Stereocontrolled synthesis of angularly fused tricyclic ring systems by means of 1-metalla-1,3,5-hexatrienes (M = Cr, W)

Article abstract of DOI:10.1002/1521-3765(20020215)8:4<910::AID-CHEM910>3.0.CO;2-T

An efficient pathway for the stereocontrolled synthesis of functionalized, angularly fused tricyclic ring systems from readily available (1-alkynyl)-carbene complexes [(OC)₅M=C(OEt)C≡CR] (M = Cr, W; R = Ph, c-C₆H₉) is described. The synthesis involves the formation of a 1-metalla-1,3,5-hexatriene from the (1-alkynyl)carbene tungsten complex [(OC)₅W=C(OEt)C≡Cc-C₆H₉] and a secondary amine, and its thermally induced π-cyclization to a tetrahydroindene, which undergoes a spontaneous isomerization to another tetrahydroindene. Condensation of these tetrahydroindenes with pyran-2-ylidene complexes derived from (1-alkynyl)carbene complexes [(OC)₅M=C(OEt)C≡CPh] (M = Cr, W) proceeds smoothly giving angularly fused tricyclic ring systems, rearrangement of which may generate spiro(cyclopentane-1,1-indanes) as side products. The synthesis is highly versatile and can be applied to the formation of various ring systems, such as steroid-type ring skeletons.

Full text of DOI:10.1002/1521-3765(20020215)8:4<910::AID-CHEM910>3.0.CO;2-T

FULL PAPER
Stereocontrolled Synthesis of Angularly Fused Tricyclic Ring Systems by
Means of 1-Metalla-1,3,5-hexatrienes (M ˆ Cr, W)**
‡
He-Ping Wu, Rudolf Aumann,* Roland Frˆhlich, and Birgit Wibbeling[a]
ˆ
Abstract: An efficient pathway for the
stereocontrolled synthesis of functional-
ized, angularly fused tricyclic ring sys-
tems from readily available (1-alkynyl)-
thermally induced p-cyclization to a
tetrahydroindene, which undergoes a
spontaneous isomerization to another
tetrahydroindene. Condensation of
these tetrahydroindenes with pyran-2-
ylidene complexes derived from (1-al-
kynyl)carbene complexes [(OC)5M C-
ꢀ
(OEt)C CPh] (M ˆ Cr, W) proceeds
smoothly giving angularly fused tricyclic
ring systems, rearrangement of which
may generate spiro(cyclopentane-1,1-in-
danes) as side products. The synthesis is
highly versatile and can be applied to the
formation of various ring systems, such
as steroid-type ring skeletons.
ˆ
carbene complexes [(OC)5M C(OEt)-
ꢀ
C CR] (M ˆ Cr, W; R ˆ Ph, c-C6H9) is
described. The synthesis involves the
formation of
a 1-metalla-1,3,5-hexa-
Keywords: annulation
¥
carbene
triene from the (1-alkynyl)carbene tung-
ligands ¥ cycloaddition ¥ steroids ¥
tungsten
ˆ
ꢀ
sten complex [(OC)5W C(OEt)C C-
c-C6H9] and a secondary amine, and its
suited to the generation of highly reactive bicyclic cyclo-
pentadienes, such as tetrahydropentalenes[7, 8] or tetrahydroin-
denes.[8, 9] Additionally, it was found that pyran-2-ylidene
complexes, which are generated by condensation of (1-
alkynyl)carbene complexes with a-CH acidic carbonyl com-
pounds, undergo a cyclohexadiene annelation to electron-rich
alkene groups even under very mild conditions.[14] Keeping
these reactions in mind, we investigated the condensation of
pyran-2-ylidene complexes with tetrahydroindenes as a means
of generating angularly fused tricyclic ring systems.
Introduction
New strategies for the synthesis of angularly fused tricyclic
systems have gained considerable prominence recently as
these frameworks exist in many naturally occurring com-
pounds.[1] We became interested in employing 1-metalla-1,3,5-
hexatrienes for the construction of angularly fused
tri- and polycyclic ring systems. Earlier, we reported
on the application of (1-alkynyl)carbene complexes
ˆ
ꢀ
[(CO)5M C(OEt)C CR] (M ˆ W, Cr ; R ˆ aryl, alkenyl) as
stoichiometric reagents in high-yielding transformations of
potential use in organic synthesis.[2] Prominent examples
involve the formation of cyclopentadienes through the p-
cyclization of 1-metalla-1,3,5-hexatrienes,[3, 4] derived from (1-
alkynyl)carbene complexes, for example, by addition of
enamines[5] or various protic nucleophiles NuH (such as
Results and Discussion
Angularly fused tricyclic ring systems: Reaction of the (1-
alkynyl)carbene tungsten complex 1 with a secondary amine
2a 2d and a pyran-2-ylidene complex 3a or 3b affords
angularly fused tricyclic ring systems 4 [Eq. (1); for substitu-
ents and reaction conditions see Tables 1 and 2].
R(R'CO)CH2,[6] R2NH,[7, 8] R2PH,[7] RC( O)OH and
ˆ
ROH,[9, 10] RC( X)SH (X ˆ O, NH, NR),
and
[11]
ˆ
RSH[12]).[7, 13] The latter procedure was shown to be well
The reaction pathway (Scheme 1) involves addition of 2 to 1
to give a 1-tungsta-1,3,5-hexatriene 5, which undergoes p-
‡
[a] Prof. Dr. R. Aumann, Dr. H.-P. Wu, Dr. R. Frˆhlich, B. Wibbeling
cyclization to a tetrahydroindene tungsten complex 6.[4, 7]
A
Organisch-Chemisches Institut der Universit‰t M¸nster
Corrensstrasse 40, 48149 M¸nster (Germany)
Fax : (‡49)251-833-6502
tetrahydroindene 8 is obtained from 6 by ligand disengage-
ment with pyridine.[15] Tetrahydroindenes 8 have indeed been
trapped by cycloaddition reactions[15] as well as by rearrange-
ments.[8] They are notoriously unstable and readily undergo
isomerization to tetrahydroindenes 7 by 1,5-hydrogen migra-
tion.[15] It was shown by NMR spectroscopy that, for example,
E-mail: aumannr@uni-muenster.de
‡
[ ] Crystal structure analysis.
[**] Organic Synthesis via Transition-Metal Complexes, Part 114. For
Part 113 see: H.-P. Wu, R. Aumann, R. Frˆhlich, B. Wibbeling, and O.
Kataeva, Chem. Eur. J. 2001, 7, 5084.
