Organic syntheses via transition metal complexes. 116. Carbocyclic four-, five-, and six-membered rings by condensation of (alkyl,ethoxy)carbene complexes (M = W, Cr) with α,β-unsaturated tertiary acid amides

Article abstract of DOI:10.1021/om0108604

4-Amino-1-tungsta-1,3,5-hexatrienes (CO)₅W=C(OEt)CH=C(NR₂)CH=CHPh (3E)-2 and (cyclohexan-4-on-1-yl)carbene tungsten complexes 6 were obtained by condensation of (ethoxy,methyl)carbene tungsten complex (OC)₅W=C(OEt)CH₃ 1a with α,β-unsaturated tertiary acid amides PhCH=CHC(=O)NR₂ 7 in the presence of POCl₃/Et₃N and (COCl)₂/Et₃N, respectively. Compounds 2 underwent a π-cyclization to zwitterionic η¹-cyclopentadiene complexes 3. Condensation of (prim-alkyl,ethoxy)carbene complexes (CO)₅M=C(OEt)CH₂R¹ 1 (M = W, Cr; R¹ = c-C₇H₇, n-Pr) with compounds 7 afforded (cyclobutenyl)carbene complexes 9.

Full text of DOI:10.1021/om0108604

Organometallics 2002, 21, 1637-1645
1637
Or ga n ic Syn th eses via Tr a n sition Meta l Com p lexes. 116.1
Ca r bocyclic F ou r -, F ive-, a n d Six-Mem ber ed Rin gs by
Con d en sa tion of (Alk yl,eth oxy)ca r ben e Com p lexes (M )
W, Cr ) w ith r,â-Un sa tu r a ted Ter tia r y Acid Am id es
Rudolf Aumann,*,† Dominik Vogt,† Xiaolin Fu,† Roland Fro¨hlich,†,§ and
Pia Schwab‡,
Organisch-Chemisches Institut der Universita¨t Mu¨nster, Corrensstrasse 40,
D-48149 Mu¨nster, Germany, and Institut fu¨r Organische Chemie der TU Dresden,
Mommsenstrasse 13, D-01069 Dresden, Germany
Received October 2, 2001
4-Amino-1-tungsta-1,3,5-hexatrienes (CO)5WdC(OEt)CHdC(NR2)CHdCHPh (3E)-2 and
(cyclohexan-4-on-1-yl)carbene tungsten complexes 6 were obtained by condensation of
(ethoxy,methyl)carbene tungsten complex (OC)5WdC(OEt)CH3 1a with R,â-unsaturated
tertiary acid amides PhCHdCHC(dO)NR2 7 in the presence of POCl3/Et3N and (COCl)2/
Et3N, respectively. Compounds 2 underwent a π-cyclization to zwitterionic η1-cyclopentadiene
complexes 3. Condensation of (prim-alkyl,ethoxy)carbene complexes (CO)5MdC(OEt)CH2R1
1 (M ) W, Cr; R1 ) c-C7H7, n-Pr) with compounds 7 afforded (cyclobutenyl)carbene complexes
9.
Fischer carbene complexes have been applied as
stoichiometric reagents in a number of high-yielding
transformations of potential use in organic synthesis.2
Recent examples include the formation of cyclopenta-
dienes by π-cyclization of 1-metalla-1,3,5-hexatrienes,3,4
which were derived from (1-alkynyl)carbene complexes,5
e.g., by addition of enamines6 or by addition of protic
nucleophiles NuH [e.g., R(R′CO)CH2,7 R2NH,8,9 R2PH,8
RC(dO)OH and ROH,10,11 RC(dX)SH (X ) O, NH,
NR),12 and RSH13].8,14 The latter procedure provides
access to highly reactive bicyclic cyclopentadienes, such
as tetrahydropentalenes8,9 or tetrahydroindenes,9,10 and
most notable also to the attachment of nucleophilic
substituents to the cyclopentadiene ring, which is
complementary to more conventional routes by which
electrophilic substituents are introduced to cyclopenta-
diene rings.
* To whom correspondence should be addressed.
† Organisch-Chemisches Institut der Universita¨t Mu¨nster.
‡ Institut fu¨r Organische Chemie der TU Dresden.
We now wish to report on studies directed toward the
formation of cyclopentadienes from readily available
Fischer carbene complexes other than (1-alkynyl)car-
bene complexes, namely, (ethoxy,methyl)carbene com-
plexes and substituted (prim-alkyl,ethoxy)carbene com-
plexes. Up to date, only a few examples of this
transformation have been reported.
A reaction sequence leading to cyclopentadienes from
(ethoxy,methyl)carbene tungsten complex (CO)5Wd
C(OEt)CH3 (1a ) has been previously achieved but it
required four steps (Scheme 1), involving the condensa-
tion of compound 1a with an aryl carbaldehyde ArCHO
in the presence of Me3SiCl/Et3N to give a 2-ethoxy-1-
§ X-ray structure analysis.
X-ray structure analyses of compound 6b.
(1) For part 115 of this series see: Wu, H.-P.; Aumann, R.; Fro¨hlich,
R.; Wegelius, E. Eur. J . Org. Chem. 2002, 361-368.
(2) For the application of Fischer carbene complexes to organic
syntheses see: (a) Do¨tz, K.-H. Angew. Chem. 1984, 96, 573-594;
Angew. Chem., Int. Ed. Engl. 1984, 23, 587-608. (b) Wulff, W. D. In
Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.;
Pergamon: New York, 1991; Vol. 5, p 1065-1113. (c) Wulff, W. D. In
Comprehensive Organometallic Chemistry II; Abel, E. W., Stone, F.
G. A., Wilkinson, G., Eds.; Pergamon: New York, 1995; Vol. 12, pp
469-547. (d) Doyle, M. P. In Comprehensive Organometallic Chemistry
II; Abel, E. W., Stone, F. G. A., Wilkinson, G., Eds.; Pergamon: New
York, 1995; Vol. 12, pp 387-420. (e) Wulff, W. D. In Advances in Metal-
Organic Chemistry; Liebeskind, L. S., Ed.; J AI Press: Greenwich, CT,
1989; Vol. 1. (f) Harvey, D. F.; Sigano, D. M. Chem. Rev. 1996, 96,
271-288. (g) Fru¨hauf, H.-W. Chem. Rev. 1997, 97, 523-596. (h)
Schirmer, H.; Duetsch, M.; deMeijere, A. Angew. Chem. 2000, 112,
4124-4162; Angew. Chem., Int. Ed. Engl. 1994, 33, 3964-4002.
(3) For the basics of this π-cyclization reaction see: (a) Aumann,
R.; Heinen, H.; Dartmann, M.; Krebs, B. Chem. Ber. 1991, 124, 2343-
2347. (b) Aumann, R.; Heinen, H.; Hinterding, N.; Stra¨ter, B. Krebs
Chem. Ber. 1991, 124, 1229-1236.
(8) Aumann, R.; Fro¨hlich, R.; Prigge, J .; Meyer, O. Organometallics
1999, 18, 1369-1380.
(9) Wu, H.-P.; Aumann, R.; Fro¨hlich, R.; Wegelius, E. Organo-
metallics 2001, 20, 2183-2190.
(10) Wu, H.-P.; Aumann, R.; Wibbeling, B. Eur. J . Org. Chem. 2000,
1183-1192.
(4) For a recent review on 1-metallahexatrienes see: Aumann, R.
Eur. J . Org. Chem. 2000, 17-31.
(11) Wu, H.-P.; Aumann, R.; Fro¨hlich, R.; Saarenketo, P. Chem. Eur.
J . 2001, 7, 700-710.
(5) For a recent review on (1-alkynyl)carbene complexes see: Au-
mann, R.; Nienaber, H. Adv. Organomet. Chem. 1997, 41, 163-242.
(6) (a) Meyer, A. G.; Aumann, R. Synlett 1995, 1011-1013. (b)
Aumann, R.; Meyer, A. G.; Fro¨hlich, R. Organometallics 1996, 15,
5018-5827. (c) Aumann, R.; Ko¨ssmeier, M.; Zippel, F. Synlett 1997,
621-623. (d) Aumann, R.; Ko¨ssmeier, M.; J a¨ntti, A. Synlett 1998,
1120-1122. (e) Aumann, R.; Ko¨ssmeier, M.; Mu¨ck-Lichtenfels, Ch.;
Zippel, F. Eur. J . Org. Chem. 2000, 37-49.
(12) Wu, H.-P.; Aumann, R.; Fro¨hlich, R.; Wegelius, E.; Saarenketo,
P. Organometallics 2000, 19, 2373-2381.
(13) Wu, H.-P.; Aumann, R.; Venne-Dunker, S.; Saarenketo, P. Eur.
J . Org. Chem. 2000, 19, 3463-3473.
(14) For related studies, in which 1-metalla-1,3,5-trienes were
generated by addition of dienes to (1-alkynyl)carbene complexes, see:
(a) Barluenga, J .; Aznar, F.; Barluenga, S.; Ferna´ndez, M.; Mart´ın,
A.; Garc´ıa-Granda, S.; Pinera-Nicola´s, A. Chem. Eur. J . 1998, 4, 2280-
2298. (b) Barluenga, J .; Aznar, F.; Palomero, M. A.; Barluenga, S. Org.
Lett. 1999, 541-543.
(7) Aumann, R.; Go¨ttker-Schnetmann, I.; Fro¨hlich, R.; Saarenketo,
P.; Holst, Ch. Chem. Eur. J . 2001, 7, 711-720.
10.1021/om0108604 CCC: $22.00 © 2002 American Chemical Society
Publication on Web 03/15/2002

1638 Organometallics, Vol. 21, No. 8, 2002
Aumann et al.
Sch em e 1. Am in o,eth oxy Cyclop en ta d ien es fr om (Eth oxy,m eth yl)ca r ben e Tu n gsten Com p lex 1a
tungsta-1,3-butadiene (CO)5WdC(OEt)CHdCHPh.15 Ad-
dition of 1-diethylaminopropyne to the latter compound
afforded a (3Z)-2-amino-4-ethoxy-1-tungsta-1,3,5-hexa-
triene,3a which underwent a smooth π-cyclization to a
zwitterionic η1-cyclopentadiene pentacarbonyltungsten
complex already at 20 °C, and finally gave an amino,
ethoxy cyclopentadiene by disengagement of the penta-
carbonyl tungsten unit.3b
We aimed for a new and efficient approach to the
formation of cyclopentadienes, involving the generation
of 1-metalla-1,3,5-hexatrienes by condensation of (ethoxy,
methyl)carbene complexes (CO)5MdC(OEt)CH3 1 (M )
W, Cr) with R,â-unsaturated organic carbonyl com-
pounds. Condensation reactions of this type were known
of saturated aldehydes and ketones,16 acid chlorides,17
and acid amides,18 but also R,â-unsaturated ketones,
aldehydes, esters, and lactones.19 Both 1,2-addition as
well as 1,4-addition reactions were found, but in a few
cases only, these reactions have been utilized for the
generation of carbocyclic compounds.20
We now report for the first time on condensation
reactions of (alkyl,ethoxy)carbene complexes (CO)5Md
C(OEt)CH2R1 1a -e (M ) W, Cr; R1 ) H, c-C7H7, n-Pr)
with R,â-unsaturated acid amides 7a -c [PhCHd
CHC(dO)NR2], leading to formation as well of carbo-
cyclic five-, four-, and six-membered rings.
Con d en sa tion of r,â-Un sa tu r a ted Ter tia r y Acid
Am id es 7a -c w ith (Alk yl,eth oxy)ca r ben e Com -
p lexes 1a -e (M ) Cr , W). (Alkyl,ethoxy)carbene
complexes (CO)5MdC(OEt)CH2R1 1a -e undergo a con-
densation with unsaturated tertiary acid amides 7a -c
in the presence of triethylamine/phosphorus oxychloride
and triethylamine/oxalyl dichloride, respectively. The
process is initiated by the transformation of acid amides
7a -c into more reactive iminium chlorides 4a -c
(Scheme 2). Two major reaction paths, initiated by 1,2-
and 1,4-addition to these compounds, respectively, were
observed. A marked influence of substituents R1 at the
R-carbon atom of the carbene complexes 1a -e was
found. For example, the (ethoxy,methyl)carbene tung-
sten complex (CO)5WdC(OEt)CH3 (1a ) (R1 ) H) was
shown to mainly afford 1-metalla-1,3,5-hexatrienes (3E)-
2a ,b by 1,2-addition. In line with expectation, these
compounds underwent a π-cyclization to η1-cyclopenta-
diene complexes 3a ,b.3,4 While monitoring this reaction
more carefully, we found red tungsten compounds 6a ,b
as byproducts. Quite obviously, compounds 6a ,b result
from 1,4-addition of (ethoxy,methyl)carbene complex 1a
to 2 equiv of R,â-unsaturated iminium chlorides 4a ,b.
It is assumed that adducts 5 were formed as intermedi-
ates, which underwent a hitherto unknown Dieckmann
type cyclization. The overall process involves a high
diastereoselectivity, leading to an equatorial arrange-
ment of all substituents of the six-membered ring.
Other than (ethoxy,methyl)carbene complexes 1a ,b,
(prim-alkyl,ethoxy)carbene complexes (CO)5MdC(OEt)-
CH2R1 1c-e (M ) Cr, W; R1 ) c-C7H7, n-Pr) did not
yield 1-metalla-1,3,5-hexatrienes (3E)-2c-k , but instead
formed (cyclobutenyl)carbene complexes 9c-k by 1,4-
addition (Scheme 3).
The marked influence of substituents R1 at the
R-carbon atom of (alkyl,ethoxy)carbene complexes
(CO)5MdC(OEt)CH2R1 1c-e on the condensation of this
compounds with R,â-unsaturated iminium chlorides
4a -c is explained on the assumption that the conjugate
base of (alkyl,ethoxy)carbene complexes 1c-e having
a secondary R-carbon atom would be a “softer” nucleo-
phile than the conjugate base of (ethoxy,methyl)carbene
complexes 1a ,b and therefore should preferentially add
to the “soft” â-carbon atom of R,â-unsaturated iminium
chlorides 4a -c. A 1,4-addition provides indeed a good
explanation for the experimental finding that the ther-
modynamically less favorable “cis” diastereomers rel-
(3S,4S)-9c-k are obtained as major isomers, with
diastereoselectivities ranging from 2:1 to 20:1 (see
legend to Scheme 3). It appears that the “cis” configu-
ration of these compounds is determined by the stereo-
chemistry of the 1,4-adducts erythro-8 (Scheme 4).
Compounds erythro-8 are expected to be generated
preferentially over compounds threo-8, and they are
expected to be transformed through intermediates “cis”-
10 and “cis”-11 into the “cis” isomer of the corresponding
(cyclobutenyl)carbene complexes 9.
(15) Aumann, R.; Heinen, H. Chem. Ber. 1987, 120, 537-540.
(16) (a) Wulff, W. D.; Gilbertson, S. R. J . Am. Chem. Soc. 1985, 107,
503-505. (b) Wulff, W. D.; Anderson, B. A.; Toole, A. J . Am. Chem.
Soc. 1989, 111, 5485-5487. (c) Wulff, W. D.; Anderson, B. A.; Toole,
A.; Xu, Y.-C. Inorg. Chim. Acta 1994, 220, 215-231, and references
therein. (d) Powers, T. S.; Shi, Y.; Wilson, K. J .; Wulff, W.-D. J . Org.
Chem. 1994, 59, 6882-6884. (e) Wang, H.; Hsung, R. P.; Wulff, W.-D.
Tetrahedron Lett. 1998, 39, 1849-1852.
(17) (a) Casey, C. P.; Boggs, R. A.; Anderson, R. A. J . Am. Chem.
Soc. 1972, 94, 8947-8949. (b) Aumann, R.; J asper, B.; La¨ge, M.; Krebs,
B. Organometallics 1994, 13, 3510-3516.
(18) (a) Lattuado, L.; Licandro, E.; Maiorana, S.; Papagni, A.; Chiesi
Villa, A.; Guastini, C. J . Chem. Soc., Chem. Commun. 1988, 1092-
1093. (b) Aumann, R.; Hinterding, P. Chem. Ber. 1990, 123, 2047-
2051. (c) Aumann, R.; Hinterding, P. Chem. Ber. 1990, 123, 611-620.
(d) Aumann, R.; Hinterding, P. Chem. Ber. 1989, 122, 365-370.
(19) (a) Casey, C. P.; Brunsvold, W. R.; Scheck, M. D. Inorg. Chem.
1977, 16, 3059-3063. (b) Wulff, W. D.; Anderson, B. A.; Rahm, A. J .
Am. Chem. Soc. 1993, 115, 4602-4611. (c) Iyoda, M.; Zhao, L.;
Matsuyama, H. Tetrahedron Lett. 1995, 36, 3699-3702.
(20) Mongin, C.; Lugan, N.; Mathieu, R. Organometallics 1997, 16,
3873-3875.

Organic Syntheses via Transition Metal Complexes
Organometallics, Vol. 21, No. 8, 2002 1639
Sch em e 2. Con d en sa tion of (Meth yl,eth oxy)ca r ben e Tu n gsten Com p lex 1a w ith r,â-Un sa tu r a ted Ter tia r y
Acid Am id es 7a ,b In volvin g a 1,2- a n d a 1,4-Ad d ition , Resp ectively
a
Isolated yields in %, of reactions achieved by condensation with POCl3/Et3N; yields given in parentheses were obtained if
(COCl)2/Et3N was used instead of POCl3/Et3N.
Sch em e 3. Con d en sa tion of (Alk yl,eth oxy)ca r ben e Com p lexes 1c-e (M ) Cr , W) w ith r,â-Un sa tu r a ted
Ter tia r y Acid Am id es 7a -c In volvin g a 1,4-Ad d ition a s th e On ly Rea ction P a th
a
Isolated yields in %, of reactions achieved by condensation with POCl3/Et3N. b Product ratio of diastereomers “cis”-9:“trans”-9
1
according to the integration of H NMR signals.
Sp ectr oscop y a n d Cr ysta l Str u ctu r e An a lyses of
compound “cis”-9c (Figure 1). 3J ) ca. 5 Hz was typically
3
Com p ou n d s 2, 6, a n d 9. The structures of the (cyclo-
observed for the “cis” isomers and J ) ca. 1 Hz for the
1
butenyl)aminocarbene complexes 9 are based on H and
“trans” products. The cyclobutene ring exhibits a trap-
ezoid shape with C3-C4 1.342(6) Å, C4-C5 1.503(6) Å,
13C NMR spectra and on a crystal structure analysis of

1640 Organometallics, Vol. 21, No. 8, 2002
Aumann et al.
Sch em e 4. Rea ction P a th to Dia ster eom er ic (Cyclobu ten yl)ca r ben e Com p lexes 9
F igu r e 2. Molecular structure of (cyclohexanonyl)carbene
complex 6b with selected bond lengths (Å) and bond angles
(deg) (averaged values from two independent molecules):
W-C11 2.183(6), C11-C1 1.535(8), C1-C2 1.553(8), C1-
C6 1.565(8), C2-C3 1.540(8), C3-C4 1.494(9), C4-O41
1.205(8), C4-C5 1.519(8), C5-C6 1.531(8), C5-C51 1.527(8),
C51-O52 1.236(8), C51-N53 1.330(7); W-C11-C1 126.7(4),
C11-C1-C2 110.5(4), C11-C1-C6 109.6(5), C1-C2-C3
110.1(5), C2-C3-C4 112.5(5), C3-C4-C5 115.0(5), C3-
C4-O41 122.8(6), C5-C4-O41 122.3(6), C4-C5-C6
112.3(5), C5-C6-C1 112.4(5), C4-C5-C51 108.9(5), C6-
C5-C51 110.5(5), C5-C51-O52 120.3(6), C5-C51-N53
118.5(5), O52-C51-N53 121.3(6).
F igu r e 1. Molecular structure of (cyclobutenyl)carbene
complex 9c with selected bond lengths (Å), bond angles
(deg), and dihedral angle (deg): W-C2 2.283(5), C2-N1
1.302(5), C2-C3 1.460(6), C3-C4 1.342(6), C3-C6 1.535(6),
C4-O41 1.344(5), C4-C5 1.503(6), C5-C6 1.586(6); C3-
C2-W 115.6(3), C4-C3-C2 135.2(4), C4-C3-C6 91.6(4),
C2-C3-C6 131.6(4), C3-C4-O41 135.0(5), C3-C4-C5
97.7(4), C4-C5-C6 83.9(3), C3-C6-C5 86.8(3); W-C2-
C3-C4 -115.3(6).
C5-C6 1.586(6) Å, and C3-C6 1.535(6) Å. The plane
defined by the atoms W,C2,C3 is strongly tilted against
the cyclobutene ring C3,C4,C5 by 55.5°, thus implying
little if any π-conjugation.
O3-C4-W -4.1(12)°, C2-O3-C4-C5 177.9(8)°, O3-
C4-C5-C6-3.8(12)°, W-C4-C5-C6 178.1(6)°, and
C4-C5-C6-N61 158.7(8)°. The bond distances C4-C5
1.389(10) Å, C5-C6 1.426(10) Å, and C6-N61 1.324(9)
Å indicate a charge delocalization by π-conjugation
within this unit.
Con clu sion . Condensation of R,â-unsaturated acid
amides 7 with (alkyl,ethoxy)carbene complexes 1 (M )
W, Cr) in the presence of POCl3/Et3N and (COCl)2/Et3N,
respectively, has been found to provide a new and
efficient entry into the formation of carbocyclic four-,
five-, and six-membered rings. The reaction is strongly
influenced by substituents on the R-carbon atom of the
carbene complex. Thus, condensation of (ethoxy,methyl)-
carbene tungsten complexes (OC)5WdC(OEt)CH3 1a ,b
The structures of compounds 6a ,b were elucidated by
1H and 13C NMR measurements and also by a crystal
structure analysis of compound 6b (Figure 2).
The structures of the 4-amino-1-metallahexatrienes
1
(3E)-2 and (3Z)-2 are based on H and 13C NMR spectra,
including 1J (C,H) and 2,3J (C,H) correlation experiments
and NOE studies. Compound (3E)-2b was analyzed also
by a crystal structure analysis (Figure 3). The 13C
signals of the MdC unit are typically observed in a
narrow range of δ 265-268 for the tungsten compounds
and 286-289 for the chromium compounds.
The ligand backbone W-C4-C5-C6-N of compound
(3E)-2b is nearly planar and exhibits a W shape, C2-

Organic Syntheses via Transition Metal Complexes
Organometallics, Vol. 21, No. 8, 2002 1641
methane. Flash chromatography after 4 h at 25 °C on silica
gel (20 × 2 cm, 3:1 n-pentane/dichloromethane) afforded a red
fraction with compound 2a (22 mg, 8%, Rf ) 0.6 in 2:1
n-pentane/dichloromethane, orange crystals at -20 °C, dec 62
°C) and a yellow-orange fraction with compound 3a (99 mg,
36%, Rf ) 0.5 in 2:1 n-pentane/dichloromethane). Condensation
of compounds 7a with 1a with oxalyl chloride (140 mg, 1.10
mmol) (instead of phosphorus oxychloride) was complete after
30 min at 0 °C and gave a higher yield of compound (3E)-2a
(177 mg, 64%), a lower yield of compound 3a (9 mg, 3%), and
additionally also compound 6a (57 mg, 16%, Rf ) 0.3 in 10:1
dichloromethane/diethyl ether, orange crystals from 1:10
dichloromethane/n-pentane at -20 °C, dec 163 °C).
F igu r e 3. Molecular structure of 4-pyrrolidino-1-tungsta-
1,3,5-hexatriene (3E)-2b with selected bond lengths (Å),
bond angles (deg), and dihedral angles (deg): W-C4
2.250(7), C4-C5 1.389(10), C5-C6 1.426(10), C6-C7
1.468(10), C7-C8 1.325(11), C8-C81 1.461(11), C6-N61
1.324(9), C4-O3 1.362(10); C5-C4-W 120.2(5), O3-
C4-W 127.8(5), C4-C5-C6 129.8(7), C5-C6-C7 120.2(7),
C8-C7-C6 128.3(7), C7-C8-C81 125.6(8); C2-O3-
C4-W -4.1(12), C2-O3-C4-C5 177.9(8), C24-W-C4-
O3 -49.9(7), O3-C4-C5-C6 -3.8(12), W-C4-C5-C6
178.1(6), C4-C5-C6-N61 158.7(8), C5-C6-N61-C62
-2.5(11), C4-C5-C6-C7 -24.6(12), C6-C7-C8-C81
-178.9(7).
(3E)-2a : 1H NMR (CDCl3, 25 °C) δ 7.46 (2 H, “d”, Ph), 7.38
3
3
(3 H, m, Ph), 6.80 (1 H, d, J ) 16.5 Hz, 5-H), 6.73 (1 H, d, J
) 16.5 Hz, 6-H), 6.46 (1 H, s, 3-H), 4.48 (2 H, q, OCH2), 3.17
(6 H, s, 2 NCH3), 1.20 (3 H, t, OCH2CH3); 13C NMR (CDCl3,
25 °C) δ 268.2 (Cq, WdC), 204.2 and 199.9 [1:4, trans- and
cis-CO, W(CO)5], 157.2 (Cq, C4), 137.8 (CH, C6), 135.3 (i-C Ph),
129.3, 128.9 and 126.8 (1:2:2, CH each, Ph), 124.2 (CH, C5),
121.0 (CH, C3), 76.1 (OCH2), 40.0 (2 NCH3), 15.5 (OCH2CH3);
IR (n-hexane), cm-1 (%) 2055.5 (15), 1925.8 (100) [ν(CtO)];
MS (70 eV), 184W, m/e (%) 553 (2) [M+], 525 (0) [M+ - CO],
497 (3) [M+ - 2 CO], 469 (1) [M+ - 3 CO], 441 (4) [M+ - 4
CO], 413 (3) [M+ - 5 CO], 229 (79) [M+ - W(CO)5], 200 (100).
Anal. Calcd for C20H19NO6W (553.2): C, 43.42; H, 3.46; N, 2.53.
Found: C, 43.38; H, 3.59; N, 2.41.
(M ) W, Cr) with 1 equiv of R,â-unsaturated tertiary
acid amides PhCHdCHC(dO)NR2 7a ,b provides a new
access to 4-amino-1-tungsta-1,3,5-hexatrienes (CO)5Wd
C(OEt)CHdC(NR2)CHdCHPh (3E)-2a ,b with 3E con-
figuration. Compounds 2a ,b undergo a π-cyclization to
zwitterionic η1-cyclopentadiene complexes 3a ,b. Con-
densation of compounds 1a ,b with 2 equiv of 7a ,b leads
to generation of (cyclohexan-4-on-1-yl)carbene tungsten
complexes 6a ,b with high diastereoselectivity. Conden-
sation of (alkyl,ethoxy)carbene complexes (CO)5Md
C(OEt)CH2R 1c-e (M ) W, Cr; R ) c-C7H7, n-Pr) with
compounds 7a -c affords (cyclobutenyl)carbene com-
plexes 9c-k .
3a : 1H NMR (CDCl3, 25 °C) δ 7.27 (3 H, m, Ph), 7.07 (2 H,
“d”, Ph), 5.58 (1 H, s, EtOCdCH), 4.51 (1 H, s, CHPh), 4.08 (2
H, m, diastereotopic OCH2), 3.30 and 3.04 (3 H each, s each,
NCH3 each), 2.72 [1 H, CHW(CO)5], 1.36 (3 H, t, OCH2CH3);
13C NMR (CDCl3, 25 °C) δ 202.8 and 201.2 [1:4, trans- and
cis-CO, W(CO)5], 192.3 (Cq, CdN+), 183.3 (Cq, EtO-C), 141.1
(Cq, i-C Ph), 128.9, 127.0 and 126.4 (2:1:2, CH each, Ph), 94.5
(CH, C2), 68.0 (OCH2), 65.7 (CH, CHPh), 40.9 and 40.7 (NCH3
each), 38.0 [CH, CHW(CO)5-], 14.0 (OCH2CH3); IR (diffuse
reflection), cm-1 (%) 2052.6 (10), 1974.9 (70), 1891.1 (100)
[ν(CtO)], 1589.9 (25) [ν(CdN+)]; MS (70 eV), 184W, m/e (%)
553 (1) [M+], 525 (0) [M+ - CO], 497 (0) [M+ - 2 CO], 469 (3)
[M+ - 3 CO], 441 (5) [M+ - 4 CO], 413 (3) [M+ - 5 CO], 229
(81) [M+ - W(CO)5], 200 (100).
Exp er im en ta l Section
All operations were carried out under an atmosphere of
argon. All solvents were dried and distilled prior to use. All
1H and 13C NMR spectra were routinely recorded on Bruker
ARX 300 and AM 360 instruments. COSY, HMQC, HMBC,
and NOE experiments were performed on a Bruker AMX 400
and a Varian 600 U instrument. 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 silica gel 60F240, were viewed by UV light (254 nm)
and stained by iodine. Rf values refer to TLC tests. Compounds
1a ,b were prepared according to ref 21; compound 1c, accord-
ing to ref 22.
(3E ,5E )-1,1,1,1,1-P e n t a ca r b on yl-2-e t h oxy-4-N ,N -(d i-
m eth yla m in o)-6-p h en yl-1-tu n gsta -1,3,5-h exa tr ien e [(3E)-
2a ], P en ta ca r bon yl[4-eth oxy-2-(d im eth yla zon ia )-5-p h en -
yl-3-cyclop en ten yl]tu n gsta te (3a ), a n d P en ta ca r bon yl-
{1-eth oxy-1-[2,6-bisph en yl-3-(dim eth ylam in e-1-car bon yl)-
cycloh exan -4-on -1-yl]m eth ylen e}tu n gsten [(1′R*,2′R*,3′R*,
6′R*)-6a ]. To (2E)-N,N-dimethyl-3-phenylacrylamide (7a ) (175
mg, 1.00 mmol) and phosphorus oxychloride (153 mg, 1.00
mmol) in 2 mL of dry dichloromethane in a 5 mL screw-top
vessel was added after 15 min at 0 °C with stirring a solution
of (ethoxy,methyl)carbene complex 1a (198 mg, 0.50 mmol) and
triethylamine (202 mg, 2.00 mmol) in 1 mL of dichloro-
6a : 1H NMR (600 MHz, CDCl3) δ 7.33 and 7.27 (2 H each,
“t” each, m-CH Ph each), 7.23 and 7.18 (3 H each, m each, o-
3
and p-CH Ph each), 4.92 (1 H, dd, J ) 11 and 11 Hz, 1′-H),
3
4.78 (2 H, m, diastereotopic OCH2), 4.19 (1 H, d, J ) 11 Hz,
3
3′-H), 4.03 (1 H, dd, J ) 11 and 11 Hz, 2′-H), 3.45 (1 H, ddd;
2
3
3J ) 13, 11 and 4 Hz, 6′-H), 2.98 (1 H, dd, J ) -14 and J )
(21) Aumann, R.; Fischer, E. O. Chem. Ber. 1968, 101, 954-962.
(22) Aumann, R.; Runge, M. Chem. Ber. 1992, 125, 259-264.
13 Hz, 5′-Hax), 2.86 and 2.77 [3 H each, s broad each, N(CH3)2],

1642 Organometallics, Vol. 21, No. 8, 2002
Aumann et al.
2
3
3
2.74 (1 H, dd, J ) -14 and J ) 4 Hz, 5′-Heq), 1.82 (3 H, t, J
) 7 Hz, OCH2CH3); 13C NMR (CDCl3) δ 340.8 (WdC), 203.8
(Cq, C4′), 202.4 and 196.4 [Cq each, 1:4, trans- and cis-CO,
W(CO)5], 167.5 (NCO), 140.1 and 139.2 (Cq each, i-C Ph each);
129.1, 129.0, 127.9, 127.7, 127.6, and 127.5 (2:2:1:2:2:1, CH
each, Ph each), 80.1 (OCH2), 77.9 (CH, C1′), 58.9 (CH, C3′),
50.6 (CH, C2′), 48.0 (CH2, C5′), 47.2 (CH, C6′), 37.3 and 35.7
[CH3 each, broad each, N(CH3)2], 14.9 (OCH2CH3); IR (n-
hexane), cm-1 (%) 2063.8 (30), 1982.5 (5), 1959.0 (100) [ν(CtO],
1734 (50) [ν(CdO)]; MS (70 eV), 184W, m/e (%) 701 (2) [M+],
673 (5) [M+ - CO], 617 (30) [M+ - 3 CO], 589 (50) [M+ - 4
CO], 561 (20) [M+ - 5 CO]. Anal. Calcd for C29H27NO8W
(701.4): C, 49.66; H, 3.88; N, 2.00. Found: C, 49.99; H, 4.01;
N, 1.75.
3b: 1H NMR (CDCl3, 25 °C) δ 7.28 (3 H, m, Ph), 7.09 (2 H,
“d”, Ph), 5.47 (1 H, s, EtOCdCH), 4.51 (1 H, s, CHPh), 4.09 (2
H, m, diastereotopic OCH2), 3.79, 3.66, 3.58 and 3.16 (1 H each,
m each, 2 diastereotopic NCH2), 2.60 [1 H, CHW(CO)5], 2.14
and 2.08 (1:3 H, m each, 2 NCH2CH2), 1.36 (3 H, t, OCH2CH3);
13C NMR (CDCl3, 25 °C) δ 202.9 and 201.3 [1:4, trans- and
cis-CO, W(CO)5], 188.8 (Cq, CdN+), 182.9 (Cq, EtO-C), 141.3
(Cq, i-C Ph), 128.9, 126.9, and 126.4 (2:1:2, CH each, Ph), 95.1
(CH, C2), 68.0 (OCH2), 65.7 (CH, CHPh), 50.0 and 49.0 (NCH2
each), 37.5 [CH, CHW(CO)5-], 25.2 (2 NCH2CH2), 14.0
(OCH2CH3); IR (diffuse reflection), cm-1 (%) 2052.6 (10), 1974.9
(70), 1891.1 (100) [ν(CtO)], 1591.8 (30) [ν(CdN+)]; MS (70 eV),
184W, m/e (%) 579 (1) [M+], 551 (0) [M+ - CO], 523 (1) [M+
-
2 CO], 495 (3) [M+ - 3 CO], 467 (5) [M+ - 4 CO], 439 (3) [M+
- 5 CO], 255 (82) [M+ - W(CO)5], 226 (100). Anal. Calcd for
(3E,5E)-1,1,1,1,1-P en t a ca r b on yl-2-et h oxy-6-p h en yl-4-
p yr r olid in o-1-tu n gsta -1,3,5-h exa tr ien e [(3E)-2b], P en ta -
ca r bon yl[4-eth oxy-5-p h en yl-2-p yr r olid in iu m -3-cyclop en -
ten yl]tu n gsta te (3b), a n d P en ta ca r bon yl{1-eth oxy-1-[2,6-
bisp h en yl-3-(p yr r olid in e-1-ca r bon yl)cycloh exa n -4-on -1-
yl]m eth ylen e}tu n gsten [(1′R*,2′R*,3′R*,6′R*)-6b]. 3-Phenyl-
1-pyrrolidinoprop-2-en-1-one(7b)(201mg,1.00mmol),phosphorus
oxychloride (153 mg, 1.00 mmol), (ethoxy,methyl)carbene
tungsten complex 1a (198 mg, 0.50 mmol), and triethylamine
(202 mg, 2.00 mmol) were reacted as described above to give
compound (3E)-2b (35 mg, 12%, Rf ) 0.6 in 2:1 n-pentane/
dichloromethane, orange crystals, dec 65 °C) and compound
3b (122 mg, 42%, Rf ) 0.5 in 2:1 n-pentane/dichloromethane,
yellow crystals, mp 95 °C). If the condensation was performed
with oxalyl chloride as described above, it afforded compound
(3E)-2b (211 mg, 73%), compound 3b (23 mg, 8%), and also
compound 6b (56 mg, 15%, Rf ) 0.3 in 10:1 dichloromethane/
diethyl ether, orange crystals from 1:10 dichloromethane/n-
pentane at -20 °C, mp 166 °C).
C
22H21NO6W (579.3): C, 45.62; H, 3.65; N, 2.42. Found: C,
45.59; H, 3.72; N, 2.02.
6b: 1H NMR (600 MHz, CDCl3) δ 7.32 and 7.26 (2 H each,
“t” each, m-CH Ph each), 7.23 and 7.19 (3 H each, m each, o-
3
and p-CH Ph each), 4.93 (1 H, dd, J ) 11 Hz and 11, 1′-H),
4.77 (2 H, m, diastereotopic OCH2), 4.01 (1 H, dd, 3J ) 11 and
12 Hz, 2′-H), 3.95 (1 H, d, 3J ) 12 Hz, 3′-H), 3.46 (1 H, ddd; 3J
) 12, 11 and 4 Hz, 6′-H); 3.45, 3.34, 3.16, and 3.07 (1 H each,
m each, 2 NCH2), 2.95 (1 H, dd, 2J ) -15 and 3J ) 12 Hz,
2
5′-Hax), 2.74 (1 H, dd, J ) -15 and 3J ) 4 Hz, 5′-Heq); 1.86,
3
1.78, and 1.75 (2:4:2 H, m each, 2 NCH2CH2), 1.80 (3 H, t, J
) 7 Hz, OCH2CH3); 13C NMR (CDCl3) δ 340.8 (WdC), 203.8
(Cq, C4′), 202.4 and 196.4 [1:4, trans- and cis-CO, W(CO)5],
165.8 (C4′),140.2 and 139.1 (Cq each, i-C Ph each); 129.2, 129.0,
128.0, 127.7, 127.6, and 127.5 (2:2:1:2:2:1, CH each, Ph each),
80.1 (OCH2), 77.7 (CH, C1′), 61.3 (CH; C3′), 50.4 (CH, C2′),
48.0 (CH2, C5′), 47.1 (CH, C6′), 46.7 and 45.6 (broad each,
NCH2 each), 25.8 and 24.22 (broad each, NCH2CH2 each), 14.9
(OCH2CH3); IR (n-hexane), cm-1 (%) 2063.4 (30), 1980.9 (5),
1918.0 (100), [ν(CtO)], 1716.9 (50), [ν(CdO)]; MS (70 eV), 184W,
m/e (%) 643 (20) [M+ - 3 CO], 615 (35) [M+ - 4 CO], 587 (20)
[M+ - 5 CO], 403 (45) [M+ - W(CO)5]. X-ray crystal structure
(3E)-2b: 1H NMR (CDCl3, 25 °C) δ 7.48 (2 H, “d”, Ph), 7.39
3
3
(3 H, m, Ph), 6.89 (1 H, d, J ) 16.6 Hz, 5-H), 6.69 (1 H, d, J
) 16.6 Hz, 6-H), 6.38 (1 H, s, 3-H), 4.46 (2 H, q, OCH2), 3.57
(4 H, m broad, 2 NCH2), 2.01 (4 H, m broad, 2 NCH2CH2),
1.20 (3 H, t, OCH2CH3); 13C NMR (CDCl3, 25 °C) δ 267.6 (Cq,
WdC), 204.3 and 200.0 [1:4, trans- and cis-CO, W(CO)5], 153.4
(Cq, C4), 135.7 (CH, C6), 135.0 (i-C Ph), 128.7, 128.5, and 126.4
(1:2:2, CH each, Ph), 124.5 (CH, C5), 120.5 (CH, C3), 75.5
(OCH2), 50.5 (2 NCH2, broad), 24.8 (2 NCH2CH2, broad), 15.1
(OCH2CH3); IR (n-hexane), cm-1 (%) 2055.4 (15), 1924.9 (100)
[ν(CtO)]; MS (70 eV), 184W, m/e (%) 579 (1) [M+], 551 (0) [M+
- CO], 523 (4) [M+ - 2 CO], 495 (1) [M+ - 3 CO], 467 (3) [M+
- 4 CO], 439 (3) [M+ - 5 CO], 255 (82) [M+ - W(CO)5], 226
(100). Anal. Calcd for C22H21NO6W (579.3): C, 45.62; H, 3.65;
N, 2.42. Found: C, 45.59; H, 3.72; N, 2.02. X-ray crystal
structure analysis (code AUM_1078): formula C22H21NO6W,
M ) 579.25, orange crystal, 0.50 × 0.20 × 0.10 mm, a )
6.465(1) Å, b ) 11.510(1) Å, c ) 15.575(1) Å, R ) 73.21(1)°, â
) 84.07(1)°, γ ) 84.08(1)°, V ) 1100.4(3) Å3, