Organic syntheses via transition metal complexes, CV: Regiocontrol of annelation of cyclopentene-1-thiones and cyclopenten-1-ones to alkenes with the aid of (1-alkynyl)carbene complexes (M = Cr, W)

Article abstract of DOI:10.1002/1099-0690(200010)2000:20<3463::aid-ejoc3463>3.0.co;2-c

Bicyclic olefins containing a 1-oxy-3-thiocyclopentadiene unit were obtained with high regioselectivity from [2-(cyclo-alk-1-enyl)-1-alkynyl]carbene complexes 1a-d and thiols 2a-c under mild conditions. If the reaction was performed in a protic solvent like ethanol, the produced allylthiocyclopentadienes 5 spontaneously underwent a thio Claisen rearrangement to give cyclopentene-1-thione complexes 3 in 62-72% yields. In nonprotic solvents, additional cyclopentene-1-thione complexes 6 and 7 were obtained as a result of the incorporation of two and three allylthiol units, respectively. Arylthiotetrahydroindene complexes 12b and c could be isolated in 76-79% yields. The corresponding tetrahydropentalene derivative 12a was unstable, but could be trapped by [2+2] cycloaddition of (1-alkynyl)carbene complex 1a to give a stable (cyclobutenyl)carbene complex 15. Hydrolysis of compounds 12a-c afforded cyclopenten-1-ones 13a-c.

Full text of DOI:10.1002/1099-0690(200010)2000:20<3463::aid-ejoc3463>3.0.co;2-c

FULL PAPER
Organic Syntheses via Transition Metal Complexes, CV[‡]
Regiocontrol of Annelation of Cyclopentene-1-thiones and Cyclopenten-1-ones
to Alkenes with the Aid of (1-Alkynyl)carbene Complexes (M ؍ Cr, W)
He-Ping Wu,[a] Rudolf Aumann,*[a] Sabine Venne-Dunker,[a][‡‡] and Pauli Saarenketo[a][‡‡]
Dedicated to Professor Heinrich Vahrenkamp on the occasion of his 60th birthday
Keywords: Carbene complexes / Chromium / Claisen rearrangement / Cyclopentadienes / Cyclopentene-1-thiones /
1-Metallahexatrienes / Sulfur heterocycles / Tungsten
Bicyclic olefins containing a 1-oxy-3-thiocyclopentadiene
of the incorporation of two and three allylthiol units, respect-
unit were obtained with high regioselectivity from [2-(cyclo- ively. Arylthiotetrahydroindene complexes 12b and c could
alk-1-enyl)-1-alkynyl]carbene complexes 1a−d and thiols
2a−c under mild conditions. If the reaction was performed in
be isolated in 76−79% yields. The corresponding tetrahy-
dropentalene derivative 12a was unstable, but could be
a protic solvent like ethanol, the produced allylthiocyclopen- trapped by [2+2] cycloaddition of (1-alkynyl)carbene com-
tadienes 5 spontaneously underwent a thio Claisen re- plex 1a to give a stable (cyclobutenyl)carbene complex 15.
arrangement to give cyclopentene-1-thione complexes 3 in
Hydrolysis of compounds 12a−c afforded cyclopenten-1-
62−72% yields. In nonprotic solvents, additional cyclopen- ones 13a−c.
tene-1-thione complexes 6 and 7 were obtained as a result
(1-alkynyl)carbene complex 1a, which on thermolysis un-
derwent a π-cyclization involving an insertion of carbon
Introduction
monoxide to give a pentacyclic compound (Scheme 1).[8,9]
(1-Alkynyl)carbene complexes (CO)5MϭC(OEt)CϵCR
(M ϭ Cr, W) have been utilized as stoichiometric reagents
in a number of high-yield transformations, potentially use-
ful in organic synthesis.[2] We recently reported on the
formation of cyclopentadienes[3] by π-cyclization of 1-
metalla-1,3,5-hexatrienes,[4,5] which were readily derived
from [2-(cyclopent-1-enyl)-1-alkynyl]carbene complex 1a by
addition of protic nucleophiles NuH.[6] For example, forma-
tion of cyclopentadienes could be triggered by addition of
secondary amines R2NH, secondary phosphanes R2PH
(R ϭ tBu, cC6H11),[7] and oxygen nucleophiles[8] ROH (R ϭ
aryl, aroyl and acyl), respectively, to (1-alkynyl)carbene
complex 1a. Whilst nitrogen or phosphorus nucleophiles led
to production of cyclopentadiene complexes, oxygen nucle-
ophiles gave highly reactive, metal-free cyclopentadienes,
Scheme 1. Cascade reaction initiated by addition of oxygen nucleo-
philes RCO2H to [2-(cyclopent-1-enyl)-1-alkynyl]carbene tungsten
such as 1-acyloxy-3-alkoxytetrahydropentalenes. The latter complex 1a
compounds underwent a cascade of reactions initiated
by the formation of a tricyclic [2ϩ2] cycloadduct with
Reaction of sulfur nucleophiles, like thioacylates RC-
(ϭO)SϪ or thio(imino)acylates RC(ϭNH)SϪ, with [2-(cyclo-
alk-1-enyl)-1-alkynyl]carbene complexes 1a؊c were found
to afford bicyclic cyclopentadienes containing sulfur sub-
stituents.[1] We now wish to report that the allylthiocyclop-
entadienes 5 thus generated spontaneously underwent a
thio Claisen rearrangement to give cyclopentene-1-thione
complexes 3 in 62Ϫ72% yields (Scheme 2, Table 1).
[‡]
Part CIV: Ref.[1]
[‡‡]
[a]
Crystal structure analyses
Organisch-Chemisches Institut der Universität Münster,
Corrensstraße 40, 48149 Münster, Germany
Fax: (internat.) ϩ 49-(0)251/833-6502
Email: aumannr@uni-muenster.de
Eur. J. Org. Chem. 2000, 3463Ϫ3473
WILEY-VCH Verlag GmbH, D-69451 Weinheim, 2000
1434Ϫ193X/00/1020Ϫ3463 $ 17.50ϩ.50/0
3463

H.-P. Wu, R. Aumann, S. Venne-Dunker, P. Saarenketo
FULL PAPER
˚
45.0(1)°]. The C2ϪC3 distance of 1.392(5) A is much
shorter than expected for a CϪC single bond, and is similar
˚
to C3ϪC4 [1.325(7) A], implying a strong π-polarization
Ϫ
with a negative charge at W(CO)5 and a positive charge
centred at the allyl unit C2ϪC3ϪC4, in line with the down-
field shift of the signals of these carbon atoms in the NMR
spectrum (e.g. compound 3b: C4: δ ϭ 194.7; C3: δ ϭ 120.6;
C2: δ ϭ 239.9).
Scheme 2. Allylthiocyclopentadiene complexes 5 from {[2-(cyclo-
alk-1-enyl)-1-alkynyl]carbene}tungsten complexes 1 and its spon-
taneous bridgehead allylation by thio Claisen rearrangement
Table 1. Assignments of structural groups in Scheme 2
3
a
[3]%
Figure 1. Molecular structure of C-allylcyclopentene-1-thione com-
˚
plex 3b; selected bond lengths [A] and angles [°]: W1ϪS1 2.537(1),
a
b
c
CH2
CH2CH2
CH2CH2CH2
62
72
65
S1ϪC2 1.647(4), C2ϪC3 1.392(5), C2ϪC6 1.550(6), C3ϪC4
1.325(7), C4ϪC5 1.495(6), C5ϪC6 1.559(7), C5ϪC10 1.572(8),
C6ϪC14 1.539(7), C6ϪC7 1.557(13), C10ϪC9 1.503(12), C7ϪC8
1.526(18), C8ϪC9 1.482(15), C14ϪC15 1.503(16); C2ϪS1ϪW11
113.6(2), C3ϪC2ϪC6 109.2(4), C3ϪC2ϪS1 128.5(3), C6ϪC2ϪS1
120.8(3),
C4ϪC3ϪC2
109.6(4),
O11ϪC4ϪC3
130.3(4),
O11ϪC4ϪC5116.3(4),
C3ϪC4ϪC5
113.5(4),
C4ϪC5ϪC6
102.4(4), C4ϪC5ϪC10 120.0(4), C6ϪC5ϪC10 112.9(4),
C14ϪC6ϪC2 110.1(4), C14ϪC6ϪC7 110.0(5), C2ϪC6ϪC7
110.6(5),
Generation and Thio Claisen Rearrangement of
Allylthiocyclopentadiene Complexes 5
C14ϪC6ϪC5
110.2(4),
C2ϪC6ϪC5
100.4(4),
C7ϪC6ϪC5 115.1(5), C9ϪC10ϪC5 116.5(6), C8ϪC7ϪC6
113.0(8), C9ϪC8ϪC7 109.0(8), C8ϪC9ϪC10 111.3(9),
C15ϪC14ϪC6 113.9(6), C16ϪC15ϪC14 122.3(12)
Addition of allylthiol (2a) to {[2-(cycloalk-1-enyl)-1-
alkynyl]carbene}tungsten complexes 1a؊c in ethanol in the
presence of triethylamine at 20 °C (5 min) resulted in the
A marked influence of the solvent on the reaction of [2-
formation of cyclopentene-1-thione complexes 3, in which (cycloalk-1-enyl)-1-alkynyl]carbene complexes 1 and al-
an allyl group was attached to the bridgehead carbon atom lylthiol (2a) has been observed. Whilst compounds 3 were
(Scheme 2). Compounds 3 are stable enough to be isolated produced in good yields if ethanol was used as solvent, ad-
by chromatography on silica gel, since the W(CO)5 unit ditional products 6 and 7 were obtained in aprotic solvents,
functions as a protection group for the thione moiety. such as diethyl ether (Scheme 3).
Metal-free thiones of this type would not survive these con-
Compounds 6 and 7 were isolated by chromatography
and were characterized spectroscopically. It was shown on
ditions.[10,11]
Formation of compounds 3 is assumed to follow the reac- the basis of NMR measurements that the cyclopentenones
tion paths outlined in Scheme 2. Though 1-metalla-1,3,5- 6 were not formed by thiolysis of compounds 3 under the
hexatrienes 4 and cyclopentadiene complexes 5 have not reaction conditions, even if the reaction time was extended
been characterized in this case, the reaction course can be to 12 h (at 20 °C). Furthermore, similar studies ruled out
presumed on the basis of earlier studies, in which such com- possible derivation of compounds 7 from compounds 6. Ac-
pounds have been isolated and fully characterized by crystal cordingly, it is assumed that 2,4-bis(allylthio)-1-metalla-
structure analyses.[1,7]
1,3,5-hexatrienes 8 are formed as key intermediates by sub-
The structural assignment of compounds 3 is based on stitution of the 2-ethoxy group of compounds (3E)-4 by an
1H and 13C NMR spectra, including 3J(H,H)- and 2,3J(C,H) allylthio unit (Scheme 3, Table 2). π-Cyclization of com-
measurements and a crystal structure analysis of compound pounds 8 and subsequent thio Claisen rearrangement are
3b (Figure 1). The WϪS1ϪC2ϪC3 backbone is planar [di- presumed to afford allyl derivatives 6. Addition of a third
hedral angle ϭ 0.00°; angle C2ϪS1ϪW ϭ 113.6(2)°] and allylthiol (2a) is assumed to require formation of chelate
the plane defined by this unit bisects the angle between two intermediates 10 as precursors to cyclopentadiene derivat-
neighbouring carbonyl ligands [C21ϪWϪS1ϪC2
ϭ
ives 11, from which compounds 7 are finally obtained. It
3464
Eur. J. Org. Chem. 2000, 3463Ϫ3473

Organic Syntheses via Transition Metal Complexes, CV
FULL PAPER
Scheme 3. Bridgehead allylation products 6 and 7 by incorporation of two and three allylthio units, respectively
Table 2. Assigments of structural groups in Scheme 3
(metal-free) tetrahydropentalenone 13a, -tetrahydroinden-
one 13b and -hexahydroazulenone 13d, respectively.[12] Ap-
plication of an excess of (1-alkynyl)carbene complex 1a in
its reaction with phenylthiol 2b resulted in the formation of
a [2ϩ2] cycloadduct 15a between the highly reactive tetra-
hydropentalene 14a and compound 1a.[8,13] [2ϩ2] Cycload-
ducts (15b and c) to the SCϭC units of tetrahydroindene-
and hexahydroazulenes 14b and 14d were not obtained. If
the reaction between (1-alkynyl)carbene complex 1a and
compound 2b was performed in the presence of triethylam-
ine at Ϫ20 °C, it resulted in the formation of an isomer
(17a) of compound 12a in 85% isolated yield. (1-Alkynyl)-
carbene complex 1b under similar conditions gave tetrahy-
droindene complexes 16b and c, which could be isolated in
80Ϫ82% yield by crystallization, but which were trans-
formed into tetrahydroindenones 18 if chromatography on
silica gel was attempted.
3؊6
M
a
[3]%
[6]%
[7]%
a
b
c
W
W
W
Cr
CH2
17
15
49
46
37
41
Ϫ
9
13
11
Ϫ
CH2CH2
CH2CH2CH2
CH2CH2
d
Ϫ
should be noted that reactions involving a chain extension
of allyl-type carbene complexes have not been reported to
date.
In an attempt to provide experimental evidence that 1-
oxy-3-thiotetrahydropentalenes, -indenes and -hexahy-
droazulenes were indeed generated from [2-(cycloalk-1-
enyl)-1-alkynyl]carbene complexes (Schemes 2 and 3), we
studied the formation of supposedly more stable arylthio
derivatives of this type. Compounds of the latter type could
indeed be obtained, but were found to readily undergo
(base-induced) rearrangement reactions and also (acid-in-
duced) hydrolysis, depending on the reaction conditions.
The structural assignment of compounds 12؊18 is based
1
on H- and 13C-NMR spectra. The compounds are easily
distinguished by the different chemical shifts of the olefinic
proton signals, each in a narrow range, for cyclopentadienes
(e.g. 12b: 2-H: δ ϭ 5.18; 16b: 2-H: δ ϭ 5.02; 16c: 2-H: δ ϭ
Reaction of (1-Alkynyl)carbene Complexes 1a؊c 5.13) and cyclopentenones (e.g. 13b: 2-H: δ ϭ 5.59), a char-
acteristic signal shift of the methine proton signals of iso-
with Arylthiols 2b and c
mers 12, 16 and 17 (e.g. 12b: 3a-H: δ ϭ 2.86; 16b: 1-H: δ ϭ
Addition of arylthiols 2b and c to [2-(cyclohex-1-enyl)-1- 3.93; 17a: 2-H2: δ ϭ 3.56), and the characteristic pattern of
alkynyl]carbene complex 1b (20 °C, 2 h) yielded tetrahy- CH2 and ϭCH signals of isomers 13 and 18 (e.g. 13a: 2-H:
droindene derivatives 12b and c, which could be isolated δ ϭ 5.60; 18a: 2-H2: δ ϭ 2.07). Hydrolysis of cyclopentadi-
from the reaction mixture by crystallization (Scheme 4, enes 12 to cyclopentenones results in drastic changes in
Table 3). Attempts to isolate compounds 12a,b and d by chemical shifts (e.g. 12b/13b: C-1: δ ϭ 143.0/182.1; C-2: δ ϭ
chromatography on silica gel led to the production of 100.9/123.5; C-3: δ ϭ 169.1/203.7). It should be noted that
Eur. J. Org. Chem. 2000, 3463Ϫ3473
3465

H.-P. Wu, R. Aumann, S. Venne-Dunker, P. Saarenketo
FULL PAPER
˚
˚
˚
systematic shift changes are imposed by ring strain effects 1.360(4) A, C5ϪC6 ϭ 1.532(4) A, C51ϪC61 ϭ 1.513(4) A,
˚
within the bicyclic system (e.g. 13a: 3a-H and 6a-H/C-3a C6ϪC61 ϭ 1.598(4) A] and bond angles [C51ϪC5ϪC6 ϭ
and C-6a: δ ϭ 2.94 and 2.59/52.5 and 48.7; 13b: 3a-H and 93.7(2)°, C5ϪC51ϪC61
7a-H/C-3a and C-7a: δ ϭ 2.62 and 2.30/47.5 and 43.2; 13d: 85.3(3)°, C51ϪC61ϪC6 ϭ 85.5(2)°].
3a-H and 8a-H/C-3a and C-8a: δ ϭ 2.90 and 2.44/52.6 and Structural details for compound 17a were also obtained
49.2; 18a: C-3a and C-6a: δ ϭ 181.9 and 151.2; 18b: C-3a by a crystal structure analysis (Figure 3). The plane defined
and C-7a: δ ϭ 168.6 and 141.4).[14]
by the atoms W, S1 and C130 is strongly inclined against
ϭ 95.1(2)°, C5ϪC6ϪC61 ϭ
Structural details for the (cyclobutenyl)carbene complex the almost planar adjacent ring [WϪS1ϪC2ϪC3 ϭ
15a were derived from a crystal structure analysis (Fig-
ure 2). The WϭC4ϪC5ϭC51 unit is twisted by 120.7(4) °,
whilst the C5ϭC51ϪC52ϭC56 moiety adopts an almost
planar s-trans configuration with an dihedral angle of
Ϫ178.8(4)°. The cyclobutenyl ring exhibits a trapezoidal
shape, with the typical pattern of bond lengths [C5ϭC51 ϭ
Figure 2. Molecular structure of cyclopentadiene complex 15a; se-
˚
lected bond lengths [A] and angles [°]: WϪC4 2.187(3), O3ϪC4
1.318(4), C4ϪC5 1.472(4), C5ϪC51 1.360(4), C5ϪC6 1.532(4),
C51ϪC52 1.444(4), C51ϪC61 1.513(4), C52ϪC56 1.332(4),
C52ϪC53 1.505(4), C6ϪC67 1.490(5), C6ϪC61 1.598(4), C6ϪS
1.833(3), C61ϪC65 1.546(4), C65ϪC66 1.494(4), C66ϪC67
1.329(4), SϪC71 1.776(4); O3ϪC4ϪC5 105.6(3), O3ϪC4ϪW
130.7(2),
C5ϪC4ϪW
123.0(2),
C51ϪC5ϪC4
132.3(3),
C51ϪC5ϪC6 93.7(2), C4ϪC5ϪC6 134.0(2), C5ϪC51ϪC52
135.1(3), C5ϪC51ϪC61 95.1(2), C52ϪC51ϪC61 129.2(3),
C56ϪC52ϪC51
124.6(3),
C56ϪC52ϪC53
110.8(3),
C51ϪC52ϪC53 124.6(3), C67ϪC6ϪC5 119.7(3), C67ϪC6ϪC61
103.3(2), C5ϪC6ϪC61 85.3(2), C67ϪC6ϪS 107.9(2), C5ϪC6ϪS
117.9(2), C61ϪC6ϪS 120.9(2), C51ϪC61ϪC62 119.3(3),
C51ϪC61ϪC65 119.6(3), C62ϪC61ϪC65 105.9(2), C51ϪC61ϪC6
85.5(2), C62ϪC61ϪC6 118.6(2), C65ϪC61ϪC6 106.7(2),
C66ϪC65ϪC61
C61ϪC65ϪC64
C67ϪC66ϪC65
102.6(2),
105.8(3),
115.4(3),
C66ϪC65ϪC64
C67ϪC66ϪO68
O68ϪC66ϪC65
114.6(3),
128.8(3),
115.7(3),
Scheme 4. 1-Alkoxy-3-arylthiocyclopentadienes and related com-
pounds generated from {[2-(cycloalk-1-enyl)-1-alkynyl]carbene}-
tungsten complexes 1a؊c and arylthiols 2b,c
C66ϪC67ϪC6 111.7(3)
Table 3. Assignments of structural groups in Scheme 4
1
a
2
Ar
a
b
c
CH2
CH2CH2
CH2CH2CH2
b
c
C6H5
o-MeOC6H4
[a]
12؊18
a
Ar
Reaction cond.[b]
[12][c]
[13][d]
[15]
[16][c]
[17][c]
[18][d]
a
a
a
b
b
b
c
c
c
d
CH2
C6H5
1a, 2b
1a, 2b
1a, 2b
1b, 2b
1b, 2b
1b, 2b
1b, 2c
1b, 2c
1b, 2c
1c, 2b
20 °C, 12 h
Ϫ
Ϫ
Ϫ
79
Ϫ
Ϫ
76
Ϫ
Ϫ
Ϫ
58
12
Ϫ
62
Ϫ
Ϫ
Ϫ
Ϫ
Ϫ
58
15
Ϫ
Ϫ
Ϫ
Ϫ
Ϫ
Ϫ
Ϫ
Ϫ
Ϫ
Ϫ
Ϫ
Ϫ
Ϫ
Ϫ
82
Ϫ
Ϫ
80
Ϫ
Ϫ
Ϫ
85
Ϫ
Ϫ
Ϫ
Ϫ
Ϫ
Ϫ
Ϫ
Ϫ
30
Ϫ
Ϫ
39
Ϫ
Ϫ
45
Ϫ
Ϫ
CH2
C6H5
50 °C, 4 h, ϩ B
Ϫ20 °C, 24 h, ϩ B
20 °C, 12 h
CH2
C6H5
CH2CH2
CH2CH2
CH2CH2
CH2CH2
CH2CH2
CH2CH2
CH2CH2CH2
C6H5
C6H5
50 °C, 4 h, ϩ B
Ϫ20 °C, 24 h, ϩ B
20 °C, 12 h
50 °C, 4 h, ϩ B
Ϫ20 °C, 24 h, ϩ B
20 °C, 12 h
C6H5
2-MeOC6H4
2-MeOC6H4
2-MeOC6H4
C6H5
[a]
[b]
Starting material, molar ratio of compounds 1:6 ϭ 1:1. Ϫ Reaction temperature, reaction time, ϩ B ϭ in the presence of Et3N. Ϫ
[c]
Yields of corresponding products isolated by crystallization at Ϫ20 °C. Ϫ [d] Isolated yields of corresponding products after chromato-
graphy on silica gel.
3466
Eur. J. Org. Chem. 2000, 3463Ϫ3473

Organic Syntheses via Transition Metal Complexes, CV
FULL PAPER
59.7(11)°]. In line with expectation, a trigonal-pyramidal S1
Cyclopentenones 13 could be readily obtained in a one-
atom geometry, which is indicated by the sum of bond pot procedure by reaction of [2-(cycloalk-1-enyl)-1-alkynyl]-
angles (329.5°) between the atoms attached to it, leads to carbene complexes 1a؊c with phenylthiol (2b) in ethanol
the production of an enantiomeric mixture. The enanti- (instead of diethyl ether) (Scheme 5, Table 4).
omers separated spontaneously on crystallization, and only
one enantiomer was analysed by crystal structure analysis.
Experimental Section
All operations were carried out under argon. All solvents were
1
dried and distilled prior to use. Ϫ All H- and 13C-NMR spectra
were routinely recorded with Bruker ARX 300 and AM 360 instru-
ments. Ϫ IR spectra were recorded with a Biorad Digilab Division
FTS-45 FT-IR spectrophotometer. Ϫ Elemental analysis were de-
termined with a PerkinϪElmer 240 elemental analyser. Ϫ Analyt-
ical TLC plates, Merck DC-Alufolien Kieselgel 60F240, were viewed
by UV light (254 nm) and stained by iodine. Rf values refer to TLC
tests. Chromatographic purifications were performed on Merck
Kieselgel 100. Pentacarbonyl[3-(cyclopent-1-enyl)-1-ethoxy-2-pro-
pyn-1-ylidene]tungsten (1a), pentacarbonyl[3-(cyclohex-1-enyl)-1-
ethoxy-2-propyn-1-ylidene]tungsten (1b), pentacarbonyl[3-(cyclo-
hept-1-enyl)-1-ethoxy-2-propyn-1-ylidene]tungsten (1c) and penta-
carbonyl[3-(cyclohex-1-enyl)-1-ethoxy-2-propyn-1-ylidene]-
chromium (1d) were prepared according to ref.[7]
(6a-Allyl-3-ethoxy-4,5,6,6a-tetrahydro-3aH-pentalene-3-thione-S)-
pentacarbonyltungsten (3a), (6a-Allyl-3-allylthio-4,5,6,6a-tetra-
hydro-3aH-pentalene-3-thione-S)pentacarbonyltungsten (6a) and
(6a-Allyl-3-allylthiopropylthio-4,5,6,6a-tetrahydro-3aH-pentalene-
3-thione-S)pentacarbonyltungsten (7a): Pentacarbonyl(3-cyclopen-
tenyl-1-ethoxy-2-propyn-1-ylidene)tungsten
(1a)
(236 mg,
Figure 3. Molecular structure of tetrahydropentalene complex 17a;
˚
0.50 mmol) was added with stirring at 20 °C to allylthiol (2a)
(37 mg, 0.50 mmol) and triethylamine (25 mg, 0.25 mmol) in 2 mL
of ethanol in a 2 mL screw-top vessel. Compound 1a was com-
pletely consumed within 5 min, to give a orange solution. The solv-
ent was removed after 0.5 h at 20 °C and the residue was separated
by rapid chromatography on silica gel (column 20 ϫ 2 cm) with n-
pentane/dichloromethane (10:1) to afford an orange fraction con-
taining compound 3a (169 mg, 62%, Rf ϭ 0.4 in n-pentane/dichlor-
omethane, 5:1; m.p. 67 °C). If the reaction was performed in diethyl
ether (instead of ethanol) for 6 h at 20 °C, it afforded two violet
compounds 6a and 7a in addition to compound 3a. Rapid chroma-
tography on silica gel (column 20 ϫ 2 cm) with n-pentane/dichloro-
methane (10:1) gave compound 6a (101 mg, 37%, Rf ϭ 0.5 in n-
pentane/dichloromethane, 5:1, violet crystals from n-pentane at
Ϫ15 °C, m.p. 49 °C), an orange fraction containing compound 3a
(46 mg, 17%) and a red fraction of compound of 7a (41 mg, 13%,
Rf ϭ 0.3 in n-pentane/ dichloromethane, 5:1, red oil). Compounds
3a, 6a and 7a are unstable in solution.
selected bond lengths [A] and angles [°]: WϪS1 2.561(3), S1ϪC2
1.764(11), S1ϪC130 1.810(12), C2ϪC9 1.332(16), C2ϪC3
1.513(16), C3ϪC4 1.518(17), C4ϪC5 1.325(17), C4ϪO10
1.338(15), C5ϪC9 1.464(18), C5ϪC6 1.494(17), C6ϪC7 1.50(2),
C7ϪC8 1.50(2), C8ϪC9 1.477(17), O10ϪC11 1.431(17), C11ϪC12
1.57(2);
C130ϪS1ϪW 115.3(4), C9ϪC2ϪC3 109.7(10), C9ϪC2ϪS1
124.7(9), C3ϪC2ϪS1 125.6(9), C2ϪC3ϪC4 101.2(10),
C2ϪS1ϪC130
103.4(5),
C2ϪS1ϪW
110.8(4),
C5ϪC4ϪO10 133.2(13), C5ϪC4ϪC3 110.4(12), O10ϪC4ϪC3
116.3(11), C4ϪC5ϪC9 108.8(12), C4ϪC5ϪC6 142.5(14),
C9ϪC5ϪC6 108.5(11), C5ϪC6ϪC7 105.8(12), C8ϪC7ϪC6
109.6(11), C9ϪC8ϪC7 105.7(11), C2ϪC9ϪC5 109.8(11),
C2ϪC9ϪC8 139.9(13), C5ϪC9ϪC8 110.3(10)
Scheme 5. Production of cyclopentenones 13 in a one-pot proced-
ure
Table 4. Assignments of structural groups in Scheme 5
1
Compound 3a: H NMR (C6D6): δ ϭ 6.52 (s, 1 H, 2-H), 5.40 (m,
13
a
[13]%
1 H, 2Ј-H), 4.90 (m, 2 H, 3Ј-H2), 3.49 (2 H, OCH2), 2.65 (dd, 1 H,
3a-H), 2.48 and 2.06 (each dd, each 1 H, diastereotopic 1Ј-H2),
1.84 (m, 1 H), 1.42 (m, 1 H), 1.25Ϫ1.02 (m, 4 H), 0.81 (t, 3 H,
OCH2CH3). Ϫ 13C NMR (C6D6): δ ϭ 239.8 (Cq, CϭS), 201.8 and
198.4 [trans- and cis-CO of W(CO)5], 193.7 (Cq, C-3), 133.2 (CH,
a
b
d
CH2
CH2CH2
CH2CH2CH2
83
75
80
Eur. J. Org. Chem. 2000, 3463Ϫ3473
3467

H.-P. Wu, R. Aumann, S. Venne-Dunker, P. Saarenketo
FULL PAPER
C-2Ј), 121.6 (CH, C-2), 119.0 (CH2, C-3Ј), 69.5 (OCH2), 66.7 (Cq, in diethyl ether (instead of ethanol) for 6 h at 20 °C, it afforded two
C-6a), 55.6 (CH, C-3a), 43.9 (CH2, C-1Ј), 38.4, 28.2 and 24.6 (each violet compounds 6b and 7b in addition to compound 3b. Rapid
CH2, C-4ϪC-7), 13.6 (OCH2CH3). Ϫ IR (hexane): ν˜ (%) ϭ 2066.8 chromatography on silica gel (column 20 ϫ 2 cm) with n-pentane/
Ϫ1
(5), 1940.9 (100), 1911.8 cm
(30) [ν(CϵO)]. Ϫ MS (70 eV); m/z
dichloromethane (10:1) gave compound 6b (113 mg, 41%, Rf ϭ 0.5
in n-pentane/dichloromethane, 5:1, violet crystals from n-pentane
184W (%): 546 (21) [Mϩ], 462 (35) [Mϩ Ϫ 3 CO], 434 (42) [Mϩ
Ϫ
4 CO], 406 (67) [Mϩ Ϫ 5 CO]. Ϫ C18H18O6SW (546.3): calcd. C at Ϫ15 °C, m.p. 46 °C), an orange fraction containing compound
39.54, H 3.29; found C 39.55, H 3.39.
3b (42 mg, 15%) and a fraction with compound 7b (36 mg, 11%,
Rf ϭ 0.5 in n-pentane/dichloromethane, 5:1, red oil). Compounds
3b, 6b and 7b are unstable in solution.
1
Compound 6a: H NMR (C6D6): δ ϭ 7.01 (s, 1 H, 2-H), 5.44 (m,
1 H, 2ЈЈ-H), 5.33 (m, 1 H, 2Ј-H), 5.06 (dd, 2 H, 3ЈЈ-H), 4.88 (m, 2
H, 3Ј-H), 3.05 (m, 2 H, 1ЈЈ-H), 2.38 and 2.03 (each dd, each 1 H,
diastereotopic 1Ј-H2), 2.78 (dd, 1 H, 3a-H), 1.71 (m, 1 H), 1.39 (m,
2 H), 1.18 (m, 3 H). Ϫ 13C NMR (C6D6): δ ϭ 236.3 (Cq, CϭS),
201.7 and 198.1 [trans- and cis-CO of W(CO)5], 137.2 (CH, C-2),
133.1 (CH, C-2Ј), 130.2 (CH, C-2ЈЈ), 120.2 (CH2, C-3ЈЈ), 118.9
(CH2, C-3Ј), 70.4 (Cq, C-6a), 60.3 (CH, C-3a), 44.4 (CH2, C-1Ј),
1
Compound 3b: H NMR (C6D6): δ ϭ 6.54 (s, 1 H, 2-H), 5.41 (m,
1 H, 2Ј-H), 4.89 (m, 2 H, 3Ј-H2), 3.54 (2 H, OCH2), 2.50 (dd, 1 H,
3a-H), 2.34 and 2.04 (each dd, each 1 H, diastereotopic 1Ј-H2),
1.58, 1.35 and 1.10 (each m, 1:4:3 H, 4-H2Ϫ7-H2), 0.83 (t, 3 H,
OCH2CH3). Ϫ 13C NMR (C6D6): δ ϭ 239.9 (Cq, CϭS), 201.9 and
198.5 [trans- and cis-CO of W(CO)5], 194.7 (Cq, C-3), 133.0 (CH,
C-2Ј), 120.6 (CH, C-2), 119.2 (CH2, C-3Ј), 69.3 (OCH2), 58.1 (Cq,
C-7a), 50.3 (CH, C-3a), 44.5 (CH2, C-1Ј); 34.3, 22.8, 18.6 and 18.4
36.0 (CH2, C-1ЈЈ); 38.2, 30.9, 24.6 (each CH2, C-4 Ϫ C-6). Ϫ IR
Ϫ1
(hexane): ν˜ (%) ϭ 2067.5 (5), 1941.5 (100), 1912.2 cm
(30)
[ν(CϵO)]. Ϫ MS (70 eV), m/z 184W (%): 574 (35) [Mϩ], 462 (75)
[Mϩ Ϫ 4 CO], 434 (68) [Mϩ Ϫ 5 CO]. Ϫ C19H18O5S2W (574.3):
calcd. C 39.70, H 3.13; found C 39.68, H 3.34.
(each CH2, C-4ϪC-7), 13.6 (OCH2CH3). Ϫ IR (hexane): ν˜ (%) ϭ
Ϫ1
2067.0 (5), 1940.8 (100), 1912.0 cm
(30) [ν(CϵO)]. Ϫ MS
(70 eV), m/z 184W (%): 560 (17) [Mϩ], 476 (33) [Mϩ Ϫ 3 CO], 448
(30) [Mϩ Ϫ 4 CO], 420 (100) [Mϩ Ϫ 5 CO]. Ϫ C19H20O6SW
(560.3): calcd. C 40.69, H 3.57; found C 40.68, H 3.65.
X-ray Crystal Structure Analysis of Compound 3b: Formula
C19H20O6SW, M ϭ 560.26 gmolϪ1, 0.30 ϫ 0.20 ϫ 0.10 mm, a ϭ
3
˚
˚
11.532(1), b ϭ 11.572(1), c ϭ 15.896(1) A, V ϭ 2121.3(3) A ,
Dcalcd. ϭ 1.754 gcmϪ3, µ ϭ 55.74 cmϪ1, empirical absorption cor-
rection via SORTAV (0.286 Յ T Յ 0.606), Z ϭ 4, orthorhombic,
˚
space group Pnma (No. 62), λ ϭ 0.71073 A, T ϭ 198(2) K, ω and
scans, 4611 reflections collected (Ϯh, Ϯk, Ϯl), [(sinΘ)/λ]max ϭ 0.65
˚
A
Ϫ1, 2552 independent reflections and 2248 observed reflections [I
Compound 7a: 1H NMR (C6D6): δ ϭ 7.07 (1 H, s, 2-H), 5.62 (1 H,
m, 2ЈЈЈ-H), 5.37 (1 H, m, 2Ј-H), 4.91 (4 H, m, 3Ј-H and 3ЈЈЈ-H),
2.80 (2 H, m, 1ЈЈЈ-H2), 2.67 and 2.24 (each 2 H, each t, 1ЈЈ- and
3ЈЈ-H2), 2.38 (1 H, dd, 3a-H), 2.42 and 2.06 (each 1 H, each dd,
diastereotopic 1Ј-H2), 1.64 (2 H, m, 2ЈЈ-H2), 1.74 (1 H, m), 1.40 (2
H, m) and 1.20 (3 H, m) (4-H2Ϫ6-H2). Ϫ 13C NMR (C6D6): δ ϭ
236.0 (Cq, CϭS), 201.7 and 198.2 [trans- and cis-CO of W(CO)5],
136.9 (CH, C-2), 134.6 (CH, C-2Ј), 133.1 (CH, C-2ЈЈЈ), 119.0 (CH2,
C-3Ј), 116.9 (CH2, C-3ЈЈЈ), 70.5 (Cq, C-6a), 60.3 (CH, C-3a), 44.4
(CH2, C-1Ј), 34.9 (CH2, C-1ЈЈЈ); 32.4, 29.3 and 27.8 (each 2 H, t,
t, ‘‘quint‘‘, each CH2, C-1ЈЈϪC-3ЈЈ); 34.8, 31.0 and 24.6 (each CH2,
C-4ϪC-7). Ϫ IR (hexane): ν˜ (%) ϭ 2067.5 (5), 1939.6 (100), 1922.0
(40) [ν(CϵO)] cm Ϫ1. Ϫ MS (70 eV), m/z 184W (%): 648 (6) [Mϩ],
324 (40) [Mϩ Ϫ W(CO)5], 283 (50) [324 Ϫ C3H5], 209 (30) [283 Ϫ
C3H6S], 91 (100).
Ն 2σ(I)], 176 refined parameters, R ϭ 0.024, Rw2 ϭ 0.056, max./
min. residual electron density ρ ϭ 1.89/Ϫ1.32 eAϪ3, hydrogen
˚
atoms calculated and riding, molecule is located on a mirror plane;
therefore the cyclohexane ring and the propylene unit are disor-
dered.[15]
1
Compound 6b: H NMR (C6D6): δ ϭ 7.07 (s, 1 H, 2-H), 5.45 (m,
1 H, 2ЈЈ-H), 5.38 (m, 1 H, 2Ј-H), 5.06 (dd, 2 H, 3ЈЈ-H), 4.88 (m, 2
H, 3Ј-H2), 3.11 (m, 2 H, 1ЈЈ-H), 2.62 (dd, 1 H, 3a-H), 2.25 and 2.03
(each dd, each 1 H, diastereotopic 1Ј-H2), 1.53 (m, 1 H), 1.36 (m,
3 H), 1.05 (m, 4 H). Ϫ 13C NMR (C6D6): δ ϭ 236.2 (Cq, CϭS),
201.8 and 198.2 [trans- and cis-CO of W(CO)5], 188.2 (Cq, C-3),
136.5 (CH, C-2), 133.0 (CH, C-2Ј), 130.0 (CH, C-2ЈЈ), 120.2 (CH2,
C-3ЈЈ), 119.0 (CH2, C-3Ј), 62.0 (Cq, C-7a), 55.1 (CH, C-3a), 45.1
(CH2, C-1Ј), 34.8 (CH2, C-1ЈЈ); 34.6, 26.4, 19.1 and 18.9 (each CH2,
C-4ϪC-7). Ϫ IR (hexane): ν˜ (%) ϭ 2067.0 (5), 1940.9 (100),
1912.5 cm Ϫ1 (30) [ν(CϵO)]. Ϫ MS (70 eV), m/z 184W (%): 588 (30)
[Mϩ], 476 (54) [Mϩ Ϫ 4 CO], 448 (29) [Mϩ Ϫ 5 CO]. Ϫ
C20H20O5S2W (588.4): calcd. C 40.79, H 3.40; found C 41.03, H
3.79.
(7a-Allyl-3-ethoxy-3a,4,5,6,7,7a-hexahydroindene-1-thione-S)-
pentacarbonyltungsten (3b), (7a-Allyl-3-allylthio-3a,4,5,6,7,7a-hexa-
hydroindene-1-thione-S)pentacarbonyltungsten (6b) and (6a-Allyl-3-
allylsulfidopropylthio-4,5,6,6a-tetrahydro-3aH-indene-3-thione-S)-
pentacarbonyltungsten (7b): Pentacarbonyl(3-cyclopentenyl-1-
ethoxy-2-propyn-1-ylidene)tungsten (1*b) (243 mg, 0.50 mmol) was Compound 7b: 1H NMR (C6D6): δ ϭ 7.09 (1 H, s, 2-H), 5.62 (1 H,
added to allylthiol (2a) (37 mg, 1.00 mmol) and triethylamine
(25 mg, 0.25 mmol) in 2 mL of ethanol as described above to give
an orange compound 3b (201 mg, 72%, Rf ϭ 0.6 in n-pentane/
dichloromethane, 5:1, m.p. 65 °C). Ϫ If the reaction was performed
m, 2ЈЈЈ-H), 5.39 (1 H, m, 2Ј-H), 4.90 (4 H, m, 3Ј- and 3ЈЈЈ-H), 2.79
(2 H, m, 1ЈЈЈ-H2), 2.70 and 2.25 (each 2 H, each t, 1ЈЈ- and 3ЈЈ-H2),
2.63 (1 H, dd, 3a-H), 2.26 and 2.03 (each 1 H, each dd, diastereo-
topic 1Ј-H2), 1.66 (2 H, m, 2ЈЈ-H2), 1.56 (1 H, m), 1.36 (4 H, m)
3468
Eur. J. Org. Chem. 2000, 3463Ϫ3473

Organic Syntheses via Transition Metal Complexes, CV
and 1.10 (3 H, m) (4-H2Ϫ7-H2). Ϫ 13C NMR (C6D6): δ ϭ 235.9 [Mϩ Ϫ 4 CO], 288 (89) [Mϩ Ϫ 5 CO]. Ϫ C19H20O6SCr (428.4):
FULL PAPER
(Cq, CϭS), 201.7 and 198.2 [trans- and cis-CO of W(CO)5], 136.0
(CH, C-2), 134.6 (CH, C-2Ј), 132.9 (CH, C-2ЈЈЈ),119.0 (CH2, C-3Ј),
116.9 (CH2, C-3ЈЈЈ), 62.0 (Cq, C-7a), 55.0 (CH, C-3a), 44.9 (CH2,
C-1Ј), 34.9 (CH2, C-1ЈЈЈ); 32.9, 29.3 and 27.7 (each CH2, C-1ЈЈϪC-
3ЈЈ); 34.7, 26.3, 19.0 and 18.9 (each CH2, C-4ϪC-7). Ϫ IR (hexane):
ν˜ (%) ϭ 2067.5 (5), 1939.0 (100), 1922.2 (40) [ν(CϵO)] cm Ϫ1. Ϫ
MS (70 eV), m/z 184W (%): 662 (4) [Mϩ], 338 (40) [Mϩ Ϫ W(CO)5],
297 (45) [338 Ϫ C3H5], 223 (35) [297 Ϫ SC3H6], 115 (100).
calcd. C 53.27, H 4.71; found C 53.05, H 4.69.
1
Compound 6d: H NMR (C6D6): δ ϭ 7.05 (s, 1 H, 2-H), 5.38 (m,
2 H, 2Ј- and 2ЈЈ-H), 4.94 (m, 4 H, 3Ј- and 3ЈЈ-H), 3.19 (m, 2 H,
1ЈЈ-H), 2.50 (dd, 1 H, 3a-H), 2.26 and 2.04 (each dd, each 1 H,
diastereotopic 1Ј-H2); 1.58, 1.35 and 1.06 (each m, 1:3:4 H, 4-
H2Ϫ7-H2). Ϫ 13C NMR (C6D6): δ ϭ 238.7 (Cq, CϭS), 221.6 and
216.5 [trans- and cis-CO of W(CO)5], 188.0 (Cq, C-3), 133.9 (CH,
C-2), 132.8 (CH, C-2Ј), 130.4 (CH, C-2ЈЈ), 120.1 (CH2, C-3ЈЈ),
119.2 (CH2, C-3Ј), 62.9 (Cq, C-7a), 54.6 (CH, C-3a), 45.2 (CH2, C-
1Ј), 35.7 (CH2, C-1ЈЈ); 34.7, 26.3, 19.0 and 18.9 (each CH2, C-4ϪC-
(8a-Allyl-3-ethoxy-4,5,6,7,8,8a-hexahydro-3aH-azulene-1-thione-S)-
pentacarbonyltungsten
(3c):
Pentacarbonyl(3-cycloheptenyl-1-
Ϫ1
7). Ϫ IR (hexane): ν˜ (%) ϭ 1962.8 (5), 1932.1 (100), 1903.2 cm
ethoxy-2-propyn-1-ylidene)tungsten (1d) (250 mg, 0.50 mmol) was
treated with allylthiol (2a) (37 mg, 0.50 mmol) in the presence of
triethylamine (25 mg, 0.25 mmol) in 2 mL of ethanol as described
above. Chromatography after 3 h at 20 °C afforded compound 3c
(185 mg, 65%, Rf ϭ 0.7 in n-pentane/dichloromethane, 5:1, orange
oil). If the reaction was performed in toluene (instead of ethanol)
it gave compound 3c in 49% yield (140 mg).
(30) [ν(CϵO)]. Ϫ MS (70 eV), m/z (%): 456 (6) [Mϩ], 428 (10) [Mϩ
Ϫ 1 CO], 316 (57) [Mϩ Ϫ 5 CO]. Ϫ C20H20O5S2Cr (456.5): calcd.
C 52.62, H 4.42; found C 52.43, H 4.40.
(6aR*,3aS*)-3-Phenylthio-4,5,6,6a-tetrahydro-3aH-pentalen-1-one
(13a) and (1S*,4R*,7R*)-2-(Cyclopent-1-enyl)-6-ethoxy-3-
(1,1,1,1,1-pentacarbonyl-2-ethoxy-1-tungsta-2-ethenyl)-4-phenyl-
thiospirotricyclo[5.3.01,4.01,7]deca-2,5-diene (15a): To pentacar-
bonyl(3-cyclopentenyl-1-ethoxy-2-propyn-1-ylidene)tungsten (1a)
(236 mg, 0.50 mmol) in 1 mL of diethyl ether was added dropwise
at 20 °C a solution of thiophenol (55 mg, 0.50 mmol) (2b) in 1 mL
of diethyl ether. According to a TLC test, compound 1a was con-
sumed completely after 2 h at 20 °C. After stirring for 10 h at 20
°C, the mixture was centrifuged in order to remove W(CO)6. Fast
chromatography on silica gel (column 20 ϫ 2 cm) with n-pentane/
dichloromethane (6:1) afforded a red fraction containing com-
pound 15a (27 mg, 15%, Rf ϭ 0.5 in n-pentane/dichloromethane
4:1, m.p. 74 °C). Subsequent elution with n-pentane/diethyl ether
(3:1) gave a colourless polar fraction containing compound 13a
(67 mg, 58%, Rf ϭ 0.4 in n-pentane/diethyl ether, 3:1). Compound
15a was not formed if the (1-alkynyl)carbene complex 1a was
treated with an excess of 1.5 equivalents of thiophenol (2b), thus
indicating that the reaction of the (1-alkynyl)carbene complex 1a
with thiophenol (2b) is faster than the [2ϩ2] cycloaddition of 1a to
compound 14a. If a solution of thiophenol (55 mg, 0.50 mmol) (2b)
in 2 mL of ethanol was added to pentacarbonyl(3-cyclopentenyl-1-
ethoxy-2-propyn-1-ylidene)tungsten (1a) (236 mg, 0.50 mmol) at 20
°C, the starting material was consumed after a few minutes (TLC
test) to give cyclopenten-1-one 13a in 83% yield.
1
Compound 3c: H NMR (C6D6): δ ϭ 6.66 (s, 1 H, 2-H), 5.38 (m,
1 H, 2Ј-H), 4.90 (m, 2 H, 3Ј-H2), 3.58 (2 H, OCH2), 2.62 (dd, 1 H,
3a-H), 2.18 and 2.08 (each dd, each 1 H, diastereotopic 1Ј-H2);
1.89, 1.65, 1.51, 1.32 and 0.96 (each m, 1:2:1:4:3 H, 4-H2Ϫ8-H2),
0.85 (t, 3 H, OCH2CH3). Ϫ 13C NMR (C6D6): δ ϭ 240.0 (Cq, Cϭ
S), 201.8 and 198.4 [trans- and cis-CO of W(CO)5], 194.4 (Cq, C-
3), 132.7 (CH, C-2Ј), 119.5 (CH, C-2), 118.1 (CH2, C-3Ј), 69.1
(OCH2), 58.9 (Cq, C-8a), 49.8 (CH, C-3a), 44.6 (CH2, C-1Ј); 34.4,
22.7, 18.5 and 18.3 (each CH2, C-4ϪC-7), 13.6 (OCH2CH3). Ϫ
Ϫ1
IR (hexane): ν˜ (%) ϭ 2067.9 (5), 1941.4 (100), 1912.2 cm
(30)
[ν(CϵO)]. Ϫ MS (70 eV), m/z 184W (%): 574 (13) [Mϩ], 490 (19)
[Mϩ Ϫ 3 CO], 434 (39) [Mϩ Ϫ 5 CO]. Ϫ C20H22O6SW (574.3):
calcd. C 41.83, H 3.86; found C 42.57, H 3.98.
(7a-Allyl-3-ethoxy-3a,4,5,6,7,7a-hexahydroindene-1-thione-S)-
pentacarbonylchromium (3d) and (7a-Allyl-3-allylthio-3a,4,5,6,7,7a-
hexahydroindene-1-thione-S)pentacarbonylchromium (6d): Pentacar-
bonyl(3-cyclohexenyl-1-ethoxy-2-propyn-1-ylidene)chromium (1d)
(178 mg, 0.50 mmol) was treated with allylthiol (2a) (37 mg,
0.50 mmol) in the presence of triethylamine (25 mg, 0.25 mmol) in
2 mL of toluene as described above to give compound 6d (20 mg,
9%, Rf ϭ 0.8 in n-pentane/dichloromethane, 5:1, violet crystals,
m.p. 42 °C) and compound 3d (98 mg, 46%, Rf ϭ 0.7 in n-pentane/
dichloromethane, 5:1, orange crystals from n-pentane at Ϫ15 °C,
m.p. 58 °C).
1
Compound 13a: H NMR (C6D6): δ ϭ 7.22 (d, 2 H, o-H Ph), 6.94
(m, 3 H, p-H and m-H Ph), 5.60 (s, 1 H, 2-H), 2.94 and 2.59 (each
m, each 1 H, 3a-H and 6a-H), 1.97 (m, 1 H), 1.76 (m, 1 H),
1.39Ϫ1.21 (m, 4 H). Ϫ 13C NMR (C6D6): δ ϭ 205.0 (Cq, CϭO),
181.5 (Cq, C-3); 134.7, 129.8 and 129.7 (each CH, 2:2:1, Ph), 130.0
(i-C, Ph), 126.3 (CH, C-2), 52.5 and 48.7 (each CH, C-3a and C-
1
Compound 3d: H NMR (C6D6): δ ϭ 6.50 (s, 1 H, 2-H), 5.39 (m,
6a), 30.9, 29.4 and 24.2 (each CH2, C-4ϪC-6). Ϫ IR (diethyl ether):
1 H, 2Ј-H), 4.86 (m, 2 H, 3Ј-H), 3.51 (2 H, OCH2), 2.51 (dd, 1 H,
3a-H), 2.34 and 2.03 (each dd, each 1 H, diastereotopic 1Ј-H2);
1.58, 1.36 and 1.10 (each m, 1:4:3 H, 4-H2Ϫ7-H2), 0.85 (t, 3 H,
OCH2CH3). Ϫ 13C NMR (C6D6): δ ϭ 241.9 (Cq, CϭS), 223.6 and
216.8 [trans- and cis-CO of W(CO)5], 194.9 (Cq, C-3), 133.0 (CH,
C-2Ј), 119.1 (CH, C-2), 118.1 (CH2, C-3Ј), 69.1 (OCH2), 58.9 (Cq,
C-7a), 49.8 (CH, C-3a), 44.6 (CH2, C-1Ј); 34.4, 22.7, 18.5 and 18.3
Ϫ1
ν˜ (%) ϭ 1701.9 cm
(70) [ν(CϭO)]. Ϫ MS (70 eV), m/z (%): 230
(100) [Mϩ]. Ϫ C14H14OS (230.3): calcd. C 73.01, H 6.13; found C
72.97, H 6.04.
(each CH2, C-4ϪC-7), 13.6 (OCH2CH3). Ϫ IR (hexane): ν˜ (%) ϭ
Ϫ1
1961.7 (5), 1932.1 (100), 1902.1 cm
(30) [ν(CϵO)]. Ϫ MS
(70 eV), m/z (%): 428 (13) [Mϩ], 344 (6) [Mϩ Ϫ 3 CO], 316 (25)
Eur. J. Org. Chem. 2000, 3463Ϫ3473
3469

H.-P. Wu, R. Aumann, S. Venne-Dunker, P. Saarenketo
FULL PAPER
Compound 15a: 1H NMR (C6D6): δ ϭ 7.57, 7.03 and 6.94 (each m, (each CH2, C-4ϪC-7), 14.3 (OCH2CH3). Ϫ IR (diethyl ether): ν˜
2:1:2, Ph), 5.73 (m, 1 H, 2Ј-H), 5.37 (s, 1 H, 5-H), 4.56 and 4.31 (%) ϭ 2062.9 (5), 1933.8 (100), 1905.7 cmϪ1 (30) [ν(CϵO)]. Ϫ MS
(each m, each 1 H, diastereotopic WϭCOCH2), 3.80 and 3.60 (each
m, each 1 H, diastereotopic 6-OCH2), 3.23 (dd, 1 H, 7-H), 2.62 (m,
1 H), 2.19 (m, 3 H), 1.92 (m, 2 H), 1.64 (m, 5 H), 1.03 (t, 6 H, 2
OCH2CH3). Ϫ 13C NMR (C6D6): δ ϭ 316.2 (WϭC), 204.3 and
198.3 [each Cq, trans- and cis- CO of W(CO)5], 164.1 (Cq, C-6),
159.8 (Cq, broad, C-3); 136.6, 136.0, 135.3 and 135.1 (each Cq, C-
1Ј, C-2Ј, C-2 and i-C, Ph), 136.1, 128.8 and 128.2 (each CH, 2:2:1,
Ph), 100.6 (CH, C-5), 78.2 (dynamically broadened WϭCOCH2),
75.2 (Cq, C-4), 65.3 (6-OCH2), 64.0 (Cq, C-1), 49.9 (CH, C-7), 34.3,
33.5 and 23.6 (each CH2, C-3ЈϪC-5Ј ); 33.4, 30.8 and 26.5 (each
(70 eV), m/z 184W (%): 596 (1) [Mϩ], 456 (5) [Mϩ Ϫ 5 CO]. Ϫ
C22H20O6SW (596.3): calcd. C 44.31, H 3.38; found C 44.21, H
3.35.
CH2, C-8ϪC-10), 14.5 (2 OCH2CH3). Ϫ IR (diethyl ether): ν˜ (%) ϭ
1
Compound 13b: H NMR (C6D6): δ ϭ 7.27 (d, 2 H, o-H Ph), 6.97
Ϫ1
2068.9 (5), 1947.1 (100), 1911.7 cm
(30) [ν(CϵO)]. Ϫ MS
(m, 3 H, m-H and p-H Ph), 5.59 (s, 1 H, 2-H), 2.62 and 2.30 (each
m, each 1 H, 3a-H and 7a-H), 2.11 (m, 1 H), 1.81 (m, 1 ), 1.42Ϫ1.10
(m, 6 H). Ϫ 13C NMR (C6D6): δ ϭ 203.7 (Cq, CϭO), 182.1 (Cq,
C-3); 134.2, 129.8 and 129.7 (each CH, 2:2:1, Ph), 130.0 (Cq, i-C,
Ph), 123.5 (CH, C-2), 47.5 and 43.2 (each CH, C-3a and C-7a),
(70 eV), m/z 184W (%): 730 (5) [Mϩ], 702 (20) [Mϩ Ϫ CO], 618
(100) [Mϩ Ϫ 4 CO], 590 (20) [Mϩ Ϫ 5 CO]. Ϫ C31H30O7SW
(730.5): calcd. C 50.83, H 4.11; found C 50.97, H 4.47.
X-ray Crystal Structure Analysis of Compound 15a: Formula
C31H30O7SW, M ϭ 730.46 gmolϪ1, 0.25 ϫ 0.25 ϫ 0.20 mm, a ϭ
30.0, 22.7 and 21.6 (each CH2, 1:1:2, C-4ϪC-7). Ϫ IR (diethyl
Ϫ1
ether): ν˜ (%) ϭ 1699.8 cm
(70) [ν(CϭO)]. Ϫ MS (70 eV), m/z
˚
15.558(1), b ϭ 18.648(1), c ϭ 10.051(1) A, β ϭ 94.49(1) °, V ϭ
(%): 244 (100) [Mϩ]. Ϫ C15H16OS (244.4): calcd. C 73.73, H 6.60;
3
2907.1(4) A , Dcalcd. ϭ 1.669 gcmϪ3, µ ϭ 40.91 cmϪ1, empirical
˚
found C 73.56, H 6.52.
absorption correction by SORTAV (0.428 Յ T Յ 0.495), Z ϭ 4,
˚
monoclinic, space group P21/c (No. 14), λ ϭ 0.71073 A, T ϭ 198(2)
K, ω and scans, 21588 reflections collected (Ϯh, Ϯk, Ϯl), [(sinΘ)/
λ]max ϭ 0.71 AϪ1, 8808 independent reflections and 7197 observed
˚
reflections [I Ն 2σ(I)], 363 refined parameters, R ϭ 0.033, Rw2
ϭ
Ϫ3
˚
0.069, max./min. residual electron density ρ ϭ 1.27/Ϫ0.82 eA
,
hydrogen atoms calculated and riding.[15]
Compound 14b: 1H NMR (C6D6): δ ϭ 7.41 (m, 2 H, o-H Ph), 6.86
(m, 3 H, m-H and p-H Ph), 5.08 (s, 1 H, 2-H), 3.34 (m, 2 H, OCH2),
3.06 (dd, 1 H, 3a-H), 2.68 (m, 1 H), 2.37 (m, 1 H), 1.94 (m, 1 H),
1.64 (m, 1 H), 1.51Ϫ1.16 (m, 4 H), 1.01 (t, 3 H, OCH2CH3). Ϫ 13C
NMR (C6D6): δ ϭ 169.1 (Cq, C-3), 142.6 (Cq, C-1), 134.7 (Cq, i-
C, Ph); 129.8, 129.2 and 128.2 (each CH, 2:2:1, Ph), 123.5 (Cq, C-
7a), 97.8 (CH, C-2), 65.2 (OCH2), 51.4 (CH, C-3a), 31.6, 29.1, 26.4
and 25.3 (each CH2, C-4ϪC-7), 14.4 (OCH2CH3).
(3aS*)-Pentacarbonyl(3-ethoxy-1-phenylthio-4,5,6,7-tetrahydro-
3aH-indene-S)tungsten (12b), 3-Phenylthio-3a,4,5,6,7,7a-hexahy-
droinden-1-one (13b) and 3-Ethoxy-1-phenylthio-4,5,6,7-tetrahydro-
3aH-indene (14b): Thiophenol (2b) (55 mg, 0.50 mmol) was treated
with pentacarbonyl(3-cyclohexenyl-1-ethoxy-2-propyn-1-ylidene)-
tungsten (1b) (243 mg, 0.50 mmol) in 2 mL of diethyl ether for 2 h
as described above. Fast chromatography with n-pentane/dichloro-
methane (10:1) afforded a yellow fraction containing compound
12b (235 mg, 79%, Rf ϭ 0.8 in n-pentane/dichloromethane, 4:1,
m.p. 67 °C). Compound 12b in [D6]benzene was transformed into
the metal-free ligand 14b and W(CO)6 within 15 h at 20 °C accord-
ing to NMR measurements. Chromatography of the reaction mix-
ture resulting from compounds 1b and 2b after 12 h at 20 °C gave
compound 13b (76 mg, 62%, Rf ϭ 0.5 in n-pentane/diethyl ether,
3:1, colourless oil). If a solution of thiophenol (55 mg, 0.50 mmol)
(2b) in 2 mL of ethanol was added to pentacarbonyl(3-cyclohex-
enyl-1-ethoxy-2-propyn-1-ylidene)tungsten (1b) (243 mg, 0.50
mmol) at 20 °C, starting material was consumed after few min
(TLC test) to give cyclopenten-1-one 13b in 75% yield.
(3aS*)-Pentacarbonyl[3-ethoxy-1-(2-methoxyphenylthio)-4,5,6,7-
tetrahydro-3aH-indene-S]tungsten (12c): Pentacarbonyl(3-cyclohex-
enyl-1-ethoxy-2-propyn-1-ylidene)tungsten (1b) (243 mg, 0.50
mmol) was treated with 2-methoxythiophenol (2c) (70 mg, 0.50
mmol) at 20 °C as described above to give compound 12c (238 mg,
76%, Rf ϭ 0.5 in n-pentane/dichloromethane, 1:3, m.p. 68 °C). Ϫ
1H NMR (C6D6): δ ϭ 7.40 and 6.39 (each d, each 1 H, 3-H and
6-H of C6H4), 6.91 and 6.62 (each t, each 1 H, 4-H and 5-H of
C6H4), 5.18 (s, 1 H, 2-H), 3.37 (m, 2 H, 3-OCH2), 3.35 (s, 3 H,
OCH3), 2.84 (dd, 1 H, 3a-H), 2.69 (m, 1 H), 2.22 (m, 1 H), 1.83
(m, 1 H), 1.63 (m, 1 H), 1.44Ϫ1.16 (m, 4 H), 0.98 (t, 3 H,
OCH2CH3). Ϫ 13C NMR (C6D6): δ ϭ 201.2 and 197.9 [each Cq,
trans- and cis-CO of W(CO)5], 169.1 (Cq, C-3), 143.0 (Cq, C-1),
158.1 (Cq, C-2 of C6H4), 132.2 and 131.3 (each CH, C-4 and C-6
of C6H4), 123.7 (Cq, C-1 of C6H4), 121.1 and 111.7 (each CH, C-
3 and C-5 of C6H4), 125.2 (Cq, C-7a), 100.9 (CH, C-2), 65.5
(OCH2), 55.4 (OCH3), 51.6 (CH, C-3a); 31.4, 28.7, 26.7 and 24.7
(each CH2, C-4ϪC-7), 14.3 (OCH2CH3). Ϫ IR (diethyl ether): ν˜
(%) ϭ 2062.7 (5), 1933.8 (100), 1905.7 cmϪ1 (30) [ν(CϵO)]. Ϫ MS
(70 eV), m/z 184W (%): 626 (5) [Mϩ], 486 (10) [Mϩ Ϫ 5 CO]. Ϫ
C23H22O7SW (626.3): calcd. C 44.07, H 3.51; found C 43.87, H
3.62.
Compound 12b: 1H NMR (C6D6): δ ϭ 7.52 (m, 2 H, o-H Ph), 6.97
(m, 3 H, m-H and p-H Ph), 5.18 (s, 1 H, 2-H), 3.39 (m, 2 H, OCH2),
2.86 (dd, 1 H, 3a-H), 2.68 (m, 1 H), 2.23 (m, 1 H), 1.83 (m, 1 H),
1.64 (m, 1 H), 1.44Ϫ1.16 (m, 4 H), 0.99 (t, 3 H, OCH2CH3). Ϫ 13C
NMR (C6D6): δ ϭ 201.2 and 197.9 [each Cq, trans- and cis-CO of
W(CO)5], 169.1 (Cq, C-3), 143.0 (Cq, C-1), 135.7 (Cq, i-C, Ph), Pentacarbonyl(1-ethoxy-3-phenylthio-2,4,5,6-tetrahydro-pentalene-
129.6, 129.5 and 128.9 (each CH, 2:2:1, Ph), 125.4 (Cq, C-7a), 100.9 S)tungsten (17a): To pentacarbonyl(3-cyclopentenyl-1-ethoxy-2-
(CH, C-2), 65.6 (OCH2), 51.5 (CH, C-3a); 31.5, 28.8, 26.7 and 24.8 propyn-1-ylidene)tungsten (1a) (236 mg, 0.50 mmol) in 1.5 mL of
3470
Eur. J. Org. Chem. 2000, 3463Ϫ3473

Organic Syntheses via Transition Metal Complexes, CV
FULL PAPER
hexane in a 2-mL screw-top vessel was added dropwise with stirring
at Ϫ20 °C a solution of thiophenol (2b) (55 mg, 0.50 mmol) and
triethylamine (20 mg, 0.20 mmol) in 0.5 mL of diethyl ether. A col-
our change from brown to yellow was observed immediately. Yel-
(OCH2), 61.3 (CH, C-1); 23.9, 22.6, 21.9 and 21.5 (each CH2, C-
4ϪC-7), 14.4 (OCH2CH3). Ϫ IR (diethyl ether): ν˜ (%) ϭ 2067.6
Ϫ1
(5), 1935.9 (100), 1898.2 cm
(50) [ν(CϵO)]. Ϫ MS (70 eV), m/z
184W (%): 596 (5) [Mϩ], 484 (16) [Mϩ Ϫ 4 CO], 272 (72) [Mϩ
Ϫ
low crystals of compound 17a were collected by centrifugation after W(CO)5]. Ϫ C22H20O6SW (596.3): calcd. C 44.27, H 3.35; found C
24 h at Ϫ20 °C and washed with precooled n-pentane at Ϫ20 °C
(218 mg, 85%, Rf ϭ 0.7 in n-pentane/diethyl ether, 3:1, m.p. 72 °C).
Compound 17a is very unstable at 20 °C and therefore should be
stored below Ϫ30 °C. NMR spectra were recorded in CDCl3 at
Ϫ20 °C.
44.36, H 3.37.
Pentacarbonyl[3-ethoxy-1-(2-methoxyphenylthio)-4,5,6,7-tetrahydro-
1H-indene-S]tungsten (16c): Pentacarbonyl(3-cyclohexenyl-1-
ethoxy-2-propyn-1-ylidene)tungsten (1b) (243 mg, 0.50 mmol) was
treated with 2-methoxythiophenol (2c) (70 mg, 0.50 mmol) in the
presence of triethylamine as described above. Workup as described
above afforded compound 16c (250 mg, 80%, Rf ϭ 0.6 in n-pent-
ane/dichloromethane, 1:3, m.p. 64 °C).
Compound 17a: 1H NMR (360 MHz, 253 K, CDCl3): δ ϭ 7.45,
7.41 and 7.33 (each m, 2:2:1, Ph), 4.09 (m, 2 H, OCH2), 3.56 (s, 2
H, 2-H ), 2.58 and 2.43 (each ‘‘t’’, each 2 H, 4-H2 and 6-H2), 2.16
(m, 2 H, 5-H2), 1.33 (t, 3 H, OCH2CH3). Ϫ 13C NMR (360 MHz,
253 K, CDCl3): δ ϭ 200.8 and 197.2 [each Cq, trans- and cis-CO
of W(CO)5], 165.4 (Cq, C-1), 155.8 (Cq, C-3), 138.3 (Cq, i-C, Ph),
129.2, 129.0 and 128.6 (each CH, 2:2:1, Ph), 119.7 and 106.2 (each
Cq, C-3a and C-6a), 66.0 (OCH2), 47.3 (CH2, C-2); 29.9, 25.8 and
1
Compound 16c: H NMR (C6D6): δ ϭ 7.42 and 6.39 (each d, each
1 H, 3-H and 6-H of C6H4), 6.94 and 6.65 (each t, each 1 H, 4-H
and 5-H of C6H4), 5.13 (d, 1 H, 2-H), 4.56 (d, 1 H, 1-H), 3.84 and
3.67 (each m, each 1 H, diastereotopic OCH2), 3.35 (s, 3 H, OCH3),
2.13 (m, 1 H), 2.02 (m, 2 H), 1.67 (m,1 H), 1.37 (m, 4 H), 1.05 (t,
3 H, OCH2CH3). Ϫ 13C NMR (C6D6): δ ϭ 200.6 and 198.2 [each
Cq, trans- and cis-CO of W(CO)5], 163.8 (Cq, C-3), 158.1 (Cq, C-2
of C6H4), 139.7 and 139.2 (each Cq, C-3a and C-7a), 132.3 and
131.3 (each CH, C-4 and C-6 of C6H4), 123.9 (Cq, C-1 of C6H4),
121.1 and 111.6 (each CH, C-3 and C-5 of C6H4), 95.2 (CH, C-2),
65.4 (CH2, OCH2), 58.2 (CH, C-1), 55.4 (OCH3); 24.4, 22.8, 22.0
and 21.7 (each CH2, C-4ϪC-7), 14.4 (OCH2CH3). Ϫ IR (diethyl
25.7 (each CH2, C-4ϪC-6), 15.0 (OCH2CH3). Ϫ IR (diethyl ether):
Ϫ1
ν˜ (%) ϭ 2062.6 (5), 1934.6 (100), 1905.3 cm
(30) [ν(CϵO)]. Ϫ
MS (70 eV), m/z 184W (%): 582 (2) [Mϩ], 470 (8) [Mϩ Ϫ 4 CO],
258 (59) [Mϩ Ϫ W(CO)5], 229 (100) [Mϩ Ϫ W(CO)5 Ϫ Et].
ϪC21H18O6SW (582.3): calcd. C 43.30, H 3.09; found C 43.58, H
3.17.
X-ray Crystal Structure Analysis of Compound 17a: Formula
C21H18O6SW, M ϭ 582.26 gmolϪ1, 0.30 ϫ 0.30 ϫ 0.20 mm, a ϭ
3
˚
˚
Ϫ1
7.297(1), b ϭ 13.188(1), c ϭ 22.343(2) A, V ϭ 2150.1(4) A ,
Dcalcd. ϭ 1.799 gcmϪ3, µ ϭ 55.03 cmϪ1, empirical absorption cor-
rection by ψ scan data (0.289 Յ T Յ 0.406), Z ϭ 4, orthorhombic,
ether): ν˜ (%) ϭ 2062.8 (5), 1934.9 (100), 1905.8 (30) cm
[ν(CϵO)]. Ϫ MS (70 eV), m/z 184W (%): 626 (5) [Mϩ], 514 (27)
[Mϩ Ϫ 4 CO], 302 (28) [Mϩ Ϫ W(CO)5]. Ϫ C23H22O7SW (626.3):
calcd. C 44.07, H 3.51; found C 43.70, H 3.53.
˚
space group P212121 (No. 19), λ ϭ 0.71073 A, T ϭ 223(2) K, ω/2θ
scans, 2505 reflections collected (ϩh, ϩk, Ϫl), [(sinΘ)/λ]max ϭ 0.62
Ϫ1, 2505 independent reflections and 2263 observed reflections [I
3-Phenylthio-4,5,6,7,8,8a-hexahydro-3aH-azulen-1-one (13d): Penta-
carbonyl(3-cycloheptenyl-1-ethoxy-2-propyn-1-ylidene)tungsten
(1c) (250 mg, 0.50 mmol) was treated with thiophenol (2b) (55 mg,
0.50 mmol) in 2 mL of diethyl ether as described above. Chromato-
graphy of the mixture after 12 h at 20 °C with n-pentane/diethyl
ether (5:1) afforded a colourless fraction containing compound 13d
(72 mg, 56%, Rf ϭ 0.3 in n-pentane/diethyl ether, 5:1). If a solution
of thiophenol (2b) (55 mg, 0.50 mmol) in 2 mL of ethanol was ad-
ded to pentacarbonyl(3-cycloheptenyl-1-ethoxy-2-propyn-1-ylid-
ene)tungsten (1d) (250 mg, 0.50 mmol) at 20 °C, starting material
was consumed after a few minutes (TLC test) to give cyclopenten-
1-one 13d in 83% yield.
˚
A
Ն 2σ(I)], 263 refined parameters, R ϭ 0.031, Rw2 ϭ 0.101, max./
min. residual electron density ρ ϭ 0.94/Ϫ0.92 eAϪ3, Flack para-
˚
meter Ϫ0.02(3), hydrogen atoms calculated and riding.[15]
Pentacarbonyl(3-ethoxy-1-phenylthio-4,5,6,7-tetrahydro-1H-indene-
S)tungsten (16b): Pentacarbonyl(3-cyclohexenyl-1-ethoxy-2-pro-
pyn-1-ylidene)tungsten (1b) (243 mg, 0.50 mmol) was treated with
thiophenol (2b) (55 mg, 0.50 mmol) in the presence of triethylamine
as described above to give compound 16b (244 mg, 82%, Rf ϭ 0.8
in n-pentane/dichloromethane, 1:3, m.p. 69 °C).
1
Compound 16b: H NMR (360 MHz, CDCl3): δ ϭ 7.44 (‘‘d’’, 2 H,
Compound 13d: 1H NMR (C6D6): δ ϭ 7.28 (‘‘d‘‘, 2 H, o-H Ph),
o-H Ph), 6.96 (m, 3 H, m-H and p-H Ph), 5.02 (d, 1 H, 2-H), 3.93 7.00 (m, 3 H, m-H and p-H Ph), 5.63 (s, 1 H, 2-H), 2.90 and 2.44
(d, 1 H, 1-H), 3.78 and 3.61 (each m, each 1 H, diastereotopic (each m, each 1 H, 3a-H and 8a-H), 1.89 (m, 2 H), 1.68Ϫ1.16 (m,
OCH2), 2.17 (m, 1 H), 2.02 (m, 2 H), 1.79 (m, 1 H), 1.39 (m, 4 H),
8 H). Ϫ 13C NMR (C6D6): δ ϭ 204.2 (Cq, CϭO), 182.3 (Cq, C-3),
1.10 (t, 3 H, OCH2CH3). Ϫ 13C NMR (90 MHz, CDCl3): δ ϭ 200.1 134.8, 129.9 and 129.3 (each CH, 2:2:1, Ph), 130.0 (Cq, i-C, Ph),
and 197.6 [each Cq, trans- and cis-CO of W(CO)5], 164.1 (Cq, C-
3), 140.0 and 139.0 (each Cq, C-3a and C-7a), 134.5 (Cq, i-C, Ph);
132.2, 130.1 and 129.1 (each CH, 2:2:1, Ph), 94.4 (CH, C-2), 65.4 ether): ν˜ (%) ϭ 1698.6 cm
125.5 (CH, C-2), 52.6 and 49.2 (each CH, C-3a and C-8a); 31.3,
31.0, 28.2, 27.6 and 27.4 (each CH2, C-4ϪC-7). Ϫ IR (diethyl
Ϫ1
(70) [ν(CϭO)]. Ϫ MS (70 eV), m/z
Eur. J. Org. Chem. 2000, 3463Ϫ3473
3471

H.-P. Wu, R. Aumann, S. Venne-Dunker, P. Saarenketo
FULL PAPER
(%): 258 (100) [Mϩ]. Ϫ C16H18OS (258.4): calcd. C 74.38, H 7.02;
found C 74.11, H 7.10.
(s, 2 H, 2-H2), 1.81 (m, 1 H), 1.28 (m, 4 H). Ϫ 13C NMR (C6D6):
δ ϭ 203.6 (Cq, CϭO), 169.1 (Cq, C-3a), 159.2 (Cq, C-2 of C6H4),
141.4 (Cq, C-7a), 133.5 and 129.0 (each CH, C-6 and C-4 of C6H4),
123.3 (Cq, i-C of C6H4), 121.1 and 111.2 (each CH, C-3 and C-5
of C6H4), 55.2 (CH3O), 47.0 (CH, C-3), 44.3 (CH2, C-2); 26.6, 22.3,
21.6 and 20.6 (each CH2, C-4ϪC-7). Ϫ IR (hexane): ν˜ (%) ϭ
1703.1 cm Ϫ1 (70) [ν(CϭO)]. Ϫ MS (70 eV), m/z (%): 274 (70) [Mϩ].
Ϫ C16H18O2S (274.1): calcd. C 70.07, H 6.62; found C 70.33, H
6.74.
3-Phenylthio-3,4,5,6-tetrahydro-2H-pentalen-1-one (18a): To penta-
carbonyl(3-cyclopentenyl-1-ethoxy-2-propyn-1-ylidene)tungsten
(1a) (236 mg, 0.50 mmol) in 1 mL of hexane was added dropwise
with stirring at 20 °C a solution of thiophenol (2b) (55 mg,
0.50 mmol) and triethylamine (20 mg, 0.80 mmol) in 1 mL of n-
pentane. After the mixture was stirred for 4 h at 50 °C, the solvent
was removed and the residue was separated by chromatography on
silica gel (column 20 ϫ 2 cm) with n-pentane/diethyl ether, 4:1, to
give a colourless oil containing compounds 13a and 18a (48 mg,
42%, 18a:13a ϭ 5:2, Rf ϭ 0.4 in n-pentane/diethyl ether, 2:1).
Crystallographic data (excluding structure factors) for the struc-
tures reported in this paper have been deposited with the Cam-
bridge Crystallographic Data Centre as supplementary publication
CCDC-142494 (15a), -142495 (17a), and -142496 (3b). Copies of
the data can be obtained free of charge on application to CCDC,
12 Union Road, CambridgeCB2 1EZ, UK [Fax: (internat.) ϩ 44-
1223/336-033, E-mail: deposit@ccdc.cam.ac.uk].
Compound 13a: See above.
Acknowledgments
This work was supported by the Deutsche Forschungsgemeinschaft
and the Fonds der Chemischen Industrie. P. S. thanks the Finnish
Academy for financial support.
1
Compound 18a: H NMR (C6D6): δ ϭ 7.21 (m, 2 H, o-H Ph), 6.97
(m, 3 H, m-H and p-H Ph), 3.67 (d, 1 H, 3-H), 2.75 (m, 1 H), 2.28
(m, 1 H), 2.07 (d, 2 H, 2-H2), 2.02Ϫ1.74 (m, 3 H), 1.28 (m, 1 H).
[1]
Ϫ
13C NMR (C6D6): δ ϭ 197.7 (Cq, CϭO), 181.9 (Cq, C-3a), 151.2
H.-P. Wu, R. Aumann, R. Fröhlich, E- Wegelius, P. Saarenketo,
Organometallics 2000, 19, 2373Ϫ2381.
(Cq, C-6a), 134.7 (Cq, i-C, Ph); 131.9, 129.2 and 127.5 (each CH,
2:2:1, Ph), 49.6 (CH, C-3), 43.2 (CH2, C-2), 30.2, 27.5 and 25.0
[2]
For a recent review on (1-alkynyl)carbene complexes see: R.
Aumann, H. Nienaber, Adv. Organomet. Chem. 1997, 41,
Ϫ1
(each CH2, C-4ϪC-6). Ϫ IR (hexane): ν˜ (%) ϭ 1708.5 cm
(70)
163Ϫ242.
[ν(CϭO)]. Ϫ MS (70 eV), m/z (%): 230 (100) [Mϩ], 121 (80) [Mϩ
Ϫ SPh]. Ϫ C14H14OS (230.3): calcd. C 73.02, H 6.13; found C
72.75, H 6.54.
[3]
For a recent review on the preparation of five-membered car-
bocyclic rings from Fischer carbene complexes see: J. W.
Herndon, Tetrahedron 2000, 56, 1257Ϫ1280.
[4]
[4a]
For the basics of this reaction type see: Ϫ
R. Aumann, H.
Heinen, P. Hinterding, N. Sträter, B. Krebs, Chem. Ber. 1991,
3-Phenylthio-2,3,4,5,6,7-hexahydro-inden-1-one (18b): Pentacar-
bonyl(3-cyclohexenyl-1-ethoxy-2-propyn-1-ylidene)tungsten (1b)
(243 mg, 0.50 mmol) was treated with thiophenol (2b) (55 mg,
0.50 mmol) in 2 mL of n-pentane in the presence of triethylamine.
Workup as described above afforded a polar, colourless oil con-
taining compound 18b (47 mg, 39%, Rf ϭ 0.6 in n-pentane/diethyl
ether, 2:1).
[4b]
124, 1229. Ϫ
See ref.[7]
[5]
[6]
For a recent review on 1-metalla-1,3,5-hexatrienes and related
compounds see: R. Aumann, Eur. J. Org. Chem. 2000, 17Ϫ31.
For related studies, in which 1-metalla-1,3,5-trienes were pro-
duced by addition of dienes to (1-alkynyl)carbene complexes,
´
see: J. Barluenga, F. Aznar, S. Barluenga, M. Fernandez, A.
´
´
´
Martın, S. Garcıa-Granda, A. Pinera-Nicolas, Chem. Eur. J.
1998, 4, 2280Ϫ2298.
[7]
[8]
R. Aumann, R. Fröhlich, Organometallics 1999, 18,
1369Ϫ1380.
H. Wu, R. Aumann, R. Fröhlich, Eur. J. Org. Chem. 2000,
19, 1183Ϫ1192.
For related transformations see: J. Barluenga, F. Aznar, M. A.
Palomero, S. Barluenga, Org. Lett. 1999, 4, 541Ϫ543.
For a review on rearrangement reactions of thiols see: T. Sher-
adsky, in The Chemistry of the Thiol Group (Ed.: S. Patai), J.
Wiley and Sons, New York, 1974, p. 702Ϫ716.
For a recent review on the thio Claisen rearrangement of allyl
[9]
[10]
Compound 18b: 1H NMR (C6D6): δ ϭ 7.21 (m, 2 H, o-H Ph), 6.97
(m, 3 H, p- and m-H Ph), 3.63 (d, 1 H, 3-H), 2.50 (m, 3 H), 2.00
(d, 2 H, 2-H2), 1.77 (m, 1 H), 1.30 (m, 4 H). Ϫ 13C NMR (C6D6):
δ ϭ 203.0 (Cq, CϭO), 168.6 (Cq, C-3a), 141.4 (Cq, C-7a), 134.2
(Cq, i-C, Ph); 132.5, 129.1 and 127.6 (each CH, 2:2:1, Ph), 48.2
(CH, C-3), 43.8 (CH2, C-2); 26.4, 22.3, 21.6 and 20.5 (each CH2,
C-4ϪC-7). Ϫ IR (hexane): ν˜ (%) ϭ 1705.6 cm Ϫ1 (70) [ν(CϭO)]. Ϫ
MS (70 eV), m/z (%): 244 (90) [Mϩ]. Ϫ C15H16OS (244.3): calcd. C
73.73, H 6.60; found C 73.64, H 6.53.
[11]
[11a]
vinyl sulfide and its application to organic synthesis, see:
P. Metzner, in Topics in Current Chemistry (Ed. P.C. B. Page),
Springer-Verlag, Berlin, Heidelberg, 1999, vol. 204, p.
[11b]
153Ϫ158. Ϫ
P. Beslin, B. Lelong, Tetrahedron 1997, 53,
17253Ϫ17264. Ϫ [11c] P. N. Devine, A. I. Meyers, J. Am. Chem.
Soc. 1994, 116, 2633Ϫ2634. Ϫ [11d] P. Metzner, Synthesis 1992,
[11e]
1185Ϫ1199. Ϫ
K. Oshima, H. Takahashi, H. Yamamoto,
[11f]
H. Nozaki, J. Am. Chem. Soc. 1973, 95, 2693Ϫ2694. Ϫ
I.
Ojima, K. Kondo, Bull. Chem. Soc. Jpn. 1973, 46, 1539Ϫ1545.
[11g]
Ϫ
J. N. Harvey, H. G. Viehe, J. Chem. Soc., Chem. Com-
3-(2-Methoxyphenylthio)-2,3,4,5,6,7-hexahydroinden-1-one
(18c):
mun. 1995, 2345Ϫ2346.
Pentacarbonyl(3-cyclohexenyl-1-ethoxy-2-propyn-1-ylidene)-
tungsten (1b) (243 mg, 0.50 mmol) was treated with thiophenol (2c)
(70 mg, 0.50 mmol) in 2 mL of n-pentane in the presence of triethy-
lamine as described above to give the polar compound 18c (62 mg,
[12] [12a]
J. D. Winler, K. E. Henegar, J. Am. Chem. Soc. 1987, 109,
2850Ϫ2851. Ϫ [12b] K. B. Wiberg, J. J. Aringi, M. G. Mattorro,
J. Am. Chem. Soc. 1990, 112, 5854Ϫ5861.
[13] [13a]
Y. Tobe, T. Hoshino, Y. Kawakami, Y. Sakai, K. Kimura,
[13b]
1
Y. Odaira, J. Org. Chem. 1978, 43, 4334Ϫ4337. Ϫ
E. A.
45%, Rf ϭ 0.7 in n-pentane/diethyl ether, 2:1, colourless oil]. Ϫ H
[13c]
Eugene, K. A. Nelson, Tetrahedron 1987, 43, 679Ϫ692. Ϫ
J. Cossy, S. Bouzbouz, Tetrahedron Lett. 1997, 38, 1931Ϫ1932.
NMR (C6D6): δ ϭ 7.27 and 6.47 (each ‘‘d’’, each 1 H, 3-H and 6-
H of C6H4), 7.02 and 6.75 (each ‘‘t’’, each 1 H, 4-H and 5-H of
C6H4), 3.85 (d, 1 H, 3-H), 3.32 (s, 3 H, OCH3), 2.50 (m, 3 H), 2.04
Ϫ
[13d] C. J. Carmelo, N. K. Dunlap, A. B. Smith, J. Org. Chem.
1987, 52, 5280Ϫ5283.
3472
Eur. J. Org. Chem. 2000, 3463Ϫ3473

Organic Syntheses via Transition Metal Complexes, CV
FULL PAPER
[14]
J. K. Whitesell, R. S. Matthews, J. Org. Chem. 1977, 42,
data SORTAV (R. H. Blessing, Acta Crystallogr. 1995, A51,
33Ϫ37; R. H. Blessing, J. Appl. Crystallogr. 1997, 30,
421Ϫ426); structure solution SHELXS-97 (G. M. Sheldrick,
Acta Crystallogr. 1990, A46, 467Ϫ473); structure refinement
SHELXL-97 (G. M. Sheldrick, Universität Göttingen, 1997);
graphics SCHAKAL (E. Keller, Universität Freiburg, 1997).
Received April 6, 2000
3878Ϫ3882.
[15]
Data sets were collected with Nonius MACH3 and
KappaCCD diffractometers, equipped with a rotating anode
generator Nonius FR591. Programs used: data collection: EX-
PRESS (Nonius B.V., 1994) and COLLECT (Nonius B.V.,
1998); data reduction: MolEN (K. Fair, EnrafϪNonius B.V.,
1990) and DenzoϪSMN (Z. Otwinowski, W. Minor, Methods
Enzymol. 1997, 276, 307Ϫ326); absorption correction for CCD
[O00175]
Eur. J. Org. Chem. 2000, 3463Ϫ3473
3473