910
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Chem. Eur. J. 2002, 8, No. 4

910 916
the tetrahydroindene 7a thus obtained reacts
smoothly with pyran-2-ylidene tungsten 3a to
give an angularly fused cyclohexadiene annela-
tion product 9a, even at 208C. The reaction
involves a [4‡2] cycloaddition of the pyranyli-
dene unit to the enol ether unit and the
subsequent elimination of M(CO)6 by a retro-
Fischer reaction.[14b, 16] The dienophilic character
of the enol portion of the 1-amino-3-alkoxybu-
tadiene unit of 7a is enhanced by p conjugation
with an enamine moiety. Compound 9a was
detected as a transient intermediate and charac-
terized by NMR spectroscopy. It was found to
eliminate ethanol spontaneously, supposedly to
give an intermediate 10a, from which 4a is
derived by deprotection. Compound 4a was
isolated by chromatography on basic alumina,
without decomposition. Thermolysis of 4a re-
sults in smooth rearrangement by a 1,2-carbon
migration and aromatization to give the spiro
compound 12a. Compound 4a is the only
product if 7a is generated and subsequently
reacts with 3a or 3b at 208C; however, 12a may
be obtained as a side product in varying amounts
Table 1. Compounds 2 and 3.
Scheme 1. Reaction pathway leading to compounds 4.
Compound
NR2
M
2a
2b
2c
2d
2e
3a
3b
NMe2
depending on the amino component and also on the reaction
conditions (Scheme 1).
morpholino
piperidino
pyrrolidino
(2S)-MMP[a]
Compound 4e could be obtained with stereoinduction
under the influence of (2S)-(2-methoxymethylene)pyrroli-
dine. The diastereomers (1S,9S)-4e and (1R,9R)-4e were
formed in a ratio of 4:1 [Eq. (2)]. This ratio corresponds to the
4:1 diastereomeric ratio of 7e under equilibrium conditions.[15]
W
Cr
[a] (2S)-(À)2-(Methoxymethylene)pyrrolidino.
Table 2. Compounds 4 10, reaction conditions, and yields [see Eq. (1) and
Scheme 1].
4
10
M
Conditions[a]
NR2
4/12/11[b]
11[c]
a
a
a
b
b
c
c
d
e
W
W
Cr
W
W
W
W
W
W
A
B
B
A
B
A
B
B
B
NMe2
NMe2
NMe2
morpholino
morpholino
piperidino
piperidino
pyrrolidino
(2S)-MMP[d]
54/27/0
83/0/0
75/0/0
0/63/13
64/14/7
28/56/0
81/0/0
86/0/0
84/0/0
35
65
Compounds 4, 9, 11, and 12 were characterized spectro-
scopically on the basis of DEPT, COSY, HMQC, and HMBC
experiments, and 4a also by a crystal structure analysis
(Figure 1). The bond lengths and bond angles are in line with
expectation.
[a] A: compounds
5 were heated with compounds 3 to 658C; B:
tetrahydroindenes 7 were generated at 658C and compounds 3 were added
subsequently. [b] Chemical yields [%] of products isolated by chromatog-
raphy on basic alumina. [c] Isolated by chromatography on silica gel.
[d] (2S)-MMP ˆ (2S)-(2-methoxymethylene)pyrrolidino.
Chem. Eur. J. 2002, 8, No. 4
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911

R. Aumann et al.
FULL PAPER
Steroid-related angularly fused ring systems: The procedure
for generation of angularly fused ring systems requires readily
available starting components. The synthesis is highly versa-
tile and can be applied to the formation of various ring
systems. For example, a hydrobenzo[14,15]-14b-19-norste-
roid[17] skeleton 14 was easily obtained by reaction of 9,10-
dihydro-2H-benzo[d]chromen-2-ylidene complexes 13[14b]
with tetrahydroindenes 7 [Eq. (3) for substituents and reac-
tion conditions, see Table 3]. The reactions at 208C of 7b with
Table 3. Compounds 14 18, conditions and yields [see Eq. (3) and
Scheme 2].
14 18
NR2
Conditions[a]
14/18
17
[b]
a
b
b
NMe2
morpholine
morpholine
B
B
A
Figure 1. Molecular structure of 4a. Selected bond lengths [ä] and angles
76/0[c]
21/62[c]
o
À
À
À
À
[ ]: C1 C2 1.478(3), C1 C13 1.513(3), C2 C3 1.373(3), C3 C4 1.447(3),
58[d]
À
À
À
À
C4 C5 1.355(3), C5 C6 1.418(3), C5 C13 1.518(3), C6 C7 1.368(3),
À
À
À
À
C7 N18 1.364(3), C7 C8 1.518(3), C8 C9 1.538(3), C8 C13 1.557(3),
[a] A: compounds
5
were heated with compounds
3
to 658C; B:
À
À
À
À
C9 C10 1.520(3), C10 C11 1.514(4), C11 C12 1.516(3), C12 C13 1.563(3);
C2-C1-C13 114.31(18), C3-C2-C1 118.9(2), C2-C3-C4 120.7(2), C5-C4-C3
120.3(2), C4-C5-C6 132.2(2), C4-C5-C13 120.0(2), C6-C5-C13 107.8(2), C7-
C6-C5 110.4(2), N18-C7-C6 126.5(2), N18-C7-C8 122.3(2), C6-C7-C8
111.2(2), C7-C8-C9 118.6(2), C7-C8-C13 101.8(2), C9-C8-C13 115.3(2),
C10-C9-C8 115.6(2), C11-C10-C9 110.6(2), C10-C11-C12 109.0(2), C11-
C12-C13 112.9(2), C1-C13-C5 110.2(2), C1-C13-C8 117.4(2), C5-C13-C8
103.42(2), C1-C13-C12 108.9(2), C5-C13-C12 105.6(2), C8-C13-C12
110.7(2).
tetrahydroindene 7 was formed at 658C and reacted subsequently with
compounds 3. [b] A 1:1 ratio of 14a and [W(pyridine)(CO)5] was observed
in the NMR spectra. [c] Chemical yields [%] of products isolated by
chromatography on basic alumina. [d] Isolated by chromatography on silica
gel.
ˆ
ꢀ
13, readily generated from [(OC)5M C(OEt)C CPh] (M ˆ
Cr, W) and 2-tetralone, produced 14b, which could be isolated
as crystals because of its poor solubility. Reaction of 5b with
the pyran-2-ylidene complex 13 and
pyridine at 658C provides a 1:3 mix-
ture of 14b and 18b. Attempts to
isolate 18b by chromatography on
silica gel resulted in formation of the
ketone 17 (Scheme 2).
Compounds 14, 17, and 18 were
characterized by 1H and 13C NMR
spectra on the basis of DEPT, COSY,
HMQC, and HMBC experiments. The
structure of 17 was confirmed by
crystal structure analysis (Figure 2).
Conclusion
The reaction of 1 with 2 and 3 provides
an efficient entry to the generation of
angularly fused tricyclic ring systems 4
from readily available starting compo-
nents. It has also been applied suc-
cessfully to the synthesis of, for exam-
ple, a hydrobenzo[14,15]-14b-19-nor-
steroid skeleton 14 from 1 and 13.
Scheme 2. Diastereoselectivity of the formation of 4e induced by (2S)-(2-methoxymethylene)pyrroli-
dine ((2S)-MMP; 2e).
912
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Chem. Eur. J. 2002, 8, No. 4

Synthesis of Fused-Ring Systems
910 916
spectroscopy in [D8]toluene immediately after addition of 3a to 7a at 08C
showed signals of 4a and 9a in a ratio of approximately 1:1 as the only
detectable products besides [W(pyridine)(CO)5]. Compound 4a was
purified by fast chromatography on basic alumina (column 2 Â 15 cm).
Elution with n-pentane/dichloromethane (3:1) gave yellow [W(pyridine)-
(CO)5]. Subsequent elution with diethyl ether/dichloromethane (1:1)
afforded 4a (143 mg, 83%, m.p. 1158C). Compound 9a was not stable
under the chromatographic conditions. Reaction of 7a with 3b as described
above gave a 1:1 mixture of 4a (total yield approximately 75%) and
pentacarbonyl(pyridine)chromium, but, according to the 1H NMR spec-
trum, no other products. Reaction of (3E)-5a (266 mg, 0.50 mmol) with 3a
(268 mg, 0.50 mmol) and pyridine (40 mg, 0.50 mmol) in toluene (2 mL) in
a 2 mL screwtop vessel at 658C for 2.5 h gave a 2:1 mixture of 4a and 12a
(140 mg, 81%, 4a/12a ˆ 2:1) together with pentacarbonyl(pyridine)tungs-
ten. The compounds could be separated by chromatography on alumina
(column 2 Â 10 cm), but chromatography on silica gel with n-pentane/
dichloromethane (2:1) gave 11 {55 mg, 35%, Rf ˆ 0.5 in n-pentane/
dichloromethane (2:1), m.p. 1598C) by hydrolysis of 12a.
Data for 4a: 1H NMR (400 MHz,
C6D6): d ˆ 7.36 and 7.15 (m, 2:3H;
C6H5), 5.74 (s, 1H; 5-H), 5.54 and
ˆ
5.23 (s, each 1H; CH2), 5.22 (s, 1H;
7-H), 2.71 (m, 1H; 9-H), 2.43 (s, 6H;
N(CH3)2), 1.90 (s, 3H; COCH3), 1.87
and 1.70 (m, each 1H), 1.85 and 1.24
(m, each 1H), 1.48 and 1.18 (m, 2H),
Figure 2. Molecular structure of the steroid-related compound 17. Selected
o
À
À
À
bond lengths [ä] and angles [ ]: C1 C2 1.533(2), C1 C5 1.564(2), C2 C3
À
À
À
À
1.515(3), C3 C4 1.529(2), C4 C5 1.562(2), C5 C21 1.520(2), C5 C6 1.5352,
À
À
À
À
C6 O1 1.207(2), C6 C7 1.513(2), C7 C8 1.505(2), C8 C9 1.380(2),
C8 C21 1.401(2), C9 C10 1.393(2), C10 C11 1.417(2), C11 C20 1.417(2),
C11 C12 1.493(2), C12 C17 1.408(2), C17 C18 1.506(2), C18 C19
1.40 and 1.25 (m, each 1H) (10-CH2 to
À
À
À
À
13
ˆ
13-CH2); C NMR (400 Hz, C6D6): d ˆ 204.7 (Cq, C O), 167.0 (Cq, C8),
À
À
À
À
161.4 (Cq, C6), 148.6, 142.3, 139.6, and 129.2 (Cq, Ci, C2 C4), 128.7, 128.6,
À
À
1.530(2), C19 C20 1.513(2), C20 C21 1.395(2); C2-C1-C5 106.3(1), C3-
C2-C1 104.7(1), C2-C3-C4 103.2(1), C3-C4-C5 104.3(1), C21-C5-C6
102.2(1), C21-C5-C4 114.7(1), C6-C5-C4 106.3(1), C21-C5-C1 117.8(1),
C6-C5-C1 111.0(1), C4-C5-C1 104.5(1), O1-C6-C7 124.8(1), O1-C6-C5,
125.1(1), C7-C6-C5 110.1(1), C8-C7-C6 103.4(1), C9-C8-C21 120.6(1), C9-
C8-C7 128.1(1), C21-C8-C7 111.3(1), C8-C9-C10 120.7(1), C9-C10-C11
119.5(1), C10-C11-C20 119.4(1), C10-C11-C12 123.4(1), C20-C11-C12
117.3(1), C17-C12-C11 118.5(1), C12-C17-C18 117.9(1), C17-C18-C19
109.4(1), C20-C19-C18 109.8(1), C21-C20-C11 119.5(1). C21-C20-C19
122.6(1), C11-C20-C19 117.9(1), C20-C21-C8 120.0(1), C20-C21-C5
128.8(1), C8-C21-C5 111.2(1).
ˆ
and 127.8 (CH, 2:2:1, C6H5), 110.7 ( CH2), 106.6 (CH, C5), 102.9 (CH, C7),
49.0 (Cq, C1), 47.5 (CH, C9), 40.9 (N(CH3)2), 31.9 (COCH3), 35.4, 24.3, 22.9,
and 18.6 (CH2, C10 C13); IR (KBr): nÄ ˆ 1699.0 cmÀ1 (100) (C O); MS
ˆ
‡
‡
(70 eV): m/z (%): 345 (100) [M] , 302 (95) [M À 43] ; elemental analysis
calcd (%) for C24H27NO(345.2): C 83.44, H 7.88, N 4.05; found: C 82.96, H
7.72, N 3.79; X-ray crystal structure analysis: formula C24H27NO, M ˆ
345.47, red crystals 0.25  0.20  0.05 mm, a ˆ 13.326(4), b ˆ 8.634(2), c ˆ
16.719(4) ä, b ˆ 98.59(2)8, Vˆ 1902.1(9) ä3, 1calcd ˆ 1.206 gcmÀ3
,
m ˆ
5.58 cmÀ1, empirical absorption correction from y scan data (0.873 ꢁ Tꢁ
0.973), Z ˆ 4, monoclinic, space group P21/c (No. 14), l ˆ 1.54178 ä, Tˆ
223 K, w/2q scans, 4013 reflections collected (Æh, ‡ k, ‡ l), [(sinq)/l] ˆ
0.62 äÀ1, 3878 independent (Rint ˆ 0.035) and 2507 observed reflections
[I ꢂ 2s(I)], 239 refined parameters, R ˆ 0.053, wR2 ˆ 0.146, max/min
residual electron density 0.28/ À 0.24 eäÀ3, hydrogen atoms calculated
and refined as riding atoms.[18]
Experimental Section
Data for 12a: 1H NMR (C6D6): d ˆ
7.45 and 7.12 (m, 2:3H; C6H5), 6.92 (s,
1H; 4-H), 5.26 (s, 1H; 3-H), 2.49 (s,
6H; N(CH3)2), 2.32 (s, 3H; 7-CH3),
2.28 1.85 (m, 8H; 2'-CH2 to 5'-CH2),
1.87 (s, 3H; COCH3); 13C NMR
All operations were carried out under an argon atmosphere. All solvents
were dried and distilled before use. All 1H and 13C NMR spectra were
routinely recorded on Bruker ARX300 and AM360 instruments. COSY,
HMQC, HMBC, and NOE experiments were performed on Varian 400 or
600 Hz instruments. IR spectra were recorded on a Biorad Digilab
Division FTS-45 FT-IR spectrophotometer. Elemental analyses were
determined on a Perkin Elmer 240 Elemental Analyzer. Analytical
TLC plates, Merck DC-Alufolien Kieselgel 60F240, were viewed by UV
light (254 nm) and stained with iodine. Rf values refer to TLC tests.
Pentacarbonyl(3-cyclohexenyl-1-ethoxy-2-propyn-1-ylidene)tungsten (1)
was prepared according to reference [7]. Pentacarbonyl(5-acetyl-6-meth-
yl-4-phenyl-2H-pyran-2-ylidene)tungsten (3a), -chromium (3b), and pen-
tacarbonyl(4-phenyl-9,10-dihydro-2H-benzo[d]chromen-2-ylidene)tung-
sten (13) were prepared according to reference [16].
ˆ
(C6D6): d ˆ 207.0 (Cq, C O), 167.4
(Cq, C2), 148.5, 145.7, 142.6, 138.2,
136.7, and 127.3 (Cq; Ci, C3a, C7a,
C5 C7), 129.4, 128.6, and 127.8 (CH,
2:2:1, C6H5), 117.1 (CH, C4), 100.4 (CH, C3), 60.9 (Cq, C1), 41.8 (N(CH3)2),
32.9 (COCH3), 34.4 and 28.1 (2CH2, C2' C5'), 16.1 (7-CH3).
Data for 9a: 1H NMR (400 MHz,
C6D6): d ˆ 7.32 and 7.10 (m, 2:3H;
C6H5), 5.97 (s, 1H; 5-H), 4.16 (s, 1H;
7-H), 3.58 and 3.40 (m, each 1H;
diastereotopic 6-OCH2), 2.75 (dd,
1H; 9-H), 2.45 (s, 6H; N(CH3)2), 1.90
(s, 3H; 2-CH3), 2.04 and 1.54 (m, each
1H), 2.03 and 1.22 (m, each 1H), 1.95
(m, 2H), 1.88 and 1.70 (m, each 1H)
3-Acetyl-8-dimethylamino-2-methylene-4-phenyltricyclo[7.4.0.01,6]deca-
3,5,7-triene (4a), 3-acetyl-8-dimethylamino-6-ethoxy-2-methyl-4-phenyl-
tricyclo[7.4.0.01,6]deca-2,4,7-triene (9a), 6-acetyl-2-dimethylamino-7-meth-
yl-5-phenylspiro(cyclopentane-1,1-indane) (12a), and 6-acetyl-7-methyl-5-
phenylspiro[cyclopentane-1,1-indan]-2-one (11): Dimethylamine (2a)
(23 mg, 0.50 mmol) in toluene (1 mL) at 08C [corresponding to 1/10 of a
solution of dimethylamine (230 mg) in toluene (10 mL)] was added
dropwise to 1 (243 mg, 0.50 mmol) in toluene (1 mL) in a 2 mL screwtop
vessel. The point of equivalence was indicated by a color change from
brown to yellow. Pyridine (40 mg, 0.50 mmol) was added, and the solution
was stirred at 658C for 2 h to give the tetrahydroindene derivative 7a.
Addition of 3a (268 mg, 0.50 mmol) at 208C led to precipitation of most of
the [W(CO)6], which was removed after 30 min by centrifugation. 1H NMR
(10-CH2 to 13-CH2), 1.60 (s, 3H; COCH3), 1.14 (t, 3H; OCH2CH3), 0.87 (t,
13
ˆ
3H; OCH CH3); C NMR (400 MHz, C6D6): d ˆ 205.3 (Cq, C O), 162.1
2
(Cq, C8), 144.1, 142.1, 135.4, and 132.9 (Cq, Ci, C2 C4), 128.5, 127.8, and
127.3 (CH, 2:2:1, C6H5), 128.5 (CH, C5), 92.2 (CH, C7), 89.8 (Cq, C6), 56.4
(6-OCH2), 52.8 (Cq, C1), 45.7 (CH, C9), 39.7 (N(CH3)2), 31.1 (COCH3),
30.0, 26.5, 25.2, and 24.9 (CH2, C10 C13), 16.1 (OCH2CH3), 15.6 (2-CH3).
Chem. Eur. J. 2002, 8, No. 4
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913

R. Aumann et al.
FULL PAPER
Data for 11: 1H NMR (400 MHz,
C6D6): d ˆ 7.36, 7.16, and 7.11 (m,
2:2:1H; C6H5), 6.75 (s, 1H; 4-H),
3.20 (s, 2H; 3-CH2), 2.14 (s, 3H;
7-CH3), 1.95 and 1.67 (m, each 4H;
2'-CH2 to 5'-CH2), 1.79 (s, 3H;
COCH3); 13C NMR (C6D6): d ˆ 218.7
(Cq, C2), 206.1 (Cq, COCH3); 144.8,
143.0, 140.9, 137.5, and 129.7 (Cq,
Data for 4c: 1H NMR (C6D6): d ˆ 7.39 and 7.11 (m, 2:3H; C6H5), 5.83 (s,
ˆ
1H; 5-H), 5.61 and 5.32 (s, each 1H; CH2), 5.28 (s, 1H; 7-H), 2.70 (m, 1H;
9-H), 2.80 and 2.63 (m, each 2H; 2NCH2), 1.91 (s, 3H; COCH3); 1.85 (m,
2H), 1.67 (m, 1H), 1.51 (m, 2H), 1.32 (m, 9H) (10-CH2 to 13-CH2, 3CH2
13
ˆ
piperidino); C NMR (C6D6): d ˆ 204.6 (Cq, C O), 166.5 (Cq, C8), 160.9
(Cq, C6), 148.5, 142.2, 138.9, and 129.6 (Cq, Ci, C2 C4), 128.9, 128.6, and
ˆ
127.8 (CH, 2:2:1, C6H5), 111.4 ( CH2), 107.6 (CH, C5), 104.0 (CH, C7), 50.5
(2NCH2), 48.5 (Cq, C1), 47.2 (CH, C9), 31.9 (COCH3), 35.0, 24.5, 23.4, and
18.7 (CH2, C10 C13), 25.6 and 24.3 (2:1CH2, 3CH2 piperidino); IR (KBr):
À1
ˆ
ˆ
1:1:1:2:1, Ci, C3a, C7a, C5 C7); 129.7, 128.8, and 127.8 (CH, 2:2:1,
C6H5), 123.8 (CH, C4), 60.6 (Cq, C1), 41.6 (CH2, C3), 32.2 (COCH3), 36.9
and 27.5 (2CH2, C2' C5'), 15.7 (7-CH3); IR (KBr): nÄ ˆ 1741.2, 1694.9 cmÀ1
nÄ ˆ 1699.0 (C O), 1699.3 cm (C O); MS (70 eV): m/z (%): 385.2 (100)
‡
[M] ; elemental analysis calcd (%) for C27H31NO(385.2): C 84.10, H 8.11,
N 3.63; found: C 83.92, H 7.99, N 3.40.
‡
‡
ˆ
(C O); MS (70 eV): m/z (%): 318 (80) [M] , 303 (100) [M À 15] ;
elemental analysis calcd (%) for C22H22O2 (318.4): C 82.99, H 6.96; found:
C 82.72, H 6.84.
1
Data for 12c: H NMR (C6D6): d ˆ 7.44 and 7.11 (m, 2:3H; C6H5), 6.95 (s,
1H; 4-H), 5.51 (s, 1H; 3-H), 2.85 (m, 4H; 2NCH2), 2.21 (s, 3H; 7-CH3), 2.21
and 1.95 (m, each 2H), 1.94 and 1.81 (m, each 2H) (2'-CH2 to 5'-CH2), 1.32
(m, 6H; 3CH2 piperidino), 1.85 (s, 3H; COCH3); 13C NMR (C6D6): d ˆ
3-Acetyl-2-methylene-4-phenyl-8-morpholinotricyclo[7.4.0.01,6]deca-3,5,7-
triene (4b) and 6-acetyl-7-methyl-5-phenyl-2-morpholinospiro(cyclopen-
tane-1,1-indane) (12b): Reaction of 1a (243 mg, 0.50 mmol) with morpho-
line (2b) (44 mg, 0.50 mmol) as described above gave 7b, which reacted
with 3a (268 mg, 0.50 mmol) to give a mixture (approximately 3:1:4) of 4b,
12b, and [W(pyridine)(CO)5] according to an 1H NMR spectrum. Fast
chromatography on basic alumina (column 2 Â 15 cm) with n-pentane/
dichloromethane (4:1) gave a yellow band of [W(pyridine)(CO)5], a
fraction containing 12b and 11 (38 mg, 21%, 12b/11 ˆ 2:1), and finally with
diethyl ether/dichloromethane (1:1) a fraction with 4b (124 mg, 64%, m.p.
1288C). A 3:1:4 mixture of 4b, 12b, and [W(pyridine)(CO)5] in [D6]ben-
zene at 658C for 30h was transformed into a 1:10:10 mixture of 4b, 12b, and
[W(pyridine)(CO)5] as shown by 1H NMR spectra. Compound (3E)-5b
(286 mg, 0.5 mmol), pyran-2-ylidene complex 3a (268 mg, 0.50 mmol), and
pyridine (40 mg, 0.50 mmol) reacted as described above to give a mixture
(approximately 1:20:20) of 4b, 12b, and [W(pyridine)(CO)5] as indicated
by 1H NMR spectra. Chromatography on basic alumina (column 2 Â 15 cm)
yielded a mixture of 12b and 11 (142 mg, 76%, 12b/11 ˆ 5:1), from which
11 (103 mg, 65%) could be isolated by chromatography on silica gel
(column 2 Â 15 cm) with n-pentane/dichloromethane (2:1).
ˆ
207.0 (Cq, C O), 168.9 (Cq, C2), 148.2, 145.2, 142.4, 137.9, and 126.9 (Cq,
1:1:1:2:1, Ci, C3a, C7a, C5 C7), 129.5, 128.6, and 127.4 (CH, 2:2:1, C6H5),
117.8 (CH, C4), 103.9 (CH, C3), 61.3 (Cq, C1), 51.2 (2NCH2), 32.8
(COCH3), 34.7 and 28.0 (2CH2, C2' C5'), 26.1 and 24.4 (2:1CH2
piperidino), 16.0 (7-CH3).
3-Acetyl-2-methylene-4-phenyl-8-pyrrolidinotricyclo[7.4.0.01,6]deca-3,5,7-
triene (4d) and 6-acetyl-7-methyl-5-phenyl-2-pyrrolidinospiro(cyclopen-
tane-1,1-indane) (12d): Tetrahydroindene 7d, which was prepared as
described above from 1a (243 mg, 0.50 mmol) and pyrrolidine (2d) (36 mg,
0.50 mmol), subsequently reacted with 3a (268 mg, 0.50 mmol) to give a
mixture (approximately 1:1) of 4d with [W(pyridine)(CO)5] as indicated by
1H NMR spectra. Fast chromatography on basic alumina (column 2 Â
15 cm) gave [W(pyridine)(CO)5] and 4d (159 mg, 86%, m.p. 1508C).
1
Data for 4d: H NMR (C6D6): d ˆ 7.48 and 7.10 (m, 2:3H; C6H5), 5.84 (s,
ˆ
1H; 5-H), 5.82 and 5.41 (s, each 1H; CH2), 5.11 (s, 1H; 7-H), 2.76 (m, 1H;
9-H), 2.78 (m, 4H; 2 NCH2), 1.98 (s, 3H; COCH3), 2.07 (m, 1H), 1.87 (m,
1H), 1.71 (m, 2H), 1.48 (m, 2H), 1.37 (m, 3H) 1.22 (m, 3H) (10-CH2 to 13-
CH2, 2CH2 pyrrolidino); 13C NMR (C6D6): d ˆ 204.0 (Cq, C O), 163.5 (Cq,
ˆ
C8), 162.0 (Cq, C6); 148.8, 142.8, 140.7, and 129.3 (Cq, Ci, C2 C4), 128.8,
1
ˆ
128.5, and 128.3 (CH, 2:2:1, C6H5), 109.8 ( CH2), 105.2 (CH, C5), 99.4 (CH,
Data for 4b: H NMR (C6D6): d ˆ 7.44 and 7.10 (m, 2:3H; C6H5), 5.93 (s,
ˆ
C7), 49.8 (2NCH2), 49.2 (Cq, C1), 48.0 (CH, C9), 32.1 (COCH3), 35.3, 24.1, 22.6,
1H; 5-H), 5.71 and 5.29 (brs, each 1H; CH2), 5.25 (s, 1H; 7-H), 3.41 (m,
and 18.9 (CH2, C10 C13), 25.6 (2CH2 pyrrolidino); IR (KBr): nÄ ˆ 1700.4 cmÀ1
;
4H; 2OCH2), 2.66 (dd, J ˆ 3.6, 5.8 Hz, 1H; 9-H), 2.40 (m, 4H; 2NCH2),
1.94 (s, 3H; COCH3); 1.90 (m, 1H), 1.80 (m, 1H), 1.60 (m, 2H), 1.38 (m,
1H), 1.20 (m, 3H) (10-CH2 to 13-CH2); 13C NMR (C6D6): d ˆ 204.5 (Cq,
‡
MS (70 eV): m/z (%): 371 (100) [M] ; elemental analysis calcd (%) for
C26H29NO(371.2): C 84.06, H 7.87, N 3.77; found: C 84.24, H 7.62, N 3.51.
ˆ
C O), 165.3 (Cq, C8), 159.5 (Cq, C6); 148.2, 141.9, 138.2, and 129.5 (Cq, Ci,
3-Acetyl-2-methylene-4-phenyl-8-[(2S)-2-(methoxymethyl)pyrrolidino]tri-
cyclo[7.4.0.01,6]deca-3,5,7-triene ((1S,9S)-4e and (1R,9R)-4e): Tetrahy-
droindene 7e, prepared as described above from 1a (243 mg, 0.50 mmol)
and 2e (58 mg, 0.50 mmol), subsequently reacted with complex 3a (268 mg,
0.50 mmol) to give a mixture (approximately 4:1:5) of (1S,9S)-4e, (1R,9R)-
4e, and [W(pyridine)(CO)5] as indicated by 1H NMR spectra. Fast
chromatography on basic alumina (column 2 Â 15 cm) gave [W(pyridine)-
(CO)5], (1S,9S)-4e, and (1R,9R)-4e (174 mg, 84%).
ˆ
C2 C4), 128.7 and 127.8 (CH, 4:1, C6H5), 112.0 ( CH2), 109.2 (CH, C5),
105.1 (CH, C7), 66.2 (2OCH2), 50.0 (2NCH2), 48.4 (Cq, C1), 46.8 (CH, C9),
31.9 (COCH3); 34.8, 24.3, 23.4, and 18.5 (CH2, C10 C13); IR (KBr): nÄ ˆ
‡
1698.6 cmÀ1 (C O); MS (70 eV): m/z (%): 387 (100) [M] ; elemental
ˆ
analysis calcd (%) for C26H29NO2 (387.2): C 80.57, H 7.55, N 3.62; found: C
80.40, H 7.45, N 3.47.
Data for 12b: 1H NMR (400 MHz, C6D6): d ˆ 7.45 and 7.14 (m, 2:3H;
C6H5), 6.99 (s, 1H; 4-H), 5.47 (s, 1H; 3-H), 3.52 (m, 4H; 2OCH2), 2.74 (m,
4H; 2NCH2), 2.33 (s, 3H; 7-CH3), 2.22 and 1.96 (m, each 2H), 1.95 and 1.80
(m, each 2H; 2'-CH2 to 5'-CH2), 1.86 (s, 3H; COCH3); 13C NMR (400 MHz,
Data for (1S,9S)-4e {(1R,9R)-4e}: 1H NMR (C6D6): d ˆ 7.46 and 7.12 {7.45
and 7.12} (m, 2:3H; o-, m-, p-H C6H5), 5.77 {5.81} (s, 1H , 5-H), 5.76 and 5.38
ˆ
{5.76 and 5.38} (s, each 1H; CH2), 5.26 {5.19} (s, 1H; 7-H), 3.58 {3.74} (m,
ˆ
C6D6): d ˆ 207.0 (Cq, C O), 168.3 (Cq, C2), 148.3, 144.5, 142.2, 138.6, 138.0,
1H; NCH), 3.29 and 3.12 {3.29 and 3.13} (m, each 1H; OCH2), 3.07 {3.07}
(m, 2H; NCH2), 3.08 {3.05} (s, 1H; OCH3), 2.81 {2.81} (b, 1H; 9-H), 2.97
{2.97} (m, 1H), 1.95 {1.95} (m, 1H), 1.82 1.62 {1.82 1.62} (m, 1H), 1.55
and 127.1 (Cq, Ci, C3a, C7a, C5 C7); 129.7, 128.7, and 127.5 (CH, 2:2:1,
C6H5), 118.3 (CH, C4), 105.3 (CH, C3), 68.7 (2OCH2), 61.1 (Cq, C1), 51.0
(2NCH2), 32.8 (COCH3), 34.3 and 27.9 (2CH2, C2' C5'), 16.0 (7-CH3).
1.22 {1.55 1.22} (m, 7H) (10-CH2 to 13-CH2, 2CH2 pyrrolidino), 1.95 {1.96}
13
ˆ
(s, 3H; COCH3); C NMR (C6D6): d ˆ 204.1 {203.9} (Cq, C O), 163.1
3-Acetyl-2-methylene-4-phenyl-8-piperidinotricyclo[7.4.0.01,6]deca-3,5,7-
triene (4c) and 6-acetyl-7-methyl-5-phenyl-2-piperidinospiro(cyclopen-
tane-1,1-indane) (12c): Tetrahydroindene 7c, which was prepared as
described above from 1a (243 mg, 0.50 mmol) and piperidine (2c)
(42 mg, 0.50 mmol), was treated with 3a (268 mg, 0.50 mmol) to give a
1:1 mixture of 4c with [W(pyridine)(CO)5] according to 1H NMR spectra.
Fast chromatography on alumina (column 2 Â 15 cm) with n-pentane/
dichloromethane (4:1) gave [W(pyridine)(CO)5], then with diethyl ether/
dichloromethane (1:1) afforded 4c (156 mg, 81%, m.p. 1518C). Reaction of
(3E)-5c (285 mg, 0.50 mmol) with 3a (268 mg, 0.50 mmol) and pyridine
(40 mg, 0.50 mmol) as described above gave a 1:2:3 mixture of 4c, 12c, and
[W(pyridine)(CO)5] according to 1H NMR spectra. Fast chromatography
on basic alumina (column 2 Â 10 cm) with n-pentane/dichloromethane/
diethyl ether (1:1:1) gave a mixture of 4c and 12c (156 mg, 83%, 4c/12c ˆ
1:2).
{162.0} (Cq, C8), 161.8 {161.6} (Cq, C6), 148.8 {148.8}, 142.6 {142.8}, 140.2
and 129.1 {140.8 and 129.3} (Cq, Ci, C2 C4); 128.8, 128.5, and 127.8 {128.8,
ˆ
128.5, and 127.8} (2:2:1, o-, m-, p-C C6H5), 110.1 {109.2} ( CH2), 105.9
914
¹ WILEY-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002
0947-6539/02/0804-0914 $ 17.50+.50/0
Chem. Eur. J. 2002, 8, No. 4

Synthesis of Fused-Ring Systems
910 916
{105.5} (CH, C5), 101.1 {100.0} (CH, C7), 73.1 {72.6} (OCH2), 59.9 {60.6}
(NCH), 58.9 {58.8} (OCH3), 50.8 {49.8} (NCH2), 49.0 {49.0} (Cq, C1), 48.7
{47.9} (CH, C9), 32.2 {32.0} (COCH3); 35.5, 24.2, 22.6, and 18.8 {35.2, 23.2,
22.5, and 19.2} (CH2, C10 C13), 29.3 and 24.7 {28.7 and 24.3} (2CH2
(CH, C6, C7), 125.3 and 125.1 (CH, C5, C8), 126.2 (CH, C3), 105.7 (CH,
C3'), 66.9 (2OCH2), 60.6 (Cq, C1'), 51.0 (2NCH2), 34.8 and 27.7 (2CH2,
C2' C5'), 29.6 and 26.3 (CH2, C9, C10).
Data for 17: 1H NMR (400 MHz,
pyrrolidino); IR (KBr): nÄ ˆ 1699.8 cmÀ1 (C O); MS (70 eV): m/z (%): 415
ˆ
C6D6): d ˆ 7.28, 7.14, and 7.12
‡
(100) [M] ; elemental analysis calcd (%) for C28H33NO2 (415.6): C 80.93, H
(2:2:1H; C6H5); 7.10 (m, 2H; C5,
8.00, N 3.37; found: C 80.74, H 7.92, N 3.56.
C8), 6.93 (s, 1H; 3-H), 6.95 and 6.77
(dt, each 1H; 6-H, 7-H), 3.26 (s, 2H;
3'-H), 2.65 and 2.51 (m, each 2H; 9-H,
10-CH2), 2.02 and 1.76 (m, each 4H;
2''-CH2 to 5''-CH2), 13C NMR
4-Phenyl-1,2(3,3a)-(1-dimethylamino-3a,4,5,6,7,7a-hexahydro-3H-indeno)-
phenanthrene (14a): Tetrahydroindene 7a (0.50 mmol), prepared as
described above, reacted with 13 (291 mg, 0.50 mmol) at 208C for 30 min
to give a 1:1 mixture of 14a with [W(pyridine)(CO)5] as indicated by
1H NMR spectra. Fast chromatography on basic alumina (column 2 Â
15 cm) gave 14a.
(400 MHz, C6D6): d ˆ 219.1 (Cq,
C2'), 144.0 (Cq, C2), 143.1, 139.6,
139.2, 136.4, 135.8, 134.6, and 133.7
Data for 14a: 1H NMR (400 MHz, C6D6): d ˆ 7.40 and 7.10 (m, 2:3H;
C6H5), 7.09 (m, 2H; 5-, 8-H), 6.89 and 6.72 (t, each 1H; 6-, 7-H), 6.05 (m,
1H; 10-H), 5.88 (s, 1H; 3-H), 5.25 (s,
(Cq, Ci, C1, C4, C4a, C4b, C8a, C10a), 130.0, 128.7, and 127.3 (CH, 2:2:1,
C6H5), 126.5 (CH, C3), 60.5 (Cq, C1'), 41.6 (CH2, C3'), 37.2 and 27.6 (2CH2,
C2' C5'), 29.8 and 26.5 (CH2, C9, C10); IR (KBr): nÄ ˆ 1741.6 cmÀ1; MS
1H; 2'-H), 3.50 (m, 2H; 9-CH2), 2.84
(d, 1H; 7'a-H), 2.39 (m, 6H;
N(CH3)2), 2.00 (m, 1H), 1.71 (m,
1H), 1.45 (m, 2H), 1.15 (m, 4H) (4'-
CH2 to 7'-CH2); 13C NMR (400 MHz,
‡
(70 eV): m/z (%): 364 (100) [M] ; elemental analysis calcd (%) for C27H24O
(364.2): C 88.97, H 6.64; found: C 88.79, H 6.51; X-ray crystal structure
analysis: formula C27H24O, M ˆ 364.46, light yellow crystal 0.15  0.15 Â
0.15 mm, a ˆ 8.389(1), b ˆ 12.283(1), c ˆ 18.895(1) ä, b ˆ 97.08(1)8, Vˆ
1932.1(3) ä3, 1calcd ˆ 1.253 gcmÀ3, m ˆ 0.74 cmÀ1, empirical absorption cor-
rection by SORTAV (0.989 ꢁ Tꢁ 0.989), Z ˆ 4, monoclinic, space group
P21/c (No. 14), l ˆ 0.71073 ä, Tˆ 198 K, w and f scans, 8482 reflections
C6D6): d ˆ 165.2 (Cq, C1'), 158.3 (Cq,
C2); 145.4, 144.5, 136.5, 136.0, and
133.8 (Cq, 1:1:1:1:2, Ci, 4, 4a, 4b, 8a,
10a), 130.0, 128.6, and 127.8 (CH,
collected (Æh, Æ k, Æ l), [(sinq)/l] ˆ 0.68 äÀ1, 4844 independent (Rint
ˆ
0.038) and 3614 observed reflections [I ꢂ 2s(I)], 253 refined parameters,
R ˆ 0.055, wR2 ˆ 0.120, max/min residual electron density 0.22/
À 0.19 eäÀ3, hydrogen atoms calculated and refined as riding atoms.[18]
2:2:1, C6H5), 129.5 and 126.9 (CH, C6, C7), 125.1 and 125.2 (CH, C5,
C8), 120.4 (CH, C10), 110.8 (CH, C3), 103.9 (CH, C2'), 48.1 (Cq, C1), 47.4
(CH, C7'a), 41.2 (N(CH3)2), 33.3 (CH2, C9), 33.9, 24.4, 23.5, and 19.1 (CH2,
Crystallographic data (excluding structure factors) for the structures
reported in this paper have been deposited with the Cambridge Crystallo-
graphic Data Centre as supplementary publication nos. CCDC-166191 and
CCDC-166192. Copies of the data can be obtained free of charge on
application to CCDC, 12 Union Road, Cambridge CB21EZ, UK (fax:
(‡44)1223-336-033; e-mail: deposit@ccdc.cam.ac.uk).
‡
C4' C7'); MS (70 eV): m/z (%): 391 (100) [M] .
4-Phenyl-1,2(3,3a)-(1-morpholino-3a,4,5,6,7,7a-hexahydro-3H-indeno)-
phenanthrene (14b), 4-phenyl-1,2(4,5)-spiro[cyclopentane-1,1-(2-morpho-
lino)cyclopentadieno]phenanthrene (18b), and 4-phenyl-1,2(4,5)-spiro[cy-
clopentane-1,1-(2-oxocyclopenteno)]phenanthrene (17): Tetrahydroin-
dene 7b (0.50 mmol), prepared as described above, reacted with 13
(291 mg, 0.50 mmol) at 208C for 30 min. The solvent was removed, and the
residue was washed three times with diethyl ether/n-pentane (1:1) (2 mL
each time), dissolved in dichloromethane (2 mL), and separated by
fast chromatography on basic alumina (column 2 Â 15 cm) with di-
chloromethane/diethyl ether (1:1) to give 14b (164 mg, 76%, m.p.
1948C). Reaction of (3E)-5b (286 mg, 0.50 mmol) with 13 (291 mg,
0.50 mmol) and pyridine (40 mg, 0.50 mmol) at 658C for 3 h gave a
mixture of 14b and 18b (180 mg, 83%, 14b/18b ˆ 1:3), which was
separated on silica gel with n-pentane/dichloromethane (1:1) to give 17
(105 mg, 58%, m.p. 1888C).
Acknowledgement
This work was supported by the Deutsche Forschungsgemeinschaft and the
Fonds der Chemischen Industrie.
[1] L. A. Paquette, A. M. Doherty, Polyquinane Chemistry. Reactivity and
Structure Concepts in Organic Chemistry, Vol. 26, Springer, Berlin,
1989.
[2] For a recent review on (1-alkynyl)carbene complexes see: R. Aumann,
H. Nienaber, Adv. Organomet. Chem. 1997, 41, 163 242.
[3] For the basics of this p-cyclization reaction see: a) R. Aumann, H.
Heinen, P. Hinterding, N. Str‰ter, B. Krebs, Chem. Ber. 1991, 124,
2343 2347; b) R. Aumann, H. Heinen, P. Hinterding, N. Str‰ter, B.
Krebs, Chem. Ber. 1991, 124, 1229 1236.
Data for 14b: 1H NMR (400 MHz, CDCl3): d ˆ 7.24 (m, 5H; C6H5), 7.11,
6.96, and 6.74 (m, 1:1:2H; 5-H 8-H), 6.18 (t, J ˆ 4.5 Hz, 1H; 10-H), 5.77 (s,
1H; 3-H), 5.26 (d, J ˆ 1.4 Hz, 1H; 2'-H), 3.78 (m, 4H; 2 OCH2), 3.54 (d, J ˆ
5.0 Hz, 2H; 9-CH2), 3.14 and 2.87 (m, each 2H; 2NCH2), 2.92 (d, J ˆ
5.9 Hz, 1H; 7'a-H), 2.06 and 1.84 (m, each 1H), 1.74 and 1.05 (m, each 1H),
1.58 and 1.20 (m, each 1H) and 1.15 (m, 2H) (4'-CH2 to 7'-CH2); 13C NMR
(400 MHz, C6D6): d ˆ 163.8 (Cq, C1'), 156.8 (Cq, C2), 144.2, 143.5, 135.7,
135.6, 132.6, and 121.0 (Cq; Ci, 4, 4a, 4b, 8a, 10a), 129.5, 128.2, and 126.5
(CH, 2:2:1, C6H5), 129.0 and 127.3 (CH, C6, C7), 125.5 and 124.7 (CH, C5,
C8), 121.1 (CH, C10), 111.9 (CH, C3), 105.1 (CH, C2'), 66.4 (2OCH2), 50.0
(2NCH2), 47.1 (Cq, C1), 46.3 (CH, C7'a), 33.0 (CH2, C9), 32.9, 24.0, 23.3,
[4] For a recent review on 1-metallahexatrienes see: R. Aumann, Eur. J.
Org. Chem. 2000, 17 31.
[5] a) A. G. Meyer, R. Aumann, Synlett 1995, 1011 1013; b) R. Aumann,
A. G. Meyer, R. Frˆhlich, Organometallics 1996, 15, 5018 5827; c) R.
Aumann, M. Kˆ˚meier, F. Zippel, Synlett 1997, 621 623; d) R.
Aumann, M. Kˆ˚meier, A. J‰ntti, Synlett 1998, 1120 1122; e) R.
Aumann, M. Kˆ˚meier, Ch. M¸ck-Lichtenfels, F. Zippel, Eur. J. Org.
Chem. 2000, 37 49.
[6] R. Aumann, I. Gˆttker-Schnetmann, R. Frˆhlich, P. Saarenketo, Ch.
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[8] H. Wu, R. Aumann, R. Frˆhlich, E. Wegelius, Organometallics 2001,
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[9] H. Wu, R. Aumann, B. Wibbeling, Eur. J. Org. Chem. 2000, 1183
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‡
and 18.8 (CH2 each, C4' C7'); MS (70 eV): m/z (%): 433 (100) [M] ;
elemental analysis calcd (%) for C31H31NO(433.2): C 85.87, H 7.21, N 3.23;
found: C 85.68, H 7.12, N 3.05.
Data for 18b: 1H NMR (400 MHz,
CDCl3): d ˆ 7.24 (m, 5H; C6H5); 7.10,
6.96, and 6.74 (m, 1:1:2H; 5-H 8-H),
7.0 (s, 1H; 3-H), 5.66 (s, 1H; 3'-H), 3.79
(m, 4H; 2OCH2), 3.06 (m, 4H;
2NCH2), 2.80 (m, 4H; 9-H, 10-CH2),
2.10 (m, 8H) (2''-CH2 to 5''-CH2);
13C NMR (400 MHz, C6D6): d ˆ 167.8
(Cq, C2'), 145.9 (Cq, C2), 142.2, 138.9,
138.7, 134.9, 133.4, and 120.5 (Cq; Ci, 4,
4a, 4b, 8a, 10a), 129.7, 128.2, and 126.6
(CH, 2:2:1, C6H5), 130.2 and 128.4
Chem. Eur. J. 2002, 8, No. 4
¹ WILEY-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002
0947-6539/02/0804-0915 $ 17.50+.50/0
915

R. Aumann et al.
FULL PAPER
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[16] R. Aumann, M. Kˆ˚meier, K. Roths, R. Frˆhlich, Tetrahedron 2000,
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[12] H. Wu, R. Aumann, S. Venne-Dunker, P. Saarenketo, Eur. J. Org.
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[13] For related studies, in which 1-metalla-1,3,5-trienes were generated by
addition of dienes to (1-alkynyl)carbene complexes, see: a) J. Bar-
[17] J. R. Bull, E. S. Sickle, Perkin 1 2000, 24, 4476 4487.
[18] Data sets were collected with Enraf-Nonius CAD4 and Nonius
KappaCCD diffractometers, the latter being equipped with a Non-
ius FR591 rotating anode generator. Programs used: data collection,
EXPRESS (Nonius B.V., 1994) and COLLECT (Nonius B.V., 1998);
data, MolEN (K. Fair, Enraf-Nonius B.V., 1990) and Denzo-SMN (Z.
Otwinowski, W. Minor, Methods Enzymol. 1997, 276, 307 326);
absorption correction for CCD data, SORTAV (R. H. Blessing, Acta
Crystallogr. Sect. A 1995, 51, 33 37; R. H. Blessing, J. Appl. Crystal-
logr. 1997, 30, 421 426); structure solution, SHELXS-97 (G. M.
Sheldrick, Acta Crystallogr. Sect. A 1990, 46, 467 473); structure
refinement, SHELXL-97 (G. M. Sheldrick, Universit‰t Gˆttingen,
1997); graphics, SCHAKAL (E. Keller, Universit‰t Freiburg, 1997).
¬
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¬
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[15] H.-P. Wu, R. Aumann, R. Frˆhlich, B. Wibbeling, O. Kataeva, Chem.
Eur. J. 2001, 7, 5084 5093.
Received: July 12, 2001 [F3411]
916
¹ WILEY-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002
0947-6539/02/0804-0916 $ 17.50+.50/0
Chem. Eur. J. 2002, 8, No. 4