t., 10 h, 95%; (d) NaH, AllBr, DMF, 0 °C to r.t., 10 h, 74%; (e) Pyr, PMBCl, 0 °C
to r.t., 24 h, 64%; (f) Amberlite 120 IR H+, MeOH/H2O (5:1), 60 °C, 24 h, 74%; (g) dimethoxypropane, CSA, DCM, r.t., 10 h, 97%;
(h) 90% acetic acid, 60 °C, 3 d, 83%; (i) 1. Amberlite 120 IR H+, EtOH/H2O (5:1), 60 °C, 10 h, 2. Pyr, Ac2O, r.t., 10 h, 92%; (j) 1. NaH,
AllBr, DMF, 0 °C to r.t., 10 h, 2. NaOAc, MeOH, 1 h, 3. Amberlite IR 120 H+, MeOH/H2O (3:1), 60 °C, 6 h, 4. Pyr, Ac2O, 10 h, 50%;
(k) NaH, AllBr, DMF, 0 °C to r.t., 10 h, 93%.
Scheme 2. Self-metathesis reactions. (a) Grubbs catalyst 2nd generation or Grubbs–Hoveyda catalyst 2nd generation, DCM, reflux, 12 h;
for yields, see Table 1, for yields of the reaction by addition of 1,4-benzoquinone, see Table 2; (b) 1. Amberlite 120 IR H+, EtOH/H2O
(3:1), 60 °C, 24 h, 2. NaOMe, MeOH, r.t., 12 h, 71%; (c) NaOMe, MeOH, r.t., 12 h, 97%.
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Table 1. Results of self-metathesis reactions.
[a] G2 = Grubbs catalyst, 2nd generation; GH2 = Grubbs–Hoveyda catalyst, 2nd generation.
This isomerisation could either occur in the starting materi- Hoveyda 2nd generation catalyst (1 mol-%), compound 18
als, leading to enol ethers 15 or 16, or after the self-metathe- was obtained in 18% yield. The recovered starting material
sis, leading to isomerised dimers 13 or 14 (see Scheme 2 and also contained isomerised starting material 16 in a ratio of
Table 1).
1:5 (16/10). By increasing the catalyst concentration to
In the case of orthoester 4, mostly isomerisation of the 8 mol-%, a product fraction with a yield of 67% of self-
starting material was observed. Using the Grubbs–Hoveyda metathesis products was obtained. This fraction consisted
2nd generation catalyst (10 mol-%), metathesis product of a mixture of 18 and isomerised dimer 14 in a ratio of
containing only 13 was obtained in 20% yield. In case of 1:10 (18/14). In addition, an increase in the amount of 16
acetylated allyl ether 10 using Grubbs 2nd generation cata- was noticed; the 10/16 ratio had become 4:1 (see Table 1).
lyst (6 mol-%), the desired dimer (i.e., 18) was obtained in
The ability of ruthenium complexes to catalyse isomeri-
52% yield without observing any isomerised self-metathesis sations of olefins has been mentioned previously.[15] Iso-
product or isomerised starting material. Using Grubbs– merisations occurring before[16,17] and after metathesis reac-
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Self-Metathesis of Polyol Allyl Ethers
Scheme 3. Self-metathesis reactions leading to compounds 22 and 23. (a) 1,4-benzoquinone, Grubbs–Hoveyda catalyst 2nd generation,
reflux, 10 h; (b) NaOMe, methanol, r.t., 10 h; (c) Pd(OH)2/charcoal, H2, r.t., 12 h; for yields, see Table 2.
tions[18,19] have likewise been noted as side-reactions occur- reverse-phase column chromatography, which removed the
ring during self-metathesis.[20] Since in most cases, isomeri- mentioned impurities. The desired compounds were ob-
sations are undesired side-reactions, different approaches to tained in moderate to high yields over two steps: 19 (42%
prevent this have been taken.[21,22] Indeed, the addition of from 4, and 92% from 10), 22 (65%), and 23 (49%). Al-
10 mol-% of 1,4-benzoquinone recommended by Grubbs et though the self-metathesis reaction of orthoester 4 to com-
al.[22] successfully prevented isomerisation side-reactions of pound 17 (59%) could be carried out, and the deprotection
4, 10, 11, and 12, and the self-metathesis products were ob- to give compound 19 (71%) worked well, the overall yield
tained exclusively (Scheme 3, Table 2).
of this pathway to compound 19 was 42%, which was no-
Compound 17 was obtained in 59% yield from 4, and ticeably lower than the overall yield of 19 derived from
derivative 10 gave 18 in 95% yield. Compounds 11 and 12 compound 10 (92%).
underwent self-metathesis reactions to give compounds 20
and 21 in 85 and 75% yields, respectively.
In an analogous approach, pentaerythtritol (24) was used
as the starting material for the synthesis of compound 30.
These compounds were not completely purified after me- The starting material for metathesis (i.e., 26) was synthe-
tathesis reactions. Following a first purification by column sised in 83% overall yield from 24 via intermediate 25,
chromatography, traces of impurities deriving from the me- which was prepared according to a known procedure.[23,24]
tathesis catalyst and 1,4-benzoquinone remained present. Compound 27 is another starting component for metathesis
Since the isolated compounds proved to be pure enough for derived from 24. Previously, a direct route from 24 leading
identification by NMR spectroscopy, no further purifica- to 27 was described in a one-pot reaction.[25] Nonetheless,
tion attempts were taken at this stage. After removal of the the synthetic route via 26 followed by removal of the ortho-
protecting groups, the desired compounds were purified by ester and subsequent acetylation was preferred due to an
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Table 2. Results of self-metathesis reactions with 1,4-benzoquinone.
[a] GH2 = Grubbs–Hoveyda catalyst, 2nd generation.
increased overall yield (77% over three steps). The self-me-
tathesis reaction was carried out under the aforementioned
conditions, and compound 29 was obtained in 76% yield.
Conclusions
The synthesis of allyl ethers of 1,4-anhydro-d-sorbitol
Compound 28 could not be isolated pure enough for unam- and pentaerythritol could be carried out to give precursors
bigious characterisation. Therefore, the fraction containing for self-metathesis reactions. Isomerisations observed in
crude 28 was deprotected, and compound 30 was obtained both the starting materials and the products could be
in merely 7% overall yield. However, following the deacetyl- prevented by using 1,4-benzoquinone. New oligo-
ation of 29, compound 30 could be obtained in 68% overall hydroxy alditol- and polyol-based metathesis products
yield, thus favouring this alternative pathway considerably could be obtained that may serve for the formation of alkyd
(Scheme 4).
resins.
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Self-Metathesis of Polyol Allyl Ethers
Scheme 4. Synthetic pathways leading to compound 30. (a) Triethyl orthoacetate, p-TSA, 80 °C, 4 h, 91%; (b) KOH, allyl bromide, 60 °C,
2 h, 91%); (c) 1. Amberlite IR120 H+, EtOH/H2O (3:1), 60 °C, 10 d; 2. Pyr, Ac2O, r.t., 10 h, 93%; (d) 1,4-benzoquinone, Grubbs–Hoveyda
catalyst 2nd generation, 10 h; (e) 1. Amberlite IR 120 H+, EtOH/H2O (3:1), reflux, 2 d; 2. NaOMe, MeOH, r.t., 12 h; (f) NaOMe, MeOH,
r.t., 12 h; for yields, see Table 2.
1 h. Afterwards, the reaction mixture was brought to room tem-
perature and stirred at room temperature until the gas evolution
Experimental Section
General Remarks: TLC was performed on aluminium sheets coated
with silica gel 60 (Merck), and detection was carried out by UV
light and heating with a 10% ethanolic solution of H2SO4. PE
means petroleum ether. Column chromatography was carried out
on silica gel 60 (40–63 μm; Merck) and silica gel RP18 (40–63 μm;
Merck). NMR spectra were recorded with Bruker AMX 400, AV
had stopped. Then the mixture was cooled to 0 °C, and allyl brom-
ide/benzyl bromide (1.5 equiv. per free OH group) was added drop-
wise. The reaction mixture was brought to room temperature and
stirred overnight. Afterwards, methanol was added, and the solu-
tion was stirred for 30 min. The solvents were removed in vacuo,
and the residue was dissolved in Et2O. This solution was washed
twice with brine and water, dried with sodium sulfate, and concen-
trated in vacuo. The crude residue was purified by column
chromatography.
1
400, AV 2400 (400 MHz for H and 100.67 MHz for 13C measure-
ments), and a Bruker DRX 500 (500 MHz for 1H and 125.48 MHz
for 13C measurements). Chemical shifts are given in ppm and refer-
enced to the corresponding solvent peak.[26] Mass spectra were re-
corded with Bruker Biflex II (MALDI-TOF, positive reflection
mode, matrix 2,5-dihydroxybenzoic acid) and Thermo Finnigan
MAT 95 XL or Agilent-6224-TOF ESI/MS (ESI mode) instru-
ments. Melting points were determined with an Apotec melting
point apparatus. The optical rotations were measured with a
Kruess P8000 polarimeter (589 nm, Na). Compounds 1,[14] 3,[14]
25,[23] and 26[24] were synthesised according to the literature.
General Procedure 2 (GP2). Self-Metathesis Reaction: The reaction
was carried out with the exclusion of moisture under nitrogen. A
solution of the monosaccharide (0.5 mm in absolute degassed
dichloromethane) was prepared. 1,4-Benzoquinone (10 mol-%) and
metathesis catalyst (5–7 mol-%) were added, and the solution was
stirred under reflux overnight. The compounds were purified by
column chromatography.
General Procedure 1 (GP1). Allylation/Benzylation: The monosac-
charide (1 g) was dissolved in N,N-dimethylformamide (20 mL) and
cooled to 0 °C. Sodium hydride (1.5 equiv. per free OH group) was
added in portions, and the reaction mixture was stirred at 0 °C for
1,4-Anhydro-6-O-trityl-D-sorbitol (2): 1,4-Anhydro-d-sorbitol (1,
4.930 g, 30.05 mmol) was dissolved in N,N-dimethylformamide
(75 mL). Triethylamine (2.5 equiv.), 4-(dimethylamino)pyridine
(catalytic amount), and triphenylmethyl chloride (1.3 equiv.) were
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1
added, and the reaction mixture was stirred at room temperature
for 10 h. The suspension was added to ice/water and extracted with
dichloromethane. The organic phase was washed three times with
saturated ammonium chloride solution and water, dried with so-
dium sulfate, and concentrated in vacuo. The crude residue was
purified by column chromatography (PE Ǟ Et2O, 0.1% triethyl-
amine) to obtain 2 (10.50 g, 25.83 mmol, 86%) as a colourless
foam. Rf = 0.34 (EtOAc). [α]2D3 = –4.4 (c = 1.24, MeOH). 1H NMR
(400 MHz, [D6]DMSO): δ = 3.00 (dd, J5,6b = 7.1, J6a,6b = 9.1 Hz,
1 H, 6b-H), 3.10 (dd, J5,6a = 2.0, J6a,6b = 9.1 Hz, 1 H, 6a-H), 3.37
(br. d, J1a,1b = 9.0 Hz, 1 H, 1b-H), 3.64 (dd, J3,4 = 2.3, J4,5 = 8.8 Hz,
= 0.80 (CH2Cl2/MeOH = 10:1). [α]2D3 = 5.9 (c = 0.94, CHCl3). H
NMR (400 MHz, [D6]DMSO): δ = 1.50 (s, 3 H, CCH3), 3.75 (dd,
J5,6b = 5.2, J6a,6b = 7.7 Hz, 1 H, 6b-H), 3.84 (s, 3 H, OCH3), 3.97
(br. d, J1a,1b = 10.3 Hz, 1 H, 1b-H), 4.00 (dd, J3,4 = 3.5, J4,5
=
2.1 Hz, 1 H, 4-H), 4.08 (br. d, J5,6a = 7.7, J6a,6b = 7.7 Hz, 1 H, 6a-
H), 4.25 (dd, J1a,2 = 3.8, J1a,1b = 10.3 Hz, 1 H, 1a-H), 4.43 (br. d,
J2,3 = 3.8, J3,4 = 3.8 Hz, 1 H, 3-H), 4.76 (bdd, J4,5 = 2.1, J5,6a
=
7.7, J5,6b = 5.2 Hz, 1 H, 5-H), 5.18 (br. d, J1a,2 = 3.8, J2,3 = 3.8 Hz,
1 H, 2-H), 7.06–7.04 (m, 2 H, 2 H-mBz), 7.94–7.91 (m, 2 H, 2 H-
oBz) ppm. 1H NMR (400 MHz, [D6]acetone): δ = 1.51 (s, 3 H,
CCH3), 3.83 (dd, J5,6b = 5.2, J6a,6b = 7.8 Hz, 1 H, 6b-H), 3.89 (s,
1 H, 4-H), 3.84 (dd, J1a,2 = 3.8, J1a,1b = 9.0 Hz, 1 H, 1a-H), 3.93– 3 H, OCH3), 4.03 (d, J1a,1b = 10.1 Hz, 1 H, 1b-H), 4.08 (dd, J3,4
=
3.89 (m, 3 H, 2-H, 3-H, 5-H), 4.85 (d, JOH,3 = 4.2 Hz, 1 H, O3-H),
4.88 (d, JOH,5 = 5.9 Hz, 1 H, O5-H), 4.98 (d, JOH,2 = 3.1 Hz, 1 H,
3.5, J4,5 = 2.2 Hz, 1 H, 4-H), 4.11 (d, J5,6a = 7.8, J6a,6b = 7.8 Hz, 1
H, 6a-H), 4.33 (dd, J1a,1b = 10.1, J1a,2 = 3.5 Hz, 1 H, 1a-H), 4.52
O2-H), 7.26–7.23 (m, 3 H, 3 H-pTrt), 7.34–7.31 (m, 6 H, 6 H-mTrt), (d, J2,3 = 3.5 Hz, 1 H, 3-H), 4.76 (ddd, J4,5 = 2.2, J5,6b = 5.2, J5,6a
7.45–7.43 (m, 6 H, 6 H-oTrt) ppm. 13C NMR (100 MHz, [D6]-
DMSO): δ = 144.1 [Cq, OC(CPh)3], 128.4 (Carom., C-oTrt), 127.7
= 7.8 Hz, 1 H, 5-H), 5.26 (br. d, J1a,2 = 3.5, J2,3 = 3.5 Hz, 1 H, 2-
H), 7.04–7.00 (m, 2 H, 2 H-mBz), 7.97–7.95 96 (m, 2 H, 2 H-oBz)
(Carom., C-mTrt), 126.8 (Carom., C-pTrt), 80.4 (C-4), 76.3 (C-2), 75.7 ppm. 13C NMR (100 MHz, [D6]DMSO): δ = 164.5 (Cq, C=O),
(C-3), 73.3 (C-1), 67.6 (C-5), 66.8 (C-6) ppm. MALDI-TOF-MS 163.3 (Cq, BzCOCH3), 131.4 (Carom., C-oBz), 121.3 (Cq, CC=O),
(DHB): m/z = 429.0 [M + Na]+, 444.9 [M + K]+.
117.6 (Cq, O3CCH3), 113.9 (Carom., C-mBz), 121.6 (Cq, BzCC=O),
118.6 (Cq, O3CCH3), 77.7 (C-2), 74.4 (C-4), 73.9 (C-5), 73.8 (C-3),
71.7 (C-1), 66.1 (C-6), 55.5 (OCH3), 21.9 (CCH3) ppm. 13C NMR
(100 MHz, [D6]acetone): δ = 164.4 (Cq, C=O, Cq, BzCOCH3),
132.6 (Carom., C-oBz), 121.6 (Cq, BzCC=O), 118.6 (Cq, O3CCH3),
114.8 (Carom., C-mBz), 79.4 (C-2), 76.2 (C-4), 75.7 (C-5), 75.5 (C-
3), 73.2 (C-1), 67.5 (C-6), 59.1 (OCH3), 21.9 (CCH3) ppm.
MALDI-TOF-MS (DHB): m/z = 323.1 [M + H]+.
2-O-Allyl-1,4-anhydro-3,5,6-tri-O-orthoacetyl- -sorbitol (4): 1,4-
D
Anhydro-3,5,6-tri-O-orthoacetyl-d-sorbitol (3, 0.765 g, 4.07 mmol)
was dissolved in N,N-dimethylformamide (20 mL), and the mixture
was cooled to 0 °C. Sodium hydride (1.5 equiv.) was added in por-
tions, and the reaction mixture was stirred at 0 °C for 1 h. After-
wards, the reaction mixture was brought to room temperature and
stirred at room temperature until the gas evolution had stopped.
The mixture was then cooled to 0 °C, and allyl bromide (1.5 equiv.)
was added dropwise. The reaction mixture was brought to room
temperature and stirred overnight. Afterwards, methanol was
added, and the solution was stirred for 30 min. The solvent was
removed in vacuo, and the residue was purified by column
chromatography (PE Ǟ PE/Et2O, 2:1, 0.1% triethylamine) to give
4 (0.691 g, 3.003 mmol, 74%) as a slightly yellowish oil. Rf = 0.20
(PE/EtOAc = 4:1).[α]2D3 = –100.2 (c = 1.15, CHCl3). 1H NMR
(400 MHz, [D6]DMSO): δ = 1.45 (s, 3 H, CH3CO3), 3.73 (dd, J5,6b
= 5.2, J6a,6b = 7.7 Hz, 1 H, 6b-H), 3.79 (br. d, J1a,1b = 9.8 Hz, 1 H,
1b-H), 3.82 (dd, J3,4 = 3.6, J4,5 = 2.2 Hz, 1 H, 4-H), 3.90 (br. d,
J1a,2 = 3.6, J2,3 = 3.6 Hz, 1 H, 2-H), 4.04–3.98 (m, 4 H, 1a-H, 6a-
H, CH2CH=), 4.30 (br. d, J2,3 = 3.6, J3,4 = 3.6 Hz, 1 H, 3-H), 4.69
Additionally, compound 6 (0.404 g, 1.35 mmol, 17%) was isolated.
1,4-Anhydro-2-O-p-methoxybenzoyl-D-sorbitol (6): 1,4-Anhydro-2-
O-p-methoxybenzoyl-3,5,6-tri-O-orthoacetyl-d-sorbitol (5, 1.75 g,
5.43 mmol) was dissolved in methanol/water (5:1, 20 mL), and Am-
berlite IR 120 H+ (10 wt-%) was added. The reaction mixture was
stirred under reflux for 24 h. The ion-exchange resin was removed
by filtration and washed several times with ethanol and water. The
solution was concentrated in vacuo, and the crude product was
purified by column chromatography (CH2Cl2 Ǟ CH2Cl2/MeOH,
20:1) to obtain pure 6 (1.20 g, 4.02 mmol, 74%) as a colourless
solid. M.p. 133.2 °C. Rf = 0.15 (CH2Cl2/MeOH = 10:1). [α]2D3
=
55.8 (c = 1.47, MeOH). 1H NMR (400 MHz, [D6]DMSO): δ =
3.44–3.38 (m, 1 H, 6b-H), 3.60 (ddd, J5,6a = 2.3, J6a,OH = 5.8, J6a,6b
= 11.5 Hz, 1 H, 6a-H), 3.75–3.71 (m, 3 H, 1b-H, 4-H, 5-H), 3.83
(s, 3 H, OCH3), 4.17 (dd, J1a,1b = 10.5, J1a,2 = 4.3 Hz, 1 H, 1a-H),
4.2 (br. s, 1 H, 3-H), 4.20 (vt, J6a,OH = 5.8, J6b,OH = 5.8 Hz, 1 H,
(dd, J4,5 = 2.2, J5,6b = 5.2 Hz, 1 H, 5-H), 5.14 (ddd, JCH2,=CHcis
1.6, J=CHcis,=CHtrans = 3.7, JCH,=CHcis = 10.5 Hz, 1 H, CH=CHcis ),
5.27 (ddd, JCH2,=CHtrans = 1.4, J=CHcis,=CHtrans = 3.7, JCH,=CHtrans
=
=
17.3 Hz, 1 H, CH=CHtrans), 5.91–5.82 (m, 1 H, CH2CH=) ppm.
13C NMR (100 MHz, [D6]DMSO): δ = 134.7 (CH2HC=CH2),
117.5 (O3CCH3), 116.6 (CH2HC=CH2), 82.3 (C-3), 74.3 (C-4), 73.8
(C-5), 73.6 (C-2), 71.9 (C-1), 69.3 (CH2HC=CH2), 66.1 (C-6), 21.9
(CCH3) ppm. MALDI-TOF-MS (DHB): m/z = 228.7 [M + H]+,
250.8 [M + Na]+.
O6-H), 4.61 (d, J5,OH = 5.2 Hz, 1 H, O5-H), 5.15 (v. br. d, J1a,2
=
4.3, J2,3 = 4.3 Hz, 1 H, 2-H), 5.40 (d, J3,OH = 4.5 Hz, 1 H, O3-H),
7.07–7.04 (m, 2 H, 2 H-mBz), 7.92–7.90 (m, 2 H, 2 H-oBz) ppm.
1H NMR (400 MHz, MeOD): δ = 3.64 (dd, J5,6b = 5.3, J6a,6b
=
11.6 Hz, 1 H, 6b-H), 3.80 (dd, J5,6a = 2.7, J6a,6b = 11.6 Hz, 1 H,
6a-H), 3.86–3.83 (m, 4 H, 1b-H, OCH3), 3.97–3.90 (m, 2 H, 4-H,
5-H), 4.32 (dd, J1a,2 = 4.4, J1a,1b = 10.5 Hz, 1 H, 1a-H), 4.39 (d,
J2,3 = 2.3, J3,4 = 1.5 Hz, 1 H, 3-H), 5.26 (dt, J1b,2 = 1.2, J2,3 = 2.3,
J1a,2 = 4.4 Hz, 1 H, 2-H), 7.02–6.98 (m, 2 H, 2 H-mBz), 7.97–7.95
(m, 2 H, 2 H-oBz) ppm. 13C NMR (100 MHz, [D6]DMSO): δ =
164.5 (Cq, C=O), 163.2 (Cq, BzCOCH3), 131.2 (Carom., C-oBz),
121.5 (Cq, BzCC=O), 113.9 (Carom., C-mBz), 80.8 (C-5), 79.3 (C-
2), 73.2 (C-3), 70.6 (C-1), 68.7 (C-4), 63.7 (C-6), 55.4 (OCH3) ppm.
13C NMR (100 MHz, MeOD): δ = 167.0 (Cq, C=O), 165. 5 (C,
BzCOCH3), 132.8 (Carom., C-oBz), 123.2 (Cq, BzCC=O), 115.0
(Carom., C-mBz), 82.3 (C-4), 81.2 (C-2), 75.7 (C-3), 72.6 (C-1), 70.9
(C-5), 65.5 (C-6), 56.5 (OCH3) ppm. MALDI-TOF-MS (DHB):
m/z = 299.1 [M + H]+, 321.1 [M + Na]+, 337.1 [M + K]+.
1,4-Anhydro-2-O-p-methoxybenzoyl-3,5,6-tri-O-orthoacetyl-D-sorb-
itol (5): 1,4-Anhydro-3,5,6-tri-O-orthoacetyl-d-sorbitol (3, 1.52 g,
8.05 mmol) was dissolved in anhydrous pyridine (25 mL) with the
exclusion of moisture. The solution was cooled to 0 °C, and 4-
methoxybenzoyl chloride (1.25 equiv.) in anhydrous pyridine
(5 mL) was added dropwise. The reaction mixture was slowly
brought to room temperature and stirred overnight. Afterwards, ice
was added, and the mixture was extracted with CHCl3. The organic
phase was washed five times with cold sulfuric acid (1 m), three
times with saturated aqueous sodium hydrogen carbonate, and
water. Then the organic phase was dried with sodium sulfate and
concentrated in vacuo. The crude product was purified by column
chromatography (CH2Cl2 Ǟ CH2Cl2/MeOH, 50:1) to obtain pure
5 (1.66 g, 5.15 mmol 64%) as a colourless solid. M.p. 115.1 °C. Rf
1,4-Anhydro-5,6-O-isopropylidene-2-O-p-methoxybenzoyl-
D-sorbitol
(7): 1,4-Anhydro-2-O-p-methoxybenzoyl-d-sorbitol (6, 0.395 g,
572
www.eurjoc.org
© 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2013, 566–577

Self-Metathesis of Polyol Allyl Ethers
1.33 mmol) was dissolved in N,N-dimethylformamide (10 mL), and
p-toluenesulfonic acid (catalytic amount) and 2,2-dimethoxypro-
pane (0.213 mL, 0.179 g, 1.72 mmol) were added. The solution was
solved in acetic acid (100 mL). Water (10 mL) was added, and the
solution was stirred at 60 °C for 3 d. Afterwards, the solvent was
removed in vacuo, and the crude residue was purified by column
stirred at room temperature for 10 h, then triethylamine was added, chromatography (PE/Et2O, 99:1 Ǟ 4:1). Pure 9 (2.61 g, 6.01 mmol,
and the mixture was concentrated in vacuo. The residue was dis-
solved in Et2O, and the solution was washed with water and brine,
and dried with sodium sulfate, then the solvent was removed in
83%) was obtained as a colourless syrup. Rf = 0.67 (PE/EtOAc =
1:1). [α]2D3 = –55.9 (c = 0.94, CHCl3). 1H NMR (400 MHz, [D6]-
DMSO): δ = 3.50 (ddd, J6,OH = 5.2, J5,6b = 6.2, J6a,6b = 11.8 Hz,
vacuo. Compound 7 (0.437 g, 1.29 mmol, 97%) was obtained as a 1 H, 6b-H), 3.71–3.67 (m, 2 H, 1b-H, 5-H), 3.83 (ddd, J5,6a = 2.1,
colourless solid. M.p. 129.2 °C. Rf = 0.38 (PE/EtOAc = 1:1). [α]2D3
= 47.3 (c = 1.14, CHCl3). H NMR (400 MHz, [D6]DMSO): δ =
J6,OH = 5.2, J6a,6b = 11.8 Hz, 1 H, 6a-H), 3.88 (dd, J3,4 = 3.3, J4,5
= 9.9 Hz, 1 H, 4-H), 4.00 (dd, J1a,2 = 4.2, J1a,1b = 9.9 Hz, 1 H, 1a-
H), 4.06 (br. d, J2,3 = 4.2, J3,4 = 3.3 Hz, 1 H, 3-H), 4.21 (br. d, J1a,2
= 4.2, J2,3 = 4.2 Hz, 1 H, 2-H), 4.44 (d, JBnCH5a,BnCH5b = 11.5 Hz,
1 H, BnCH2-5b), 4.46 (d, JBnCH3a,BnCH3b = 11.4 Hz, 1 H, BnCH2-
3b), 4.63–4.51 (m, 4 H, BnCH2-2, BnCH2-3a, OH), 4.74 (d,
1
1.27 (s, 3 H, CCH3), 1.32 (s, 3 H, CCH3), 3.77 (br. d, J1a,1b
10.4 Hz, 1 H, 1b-H), 3.84 (m, 4 H, 6b-H, OCH3), 3.92 (dd, J3,4
=
=
3.6, J4,5 = 6.5 Hz, 1 H, 4-H), 3.99 (dd, J5,6a = 6.5, J6a,6b = 8.2 Hz,
1 H, 6a-H) 4.14 (dd, J1a,2 = 4.0, J1a,1b = 10.4 Hz, 1 H, 1a-H), 4.17
(t, J2,3 = 3.6, J3,4 = 3.6 Hz, 1 H, 3-H), 4.27 (ddd, J4,5 = 6.5, J5,6a JBnCH5a,BnCH5b = 11.5 Hz, 1 H, BnCH2-5a), 7.38–7.25 (m, 15 H,
= 6.5, J5,6b = 12.8 Hz, 1 H, 5-H), 5.17 (br. d, 1 H, 2-H), 5.66 (d, 15 H-Bn) ppm. 13C NMR (100 MHz, [D6]DMSO): δ = 139.1 (Cq,
J3,OH = 4.4 Hz, 1 H, O3-H), 7.07–7.05 (m, 2 H, m-Bz), 7.93–7.91
(m, 2 H, o-Bz) ppm. H NMR (400 MHz, [D6]acetone): δ = 1.28
CH2CPh), 138.2 (Cq, CH2CPh), 138.1 (Cq, CH2CPh), 128.3, 128.3,
128.2, 128.0, 127.5, 127.4, 127.2, 127.1 (Carom., C-Bn), 81.0, (C-2),
80.9 (C-3), 78.9 (C-4), 77.2 (C-5), 71.3 (C-1), 71.2 (BnCH2), 70.9
1
(s, 3 H, CCH3), 1.34 (s, 3 H, CCH3), 3.85 (dd, J1b,2 = 0.8, J1a,1b
=
10.3 Hz, 1 H, 1b-H), 3.89 (s, 3 H, OCH3), 3.94 (dd, J5,6b = 6.0, (BnCH2), 70.5 (BnCH2), 61.1 (C-6) ppm. HRESI-MS: calcd. for
J6a,6b = 8.3 Hz, 1 H, 6b-H), 4.00 (bdd, J3,4 = 3.2, J4,5 = 6.9 Hz, 1
H, 4-H), 4.05 (dd, J5,6a = 6.4, J6a,6b = 8.3 Hz, 1 H, 6a-H), 4.25 (dd,
J1a,2 = 4.2, J1a,1b = 10.3 Hz, 1 H, 1a-H), 4.39–4.35 (m, 2 H, 3-H,
5-H), 4.68 (br. d, J3,OH = 4.5 Hz, 1 H, O3-H), 5.27 (dt, J1b,2 = 0.8,
J2,3 = 4.1, J1a,2 = 4.2 Hz, 1 H, 2-H), 7.05–7.01 (m, 2 H, 2 H-mBz),
8.00–7.96 (m, 2 H, 2 H-oBz) ppm. 13C NMR (100 MHz, [D6]-
DMSO): δ = 164.4 (Cq, C=O), 163.2 (Cq, BzCOCH3), 131.3
(Carom., C-oBz), 121.4 (Cq, BzCC=O), 113.9 (Carom., C-mBz), 107.6
[Cq, O2C(CH3)2], 81.4 (C-4), 79.4 (C-2), 72.7 (C-3), 72.6 (C-5), 70.7
(C-1), 65.9 (C-6), 55.4 (OCH3), 25.4 (CCH3), 25.2 (CCH3) ppm.
13C NMR (100 MHz, [D6]acetone): δ = 164.9 (Cq, C=O), 163.4
(Cq, BzCOCH3), 133.4 (Carom., C-oBz), 124.1 (Cq, BzCC=O), 115.7
(Carom., C-mBz), 109.2 [Cq, O2C(CH3)2], 84.0 (C-4), 81.9 (C-2), 76.0
(C-3), 75.1 (C-5), 73.1 (C-1), 68.5 (C-6), 57.0 (OCH3), 28.1 (CCH3),
26.7 (CCH3) ppm. HRESI-MS: calcd. for C17H22O7Na 361.1258
[M + Na]+; found 361.1264.
C27H30O5Na 457.1985 [M + Na]+; found 457.1992.
3,5,6-Tri-O-acetyl-2-O-allyl-1,4-anhydro- -sorbitol (10): 2-O-Allyl-
1,4-anhydro-3,5,6-tri-O-orthoacetyl-d-sorbitol (4, 2.80 g,
D
12.3 mmol) was dissolved in ethanol/water (5:1, 30 mL), and Am-
berlite IR 120 H+ (10 wt-%) was added. The reaction mixture was
stirred under reflux for 10 h. The ion-exchange resin was removed
by filtration and washed several times with ethanol and water. The
solution was concentrated in vacuo, the residue was dissolved in
absolute pyridine (40 mL), and acetic anhydride (20 mL) was added
dropwise. The solution was stirred at room temperature for 10 h.
Afterwards, the solution was concentrated in vacuo, and the residue
was co-evaporated several times with toluene. The residue was puri-
fied by column chromatography (PE/Et2O, 1:1) to obtain 10
(3.76 g, 11.3 mmol, 92%) as a slightly yellowish oil. Rf = 0.32 (PE/
1
Et2O = 1:1). [α]2D3 = –17.6 (c = 1.19, CHCl3). H NMR (400 MHz,
CDCl3): δ = 1.99 (s, 3 H, CH3), 2.03 (s, 3 H, CH3), 2.04 (s, 3 H,
1,4-Anhydro-2,3,5-tri-O-benzyl-6-O-trityl-D-sorbitol (8): 1,4-Anhy- CH3), 3.81 (dd, J1b,2 = 1.9, J1a,1b = 10.0 Hz, 1 H, 1b-H), 3.92–
dro-6-O-trityl-d-sorbitol (2, 5.01 g, 12.3 mmol) was used according
to GP1. In variation from GP1, tetra-n-butylammonium iodide
(catalytic amount) was added before the benzyl bromide was
added. The residue was purified by column chromatography (PE
Ǟ PE/Et2O, 4:1, +0.1% triethylamine) to obtain pure 8 (7.89 g,
11.7 mmol, 95%) as a colourless syrup. Rf = 0.59 (PE/EtOAc =
1:1). [α]2D3 = –47.9 (c = 0.9, CHCl3). 1H NMR (400 MHz, [D6]-
3.91 (m, 1 H, 2-H), 4.03 (ddt, JOCH2,=CH2 = 1.3, JOCH2,CH = 5.8,
JOCH2,OCH2 = 12.8 Hz, 1 H, CH2CH=), 4.92–4.08 (m, 4 H, 1a-H,
4-H, 6b-H, CH2CH=), 4.56 (dd, J5,6a = 2.4, J6a,6b = 12.3 Hz, 1 H,
6a-H), 5.21–5.17 (m, 2 H, 5-H, CH=CH2), 5.31–5.25 (m, 2 H, 3-
H, -CH=CH2), 5.91–5.82 (m, 1 H, CH2CH=) ppm. 13C NMR
(100 MHz, CDCl3): δ = 170.9 (Cq, C=O), 170.1 (Cq, C=O), 170.0
(Cq, C=O), 134.1 (CH2HC=CH2), 117.9 (CH2HC=CH2), 82.7 (C-
DMSO): δ = 3.15 (dd, J5,6b = 6.6, J6a,6b = 10.1 Hz, 1 H, 6b-H), 2), 77.4 (C-4), 75.1 (C-3), 72.9 (C-1), 71.0 (CH2HC=CH2), 68.4 (C-
3.33 (dd, J5,6a = 1.6, J6a,6b = 10.1 Hz, 1 H, 6a-H), 3.65 (dd, J1b,2
=
5), 63.7 (C-6), 21.0 (CH3) ppm. HRESI-MS: calcd. for
0.8, J1a,1b = 9.9 Hz, 1 H, 1b-H), 3.87 (ddd, J5,6a = 1.6, J5,6b = 6.6,
J4,5 = 8.7 Hz, 1 H, 5-H), 3.97–3.91 (m, 2 H, 1a-H, 4-H), 4.12 (br.
d, J2,3 = 4.1, J3,4 = 3.3 Hz, 1 H, 3-H), 4.20 (br. d, J1b,2 = 0.8, J1a,2
= 4.1, J2,3 = 4.1 Hz, 1 H, 2-H), 4.48 (d, 2 H, BnCH2-2b, BnCH2-
5b), 4.54 (d, JBnCH3a,BnCH3b = 12.0 Hz, 1 H, BnCH2-3b), 4.59 (d,
JBnCH3a,BnCH3b = 12.0 Hz, 1 H, BnCH2-3a), 4.62 (d, JBnCH2a,BnCH2b
= 11.6 Hz, 1 H, BnCH2-2a), 4.70 (d, JBnCH5a,BnCH5b = 11.3 Hz, 1
H, BnCH2-5a), 7.41–7.19 (m, 30 H, 15 H-Trt, 15 H-Bn) ppm. 13C
NMR (100 MHz, [D6]DMSO): δ = 143.9 [Cq, OC(CPh)3], 138.6
(Cq, CH2CPh), 138.2 (Cq, CH2CPh), 138.0 (Cq, CH2CPh), 128.3,
128.2, 127.8, 127.7, 127.3, 126.9 (Carom., Trt, Bn), 85.8 [Cq,
OC(CPh)3], 80.9 (C-2), 80.7 (C-3), 79.3 (C-4), 75.7 (C-5), 71.9
(BnCH2), 71.3 (C-1), 70.9 (BnCH2), 70.4 (BnCH2), 64.3 (C-6) ppm.
HRESI-MS: calcd. for C46H44O5Na 699.3081 [M + Na]+; found
699.3088.
C15H22O8Na 353.1207 [M + Na]+; found 353.1215.
2,5,6-Tri-O-acetyl-3-O-allyl-1,4-anhydro-D-sorbitol (11): 1,4-Anhy-
dro-5,6-O-isopropylidene-2-O-p-methoxybenzoyl-d-sorbitol
(7,
1.52 g, 3.99 mmol) was used according to GP1. The reaction time
was 10 h. The residue was dissolved in methanol, and sodium
methoxide (catalytic amount) was added. The solution was stirred
at room temperature for 1 h. Afterwards, the solution was concen-
trated in vacuo, and the residue was purified by flash chromatog-
raphy (PE Ǟ Et2O). The residue was dissolved in methanol/water
(3:1, 20 mL), and Amberlite IR 120 H+ (10 wt-%) was added. The
reaction mixture was stirred under reflux for 10 h. The ion-ex-
change resin was removed by filtration and washed several times
with methanol and water. The solution was concentrated in vacuo,
the residue was dissolved in absolute pyridine (10 mL), and acetic
anhydride (5 mL) was added dropwise. The solution was stirred at
1,4-Anhydro-2,3,5-tri-O-benzyl-D-sorbitol (9): 1,4-Anhydro-2,3,5- room temperature for 10 h. Afterwards, the solution was concen-
tri-O-benzyl-6-O-trityl-d-sorbitol (8, 4.88 g, 7.21 mmol) was dis-
trated in vacuo, and the residue was co-evaporated several times
Eur. J. Org. Chem. 2013, 566–577
© 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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573

M. Tober, J. Thiem
FULL PAPER
with toluene. The residue was purified by column chromatography
(PE/Et2O, 2:1) to obtain 11 (0.653 g, 1.98 mmol, 50%) as a slightly
yellowish oil. Rf = 0.30 (PE/EtOAc = 2:1). [α]2D3 = –35.0 (c = 1.09,
CHCl3). 1H NMR (400 MHz, CDCl3): δ = 2.02 (s, 3 H, CH3), 2.05
(100 MHz, [D6]DMSO): δ = 145.3 [C=C(E)], 144.2 [C=C(Z)], 117.6
(Cq, O3CCH3), 104.4 [C=CЈ(Z)], 102.5 [C=CЈ(E)], 83.6, 82.8, 82.7,
81.9 (C-2, C-2Ј), 74.3 (C-4, C-4Ј), 73.9, 73.8, 73.7, 73.6 (C-3, C-
3Ј, C-5, C-5Ј), 72.1, 71.9, 71.7 (C-1, C-1Ј), 69.1, 68.1 [OCH2(E),
OCH2(Z)], 66.3 (C-6, C-6Ј), 27.6 [CH2(E)], 24.4 [CH2(Z)], 22.0
(CCH3), 21.0 (CCH3), 20.9 (CCH3) ppm.
(s, 3 H, CH3), 2.07 (s, 3 H, CH3), 3.81 (dd, J1b,2 = 1.3, J1a,1b
10.5 Hz, 1 H, 1b-H), 3.90 (br. d, J2,3 = 3.9, J3,4 = 3.9 Hz, 1 H, 3-
H), 3.94 (ddt, JOCH2,=CH2 = 1.3, JOCH2,CH = 6.2, JOCH2,OCH2
=
=
3,5,6-Tri-O-acetyl-1,4-anhydro-2-O-(3,5,6-tri-O-acetyl-1,4-anhydro-
2-O-)but-1-enyl-D-sorbitol (14): 3,5,6-Tri-O-acetyl-2-O-allyl-1,4-
12.8 Hz, 1 H, CH2CH=), 4.20–4.11 (m, 4 H, 1a-H, 4-H, 6b-H,
CH2CH=), 4.61 (dd, J5,6a = 2.4, J6a,6b = 12.3 Hz, 1 H, 6a-H), 5.19–
5.15 (m, 2 H, 2-H, CH=CH2), 5.28–5.22 (m, 2 H, 5-H, CH=CH2),
5.84–5.74 (m, 1 H, CH2CH=) ppm. 13C NMR (100 MHz, [D6]-
DMSO): δ = 134.7 (CH2HC=CH2), 117.5 (O3CCH3), 116.6
(CH2HC=CH2), 82.3 (C-3), 74.3 (C-4), 73.8 (C-5), 73.6 (C-2), 71.9
(C-1), 69.3 (CH2HC=CH2), 66.1 (C-6), 21.9 (CCH3) ppm. HRESI-
MS: calcd. for C15H22O8Na 353.1207 [M + Na]+; found 353.1209.
anhydro-d-sorbitol (10, 0.302 g, 0.914 mmol) was dissolved in ab-
solute degassed dichloromethane (2 mL), and GH2 (8 mol-%) was
added. The solution was stirred under reflux for 12 h. Afterwards,
the crude mixture was purified by column chromatography (PE Ǟ
PE/Et2O, 1:2) and a mixture containing 14/18 in a ratio of 1:0.1
(0.193 g, 0.305 mmol, 67%) was obtained as a dark grey syrup. The
isolated fraction contained traces of metathesis catalyst and was
not purified further. Rf = 0.12 (PE/Et2O = 1:2); Rf = 0.60 (EtOAc).
1H NMR (400 MHz, CDCl3): δ = 1.99–1.98 (m, 12 H, 4 O=CCH3),
2.05–2.03 (m, 24 H, 8 O=CCH3), 2.21–2.16 [m, 2 H, CH2(E)], 3.49–
3.41 [m, 2 H, OCH2(E), OCH2(Z)], 2.40–2.28 [m, 2 H, CH2(Z)],
3.64–3.57 [m, 2 H, OCH2(E), OCH2(Z)], 3.80–3.77 [m, 2 H, 1b-
H(E), 1b-H(Z)], 3.91–3.84 [m, 4 H, 1bЈ-H(E), 1bЈ-H(Z), 2-H(E), 2-
H(Z)], 4.25–4.08 [m, 14 H, 1a-H(E), 1a-H(Z), 1aЈ-H(E), 1aЈ-H(Z),
2Ј-H(E), 2Ј-H(Z), 4-H(E), 4-H(Z), 4Ј-H(E), 4Ј-H(Z), 6b-H(E), 6b-
H(Z), 6bЈ-H(E), 6bЈ-H(Z)], 4.91–4.84 [m, 1 H, CH2CH=(E)], 4.59–
4.51 [m, 5 H, CH2CH=(Z), 6a-H(E), 6a-H(Z), 6aЈ-H(E), 6aЈ-H(Z)],
5.33–5.27 [m, 4 H, 3-H(E), 3-H(Z), 3Ј-H(E), 3Ј-H(Z)], 5.23–5.17
[m, 4 H, 5-H(E), 5-H(Z), 5Ј-H(E), 5Ј-H(Z)], 6.10 [dt, JCH2CH = 1.2,
JCH=CH(Z) = 7.5 Hz, 1 H, OCH=(Z)], 6.24–6.21 [m, 1 H, OCH=(E)]
ppm. 13C NMR (100 MHz, CDCl3): δ = 170.1 (Cq, O=CCH3),
170.0 (Cq, O=CCH3), 169.9 (Cq, O=CCH3), 145.4 [OC=C(E)],
144.0 [OC=C(Z)], 105.4 [OC=C(Z)], 103.5 [OC=C(E)], 84.1, 83.5,
83.4, 81.9 (C-2, C-2Ј), 77.4, 77.3 (C-4, C-4Ј), 75.4, 75.0, 74.9 (C-3,
C-3Ј), 72.8 (C-1), 72.4 (C-1Ј), 72.2 (C-1Ј), 70.4 [CH2(E)], 69.6
[CH2(Z)], 68.4, 68.3 (C-5, C-5Ј), 63.7, 63.6 (C-6, C-6Ј), 28.4
[CH2(E)], 25.0 [CH2(Z)], 21.1 (O=CCH3), 21.0 (O=CCH3), 20.9
(O=CCH3) ppm.
6-O-Allyl-1,4-anhydro-2,3,5-tri-O-benzyl-D-sorbitol (12): 1,4-Anhy-
dro-2,3,5-tri-O-benzyl-d-sorbitol (9, 0.700 g, 1.61 mmol) was used
according to GP1. In variation from GP1, sodium hydride
(2.5 equiv.) and allyl bromide (2 equiv.) were used. The residue was
purified by column chromatography (PE Ǟ PE/Et2O, 2:1) to obtain
12 (0.707 g, 1.49 mmol, 93%) as a colourless oil. Rf = 0.58 (PE/
EtOAc = 2:1). [α]2D3 = –40.1 (c = 1.13, CHCl3). 1H NMR (400 MHz,
[D6]DMSO): δ = 3.53 (dd, J5,6b = 5.4, J6a,6b = 10.8 Hz, 1 H, 6b-
H), 3.70 (dd, J1b,2 = 0.5, J1a,1b = 9.9 Hz, 1 H, 1b-H), 3.77 (dd, J5,6a
= 1.5, J6a,6b = 10.8 Hz, 1 H, 6a-H), 3.82 (ddd, J5,6a = 1.5, J5,6b
=
5.4, J4,5 = 8.9 Hz, 1 H, 5-H), 3.90 (dd, J3,4 = 3.2, J4,5 = 8.9 Hz, 1
H, 4-H), 3.97–3.88 (m, 2 H, CH2CH=CH2), 4.00 (dd, J1a,2 = 4.6,
J1a,1b = 9.9 Hz, 1 H, 1a-H), 4.10 (br. d, J2,3 = 4.0, J3,4 = 3.2 Hz, 1
H, 3-H), 4.49–4.44 (m, 2 H, BnCH2-2b, BnCH2-5b), 4.21 (br. d,
J2,3 = 4.0, J1a,2 = 4.6 Hz, 1 H, 2-H), 4.55 (d, JBnCH3a,BnCH3b
=
12.0 Hz, 1 H, BnCH2-3b), 4.58 (d, JBnCH3a,BnCH3b = 12.0 Hz, 1 H,
BnCH2-3a), 4.62 (d, JBnCH2a,BnCH2b = 11.6 Hz, 1 H, BnCH2-2a),
4.70 (d, JBnCH5a,BnCH5b = 11.6 Hz, 1 H, BnCH2-5a), 5.15–5.11 (m,
1 H, CH2CH=CHcis), 5.27 (ddd, J=CHtrans,CH2 = 1.6, J=CHcis,=CHtrans
= 3.5, JCH,=CHtrans = 17.3 Hz, 1 H, CH2CH=CHtrans), 5.92–5.83
(m, 1 H, CH2CH=CH2), 7.38–7.24 (m, 15 H, 15 H-Bn) ppm. 13C
NMR (100 MHz, [D6]DMSO): δ = 138.8 (Cq, CH2CPh), 138.1 (Cq,
CH2CPh), 138.0 (Cq, CH2CPh), 135.3 (CH2CH=CH2), 128.2,
128.1, 128.0, 127.5, 127.4, 127.3, 127.1, 127.0 (Carom., Bn), 116.0
(CH2CH=CH2), 81.0 (C-2), 80.9 (C-3), 79.4 (C-4), 75.7 (C-5), 71.3
(CH2CH=CH2, CH2Bn, C-1), 70.9 (CH2Bn), 70.4 (CH2Bn, C-6)
ppm. HRESI-MS: calcd. for C30H34O5Na 497.2298 [M + Na]+;
found 497.2302.
1,4-Anhydro-3,5,6-tri-O-orthoacetyl-2-O-prop-1-enyl-D-sorbitol
(15): Compound 15 was isolated as a by-product from several me-
tathesis reactions in different yields (see Table 1). The compound
was obtained as a black oil containing traces of metathesis catalyst.
1
It was not purified further. Rf = 0.63 (PE/EtOAc = 2:1). H NMR
(400 MHz, [D6]DMSO): δ = 1.47–1.46 (m, 6 H, CH3CH=CHO,
O3CCH3), 3.73 (dd, J5,6b = 5.2, J6a,6b = 7.7 Hz, 1 H, 6b-H), 3.83
(d, J1a,1b = 9.9 Hz, 1 H, 1b-H), 3.89 (br. s, 1 H, 4-H), 4.07–4.05
(m, 2 H, 1a-H, 6a-H), 4.23 (br. d, J1a,2 = 2.8 Hz, 1 H, 3-H), 4.29
(d, J2,3 = 3.2 Hz, 1 H, 2-H), 4.50–4.45 (m, 1 H, CH3CH=CHO),
4.72 (br. d, J5,6a = 3.8 Hz, 1 H, 5-H), 6.13 (dd, JCH=,H = 6.1,
JCH=,CH3 = 1.4 Hz, 1 H, CH3CH=CHO) ppm. 13 C NMR
(100 MHz, [D6]DMSO): δ = 143.8 (CH3CH=CHO), 117.6 (Cq,
O3CCH3), 102.3 (CH3CH=CHO), 83.8 (C-2), 74.4 (C-4), 74.0 (C-
5), 73.9 (C-3), 72.0 (C-1), 66.3 (C-6), 22.0 (O3CCH3), 9.3
(CH3CH=CHO) ppm.
1,4-Anhydro-3,5,6-tri-O-orthoacetyl-2-O-(1,4-anhydro-3,5,6-tri-
O-orthoacetyl-2-O-)but-1-enyl-D-sorbitol (13): 2-O-Allyl-1,4-anhy-
dro-3,5,6-tri-O-orthoacetyl-d-sorbitol (4, 0.194 g, 0.850 mmol) was
dissolved in absolute degassed dichloromethane (1 mL). GH2
(10 mol-%) was added, and the solution was stirred under reflux
for 12 h. Afterwards, the crude mixture was purified by column
chromatography (PE Ǟ PE/Et2O, 1:2) to obtain 13 (0.036 g,
0.084 mmol, 20%) as a dark grey syrup. The isolated compound
contained traces of metathesis catalyst and was not purified further.
1
Rf = 0.38 (PE/EtOAc = 1:2). H NMR (400 MHz, [D6]DMSO): δ
= 1.47–1.45 (m, 12 H, 4 CCH3), 2.11–2.06 [m, 2 H, CH2(E)], 2.20–
1,4-Anhydro-3,5,6-tri-O-orthoacetyl-2-O-(1,4-anhydro-3,5,6-tri-
2.18 [m, 2 H, CH2(Z)], 3.44–3.36 [m, 4 H, OCH2(E) OCH2(Z)], O-orthoacetyl-2-O)but-2-enyl-
D-sorbitol (17): 2-O-Allyl-1,4-anhy-
3.89–3.71 [m, 1b-H(E), 1b-H(Z), 1bЈ-H(E), 1bЈ-H(Z), 2Ј-H(E), 2Ј- dro-3,5,6-tri-O-orthoacetyl-d-sorbitol (4, 0.252 g, 1.10 mmol) and
H(Z), 4-H(E), 4-H(Z), 4Ј-H(E), 4Ј-H(Z), 6b-H(E), 6b-H(Z), 6bЈ-
H(E), 6bЈ-H], 4.12–4.00 [m, 8 H, 1-Ha(E), 1-Ha(Z), 1-HaЈ(E), 1-
HaЈ(Z), 6a-H(E), 6a-H(Z), 6aЈ-H(E), 6aЈ-H(Z)], 4.28–4.24 [m, 4 H,
3-H(E), 3-H(Z), 3Ј-H(E), 3Ј-H(Z)], 4.30–4.29 [m, 2 H, 2-H(E), 2-
GH2 (7 mol-%) were used according to GP2. The reaction time
was 20 h. The crude product was purified by column chromatog-
raphy (PE Ǟ PE/EtOAc = 2:1) to obtain 17 [(E)/(Z) = 13:1;
0.139 g, 0.324 mmol, 59%] as a black oil containing traces of me-
H(Z)], 4.48–4.43 [m, 1 H, CH2CH=(Z)], 4.80–4.68 [m, 5 H, 5-H(E), tathesis catalyst and 1,4-benzoquinone. The NMR spectroscopic
5-H(Z), 5Ј-H(E), 5Ј-H(Z), CH2CH=(E)], 6.15–6.17 [m, 1 H, assignment was carried out for the (E) isomer only: Rf = 0.11 (PE/
1
OCH=(Z)], 6.28–6.31 [m, 1 H, OCH=(E)] ppm. 13C NMR EtOAc = 2:1). H NMR (400 MHz, [D6]DMSO): δ = 1.45 (s, 6 H,
574
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© 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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Self-Metathesis of Polyol Allyl Ethers
2 CH3), 3.73 (dd, J5,6b = 4.5, J5Ј,6bЈ = 4.5, J6a,6b = 7.5, J6aЈ,6bЈ
7.5 Hz, 2 H, 6b-H, 6bЈ-H), 3.77–3.81 (m, 4 H, 1b-H, 1bЈ-H, 4-H,
=
washed with methanol. The solvent was removed in vacuo, and the
crude product was purified by reverse-phase column chromatog-
4Ј-H), 3.89 (br. s, 2 H, 2-H, 2Ј-H), 3.96–4.05 (m, 8 H, 1a-H, 1aЈ- raphy (H2O Ǟ H2O/MeOH, 2:1) to obtain pure 19 [(E)/(Z) = 13:1;
H, 6a-H, 6aЈ-H, 2 CH2), 4.28 (br. d, J3,4 = 3.2 Hz, 2 H, 3-H, 3Ј-
H), 4.68 (d, J5,6a = 3.6, J5Ј,6aЈ = 3.6 Hz, 2 H, 5-H, 5Ј-H), 5.72 (br.
s, 2 H, 2 CH=) ppm. 13C NMR (100 MHz, [D6]DMSO): δ = 128.9
(CH=CH2), 82.2 (C-2, C-2Ј), 74.3 (C-4, C-4Ј), 73.8 (C-5, C-5Ј), 73.6
(C-3, C-3Ј), 72.0 (C-1, C-1Ј), 68.3 (CH=CH2), 66.2 (C-6), 21.9
(CH3) ppm.
0.072 g, 0.19 mmol, 71%] as a viscous yellow syrup.
Method B: Compound 18 (0.257 g, 0.406 mmol) was dissolved in
methanol (5 mL). Sodium methoxide (catalytic amount) was
added. The solution was stirred at room temperature overnight.
Afterwards a small portion of Amberlite IR 120 H+ was added,
and the solution was stirred for 30 min. The ion-exchange resin was
removed by filtration and washed several times with methanol. The
solution was concentrated in vacuo, and the crude product was
purified by reversed-phase column chromatography (H2O Ǟ H2O/
MeOH, 2:1) to obtain pure 19 [(E)/(Z) = 9:1; 0.150 g, 0.394 mmol,
97%] as a yellow viscous syrup.
3,5,6-Tri-O-acetyl-1,4-anhydro-2-O-(3,5,6-tri-O-acetyl-1,4-anhydro-
2-O-)but-2-enyl-D-sorbitol (18)
Method A: The reaction was carried out under nitrogen and with
the exclusion of moisture. 3,5,6-Tri-O-acetyl-2-O-allyl-1,4-anhydro-
d-sorbitol (10, 2.36 g, 7.14 mmol) was dissolved in absolute de-
gassed dichloromethane (22.5 mL), and GH2 (1 mol-%) was added.
The solution was stirred under reflux for 12 h. Afterwards, the
crude mixture was purified by column chromatography (PE Ǟ PE/
Et2O, 1:2) to obtain 18 [(E)/(Z) = 6:1; 0.409 g, 0.647 mmol, 18%
yield] as a dark grey syrup. The isolated fraction contained traces
of metathesis catalyst and was not purified further.
The NMR spectroscopic assignment was carried out for the (E)
isomer only: Rf = 0.52 (EtOAc/MeOH/H2O = 7:3:1). 1H NMR
(400 MHz, [D6]DMSO): δ = 3.36 (dd, J5,6b = 6.2, J5Ј,6bЈ = 6.2, J6a,6b
= 11.1, J6aЈ,6bЈ = 11.1 Hz, 2 H, 6b-H, 6bЈ-H), 3.56–3.34 (m, 6 H,
1b-H, 1bЈ-H, 4-H, 4Ј-H, 6a-H, 6aЈ-H), 3.65 (ddd, J5,6 = 2.8, J5Ј,6aЈ
= 2.8, J5,6b = 6.2, J5Ј,6bЈ = 6.2, J4,5 = 8.7, J4Ј,5Ј = 8.7 Hz, 2 H, 5-H,
5Ј-H), 3.81 (br. d, J1a,2 = 4.4, J2,3 = 4.4, J1aЈ,2Ј = 4.4, J2Ј,3Ј = 4.4 Hz,
2 H, 2-H, 2Ј-H), 3.93 (dd, J1a,2 = 4.4, J1aЈ,2Ј = 4.4, J1a,1b = 9.7,
J1aЈ,1bЈ = 9.7 Hz, 2 H, 1a-H, 1aЈ-H), 3.94 (br. d, JCH2=CH = 2.5 Hz,
4 H, 2 CH2), 4.11–4.06 (m, 2 H, 3-H, 3Ј-H), 4.44 (br. d, 2 H, 2
OH), 4.80 (br. d, 2 H, 2 OH), 5.22 (br. d, 2 H, 2 OH), 5.23 (t,
JCH2=CH = 2.5 Hz, 2 H, 2 CH=) ppm. 13C NMR (100 MHz, [D6]-
DMSO): δ = 129.0 (C=C), 84.5 (C-2, C-2Ј), 80.8 (C-4, C-4Ј), 72.8
(C-3, C-3Ј), 70.8 (C-1, C-1Ј), 68.9 (C-5, C-5Ј), 68.2 (CH2), 64.0 (C-
6, C-6Ј) ppm. HRESI-MS: calcd. for C16H28O10Na 403.1575 [M +
Na]+; found 403.1567.
Method B: The reaction was carried out under nitrogen and with
the exclusion of moisture. 3,5,6-Tri-O-acetyl-2-O-allyl-1,4-anhydro-
d-sorbitol (10, 0.285 g, 0.863 mmol) was dissolved in absolute de-
gassed dichloromethane (2 mL), and G2 (6 mol-%) was added. The
solution was stirred under reflux for 12 h. Afterwards, the crude
mixture was purified by column chromatography (PE Ǟ PE/Et2O,
1:2) to obtain 18 [(E)/(Z) = 13:1; 0.143 g, 0.226 mmol, 52%] as a
dark grey syrup. The isolated fraction contained traces of metathe-
sis catalyst and was not purified further.
Method C: 3,5,6-Tri-O-acetyl-2-O-allyl-1,4-anhydro-d-sorbitol (10,
0.295 g, 0.893 mmol) and GH2 (6 mol-%) were used according to
GP2. The reaction time was 10 h. The crude product was purified
by column chromatography (PE Ǟ PE/Et2O, 1:2) to obtain 18 [(E)/
(Z) = 9:1; 0.267 g, 0.422 mmol, 95%] as a dark grey syrup contain-
ing traces of metathesis catalyst and 1,4-benzoquinone.
2,5,6-Tri-O-acetyl-1,4-anhydro-3-O-(2,5,6-tri-O-acetyl-1,4-anhydro-
3-O-)but-2-enyl-D-sorbitol (20): 2,5,6-Tri-O-acetyl-3-O-allyl-1,4-
anhydro-d-sorbitol (11, 0.328 g, 0.993 mmol) and GH2 (6 mol-%)
were used according to GP2. The reaction time was 10 h. The crude
product was purified by column chromatography (PE Ǟ PE/Et2O,
1:2) to obtain 20 [(E)/(Z) = 14:1; 0.267 g, 0.422 mmol, 85%] as a
dark grey syrup containing traces of metathesis catalyst and 1,4-
benzoquinone.
The NMR spectroscopic assignment was carried out for the (E)
isomer only: Rf = 0.12 (PE/Et2O = 1:2); Rf = 0.60 (EtOAc). 1H
NMR (400 MHz, CDCl3): δ = 1.99 (s, 6 H, 2 CH3), 2.03 (s, 6 H, 2
CH3), 2.05 (s, 6 H, 2 CH3), 3.81 (dd, J1b,2 = 1.7, J1bЈ,2Ј = 1.7, J1a,1b
= 10.1, J1aЈ,1bЈ = 10.1 Hz, 2 H, 1b-H, 1bЈ-H), 3.91–3.90 (m, 2 H,
2-H, 2Ј-H), 4.05–4.02 (m, 2 H, CH2), 5.79 (t, JCH2=CH = 2.7 Hz, 2
H, 2 CH=), 4.19–4.08 (m, 8 H, 1a-H, 1aЈ-H, 4-H, 4Ј-H, 6b-H, 6bЈ-
H, 2 CH2), 4.56 (dd, J5,6a = 2.3, J5Ј,6aЈ = 2.3, JH6a,6b = 10.1, J6aЈ,6bЈ
= 10.1 Hz, 2 H, 6a-H, 6aЈ-H), 5.20 (ddd, J5,6a = 2.3, J5Ј,6aЈ = 2.3,
J5,6b = 5.5, J5Ј,6bЈ = 5.5, J4,5 = 9.1, J4Ј,5Ј = 9.1 Hz, 2 H, 5-H, 5Ј-H),
5.29–5.28 (m, 2 H, 3-H, 3Ј-H) ppm. 13C NMR (100 MHz, CDCl3):
δ = 170.9 (Cq, O=CCH3), 170.1 (Cq, O=CCH3), 169.9 (Cq,
O=CCH3), 129.4 (C=C), 82.9 (C-2, C-2Ј), 77.4 (C-4, C-4Ј), 75.0
(C-3, C-3Ј), 72.8 (C-1, C-1Ј), 69.8 (CH2), 68.4 (C-5, C-5Ј), 63.7 (C-
6, C-6Ј), 21.0 (O=CCH3) ppm.
The NMR spectroscopic assignment was carried out for the (E)
isomer only. Rf = 0.19 (PE/EtOAc = 1:1). 1H NMR (400 MHz,
CDCl3): δ = 2.01 (s, 6 H, 2 CH3), 2.04 (s, 6 H, 2 CH3), 2.06 (s, 6
H, 2 CH3), 3.80 (dd, J1b,2 = 1.3, J1bЈ,2Ј = 1.3, J1a,1b = 10.5, J1aЈ,1bЈ
= 10.5 Hz, 2 H, 1b-H, 1bЈ-H), 3.86 (br. d, J2,3 = 4.0, J2Ј,3Ј = 4.0,
J3,4 = 4.0, J3Ј,4Ј = 4.0 Hz, 2 H, 3-H, 3Ј-H), 3.96–3.93 (m, 2 H, CH2,
CH2Ј), 4.18–4.10 (m, 8 H, 1a-H, 1aЈ-H, 4-H, 4Ј-H, 6b-H, 6bЈ-H,
CH2, CH2Ј), 4.59 (dd, J5,6a = 2.4, J5Ј,6aЈ = 2.4, J6a,6b = 12.4, J6aЈ,6bЈ
= 12.4 Hz, 2 H, 6a-H, 6aЈ-H), 5.15 (br. d, J1a,2 = 4.0, J1aЈ,2Ј = 4.0,
J2,3 = 4.0, J2Ј,3Ј = 4.0 Hz, 2 H, 2-H, 2Ј-H), 5.24 (ddd, J5,6a = 2.4,
J5Ј,6aЈ = 2.4, J5,6b = 7.8, J5Ј,6bЈ = 7.8, J4,5 = 10.5, J4Ј,5Ј = 10.5 Hz, 2
H, 5-H, 5Ј-H), 5.69 (t, JCH2=CH = 3.0 Hz, 2 H, 2 CH=) ppm. 13C
NMR (100 MHz, CDCl3): δ = 170.9 (Cq, C=O, C=OЈ), 170.3 (Cq,
C=O, C=OЈ), 169.6 (Cq, C=O, C=OЈ), 129.2 (2 C=C), 81.4 (C-3,
C-3Ј), 78.5 (C-4, C-4Ј), 76.6 (C-2, C-2Ј), 71.8 (C-1, C-1Ј), 70.5 (2
CH2), 69.2 (C-5, C-5Ј), 63.5 (C-6, C-6Ј), 21.2 (CH3), 21.1 (CH3),
21.0 (CH3) ppm.
1,4-Anhydro-2-O-(1,4-anhydro-2-O-)but-2-enyl-D-sorbitol (19)
Method A: Compound 17 (0.113 g, 0.266 mmol) was dissolved in
ethanol/water (3:1, 3 mL), and Amberlite IR 120 H+ (10 wt-%) was
added. The reaction mixture was stirred under reflux for 24 h. The
ion-exchange resin was removed by filtration and washed three
times with ethanol and water. The solution was concentrated in
vacuo, and the residue was dissolved in methanol (5 mL). Sodium
methoxide (catalytic amount) was added. The solution was stirred
at room temperature overnight. Afterwards, a small portion of Am-
berlite IR 120 H+ was added, and the solution was stirred for
30 min. The ion-exchange resin was removed by filtration and
1,4-Anhydro-2,3,5-tri-O-benzyl-6-O-(1,4-anhydro-2,3,5-tri-O-
benzyl-6-O-)but-2-enyl-D-sorbitol (21): 6-O-Allyl-1,4-anhydro-2,3,5-
tri-O-benzyl-d-sorbitol (12, 0.286 g, 0.603 mmol) and GH2 (5 mol-
%) were used according to GP2. The reaction time was 10 h. The
crude product was purified by column chromatography (PE Ǟ PE/
Et2O, 1:1) to obtain 21 [(E)/(Z) = 16:1; 0.207 g, 0.225 mmol, 75%]
Eur. J. Org. Chem. 2013, 566–577
© 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
575

M. Tober, J. Thiem
8.2, J4Ј,5Ј = 8.2 Hz, 2 H, 4-H, 4Ј-H), 3.98 (ddd, J5,6a = 2.8, J5Ј,6aЈ
2.8, J5,6b = 6.1, J5Ј,6bЈ = 6.1, J4,5 = 8.2, J4Ј,5Ј = 8.2 Hz, 2 H, 5-H,
5Ј-H), 4.14–4.09 (m, 6 H, 1a-H, 1aЈ-H, 2-H, 2Ј-H, 3-H, 3Ј-H) ppm.
13C NMR (400 MHz, MeOD): δ = 81.7 (C-4, C-4Ј), 78.5 (C-2, C-
2Ј), 70.1 (C-3, C-3Ј), 74.9 (C-1, C-1Ј), 74.4 (C-6, C-6Ј), 72.5 (2
OCH2CH2), 70.0 (C-5, C-5Ј), 27.5 (2 OCH2CH2) ppm. HRESI-
MS: calcd. for C16H31O10 383.1912 [M + H]+; found 383.1913;
calcd. for C16H30O10Na 405.1731 [M + Na]+; found 405.1726.
FULL PAPER
as a slightly grey syrup containing traces of metathesis catalyst and
1,4-benzoquinone.
=
The NMR spectroscopic assignment was carried out for the (E)
isomer only. Rf = 0.40 (PE/EtOAc = 2:1). 1H NMR (400 MHz,
CDCl3): δ = 3.67 (dd, J5,6b = 5.8, J5Ј,6bЈ = 5.8, J6a,6b = 10.8, J6aЈ,6bЈ
= 10.8 Hz, 2 H, 6b-H, 6bЈ-H) 3.84 (dd, J1b,2 = 1.5, J1bЈ,2Ј = 1.5,
J1a,1b = 9.8, J1aЈ,1bЈ = 9.8 Hz, 2 H, 1b-H, 1bЈ-H), 3.88 (dd, J5,6a
1.8, J5Ј,6aЈ = 1.8, J6a,6b = 10.8, J6aЈ,6bЈ = 10.8 Hz, 2 H, 6a-H, 6a-H),
4.02 (ddd, J5,6a = 1.8, J5Ј,6aЈ = 1.8, J5,6b = 5.8, J5Ј,6bЈ = 5.8, J4,5
=
7-Acetoxy-6,6-bis(acetoxymethyl)-4-oxahept-1-ene (27): Compound
26 (5.033 g, 25.14 mmol) was dissolved in ethanol/water (3:1,
100 mL), and Amberlite IR 120 H+ (10 wt.-%) was added. The re-
action mixture was stirred under reflux for 2 d. The ion-exchange
resin was removed by filtration and washed several times with eth-
anol and water. The solution was concentrated in vacuo, the residue
was dissolved in absolute pyridine (60 mL), and acetic anhydride
(30 mL) was added dropwise. The solution was stirred at room tem-
perature for 10 h. Afterwards, the solution was concentrated in
vacuo, and the residue was co-evaporated three times with toluene.
The residue was purified by column chromatography (PE/Et2O,
1:1) to obtain 27 (7.101 g, 23.49 mmol, 93%) as a slightly yellowish
oil (ref.[25] 11%). Rf = 0.25 (EtOAc/cyclohexane = 1:1); Rf = 0.42
(PE/Et2O = 1:2). 1H NMR (400 MHz, CDCl3): δ = 2.03 (s, 9 H,
O=CCH3), 3.39 [s, 2 H, (CH2)3CCH2OCH2], 3.92–3.90 (m, 1 H,
CH2CH=CH2), 4.11 [s, 6 H, 3 (CH2)3CCH2O], 5.13–5.16 (m, 1 H,
CH2CH=CHcis), 5.19–5.24 (m, 1 H, CH2CH=CHtrans), 5.85–5.76
(m, 1 H, CH2CH=CH2) ppm. 13C NMR (100 MHz, CDCl3): δ =
170.8 (Cq, C=O), 134.6 (CH2CH=CH2), 117.2 (CH2CH=CH2),
72.6 (CH2CH=CH2), 68.5 (CCH2OCH2), 63.1 [CCH2(O)3CH3],
42.7 (Cq, O4C), 21.0 (O=CCH3) ppm. HRESI-MS: calcd. for
C14H22O7 325.1258 [M + Na]+; found 325.1263.
=
8.8, J4Ј,5Ј = 8.8 Hz, 2 H, 5-H, 5Ј-H), 4.17–4.05 (m, 12 H, 1a-H, 1aЈ-
H, 2-H, 2Ј-H, 3-H, 3Ј-H, 4-H, 4Ј-H, 2 OCH2C=), 4.56–4.45 (m, 10
H, BnCH2-2, BnCH2-2Ј, BnCH2-3, BnCH2-3Ј, BnCH2-5b, BnCH2-
5bЈ), 4.84 (d, JBnCH5,BnCH5 = 11.6, JBnCH5Ј,BnCH5Ј = 11.6 Hz, 2 H,
BnCH2-5a, BnCH2-5aЈ), 5.84–5.83 (m, 2 H, 2 CH=), 7.39–7.25 (m,
30 H, 15 H-Bn, 15 H-BnЈ) ppm. 13C NMR (400 MHz, CDCl3): δ
= 139.3, 138.2, 138.0 (Cq, CBn, CBnЈ), 129.7 (2 C=C), 128.7, 128.6,
128.4, 128.0, 127.9, 127.8, 127.7, 127.6, 127.5 (Carom., CBn, CBnЈ),
81.9 (C-3, C-3Ј), 81.8 (C-2, C-2Ј), 80.0 (C-4, C-4Ј), 76.4 (C-5, C-
5Ј), 72.7 (BnCH2, BnCH2Ј), 72.2 (BnCH2, BnCH2Ј, C-1, C-1Ј), 71.7
(2 = CCH2), 71.6 (C-6, C-6Ј), 71.5 (BnCH2, BnCH2Ј) ppm.
1,4-Anhydro-3-O-(1,4-anhydro-3-O-)but-2-enyl-D-sorbitol (22):
Compound 20 (0.244 g, 0.386 mmol) was dissolved in methanol
(5 mL), and sodium methoxide (catalytic amount) was added. The
solution was stirred at room temperature for 10 h. Afterwards, a
small portion of Amberlite IR 120 H+ was added, and the solution
was stirred for 30 min. The ion-exchange resin was removed by fil-
tration and washed with methanol. The solution was concentrated
in vacuo, and the crude product was purified by reverse-phase col-
umn chromatography (H2O Ǟ H2O/MeOH, 2:1) to obtain pure
22 [(E)/(Z) = 14:1; 0.113 g, 0.297 mmol, 77%] as a yellowish very
hygroscopic foam.
1,12-Diacetoxy-2,2:11,11-tetrakis(acetoxymethyl)-4,9-dioxadodec-
6-ene (29): 7-Acetoxy-6,6-bis(acetoxymethyl)-4-oxa-1-hepten (27,
0.300 g, 0.992 mmol) and GH2 (5 mol-%) were used according to
GP2. The reaction time was 10 h. The crude product was purified
by column chromatography (PE Ǟ PE/Et2O, 1:2) to obtain 29 [(E)/
(Z) = 12:1; 0.218 g, 0.378 mmol, 76%] as a dark green solid con-
taining traces of metathesis catalyst and 1,4-benzoquinone.
The NMR spectroscopic assignment was carried out for the (E)
isomer only. Rf = 0.64 (EtOAc/MeOH/H2O = 7:3:1). 1H NMR
(400 MHz, MeOD): δ = 3.58 (dd, J5,6b = 5.7, J5Ј,6bЈ = 5.7, J6a,6b
=
11.4, J6aЈ,6bЈ = 11.4 Hz, 2 H, 6b-H, 6bЈ-H), 3.63 (dd, J1b,2 = 1.1,
J1bЈ,2Ј = 1.1, J1a,1b = 9.6, J1aЈ,1bЈ = 9.6 Hz, 2 H, 1b-H, 1bЈ-H), 3.77
(dd, J5,6a = 2.7, J5Ј,6aЈ = 2.7, J6a,6b = 11.4, J6aЈ,6bЈ = 11.4 Hz, 2 H,
6a-H, 6aЈ-H), 3.90–3.84 (m, 6 H, 3-H, 3Ј-H, 4-H, 4Ј-H, 5-H, 5Ј-
H), 4.05 (dd, J1a,2 = 4.3, J1aЈ,2Ј = 4.3, J1a,1b = 9.6, J1aЈ,1bЈ = 9.6 Hz,
The NMR spectroscopic assignment was carried out for the (E)
isomer only. M.p. 62.0 °C. Rf = 0.11 (PE/Et2O = 1:2). 1H NMR
(400 MHz, CDCl3): δ = 5.67–5.66 (m, 2 H, 2 CH2CH=), 4.10 (s,
12 H, 6 CCH2OAc), 3.90–3.91 (m, 4 H, 2 CH2CH=), 3.40 [s, 4 H,
2 CH2C(CH2OAc)3], 2.03 (s, 18 H, 6 CH3) ppm. 13C NMR
(400 MHz, CDCl3): δ = 170.9 (Cq, C=O), 128.9 (C=C), 71.6
(CH2C=C), 68.9 (CCH2OCH2C=), 63.1 [CCH2(O)3CH3], 42.8 (Cq
O4C), 21.0 (O=CCH3) ppm.
1a-H, 1aЈ-H), 4.21–4.10 (m, 4 H, CH2, CH2Ј), 4.30–4.24 (d, J1a,2
=
4.3, J1aЈ,2Ј = 4.3, J2,3 = 4.3, J2Ј,3Ј = 4.3 Hz, 2 H, 2-H, 2Ј-H), 5.93–
5.83 (m, 2 H, 2 CH=) ppm. 13C NMR (100 MHz, MeOD): δ =
130.7 (2 C=C), 85.2 (C-3, C-3Ј), 81.7 (C-4, C-4Ј), 75.4 (C-2, C-2Ј),
75.1 (C-1, C-1Ј), 71.2 (2 CH2), 70.6 (C-5, C-5Ј), 65.9 (C-6, C-6Ј)
ppm. HRESI-MS: calcd. for C16H29O10 381.1755 [M + H]+; found
381.1759; calcd. for C16H28O10Na 403.1575 [M + Na]+; found
403.1569; calcd. for C16H28O10K 419.1314 [M + K]+; found
419.1251.
1,12-Dihydroxy-2,2:11,11-tetrakis(hydroxymethyl)-4,9-dioxadodec-
6-ene (30): Compound 29 (0.209 g, 0.362 mmol) was dissolved in
methanol (5 mL). Sodium methoxide (catalytic amount) was
added. The solution was stirred at room temperature for 10 h. Af-
terwards, a small portion of Amberlite IR 120 H+ was added, and
the solution was stirred for 30 min. The ion-exchange resin was
removed by filtration and washed several times with methanol. The
solution was concentrated in vacuo, and the crude product was
purified by reverse-phase column chromatography (H2O Ǟ H2O/
MeOH, 1:2) to obtain pure 30 [(E)/(Z) = 12:1; 0.104 g, 0.321 mmol,
89%] as a colourless solid.
1,4-Anhydro-6-O-(1,4-anhydro-6-O-)butyl-D-sorbitol (23): Com-
pound 21 (0.187 g, 0.203 mmol) was dissolved in ethanol (3 mL),
and a small portion of palladium hydroxide on charcoal was added.
The suspension was stirred at room temperature under hydrogen.
Afterwards, the mixture was filtered through Celite, and the solvent
was removed under vacuum. The crude product was purified by
reverse-phase column chromatography (H2O Ǟ H2O/methanol,
1:1) to obtain pure 23 (0.048 g, 0.13 mmol, 64%) as a colourless
solid. M.p. 110.0 °C. Rf = 0.58 (EtOAc/MeOH/H2O = 7:3:1).
The NMR spectroscopic analysis was carried out for the (E) isomer
only. M.p. 89.5–90.5 °C. Rf = 0.58 (EtOAc/MeOH/H2O = 7:3:1).
1H NMR (400 MHz, [D6]DMSO): δ = 5.70 (br. s, 2 H, 2 CH2CH=),
[α]2D2.5 = 85.5 (c = 1.02, H2O). H NMR (400 MHz, MeOD): δ =
1
1.71–1.65 (m, 4 H, 2 OCH2CH2), 3.57–3.50 (m, 6 H, 6b-H, 6bЈ-H,
2 OCH2CH2), 3.63 (d, J1a,1b = 9.0, J1aЈ,1bЈ = 9.0 Hz, 2 H, 1b-H, 4.20 (t, JOH,CH2 = 5.1 Hz, 6 H, 6 OH), 3.89 (s, 4 H, 2 CH2CH=),
1bЈ-H), 3.67 (dd, J5,6a = 2.8, J5Ј,6aЈ = 2.8, J6a,6b = 10.3, J6aЈ,6bЈ
10.3 Hz, 2 H, 6a-H, 6aЈ-H), 3.88 (dd, J3,4 = 2.9, J3Ј,4Ј = 2.9, J4,5
=
=
3.36 (d, JCH2,CH2 = 5.1 Hz, 12 H, 6 CCH2OH), 3.29 [s, 4 H, 2
CH2C(CH2OH)3] ppm. 13C NMR (400 MHz, [D6]DMSO): δ =
576
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© 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2013, 566–577

Self-Metathesis of Polyol Allyl Ethers
[10] M. K. Hubbert, Nuclear Energy and the Fossil Fuels, Spring
Meeting of the Southern District, American Petroleum Insti-
tute, San Antonio, Texas, March 7–9, 1956.
128.8 (C=C), 70.7 (CH2C=C), 69.1 (CCH2OCH2C=), 60.8
[CCH2(O)3CH3], 45.6 (Cq, O4C) ppm. HRESI-MS: calcd. for
C14H29O8 325.1857 [M + H]+; found 325.1853; calcd. for
C14H28O8Na 347.1682 [M + Na]+; found 347.1663; calcd. for
C14H28O8K 363.1421 [M + K]+; found 363.1346.
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Acknowledgments
We thank the Fachagentur Nachwachsende Rohstoffe (FNR) for
financial support (grant numbers FKZ 8NR190/22019008 and
08NR213/22021308) and the Worlée Chemie GmbH for their coop-
eration.
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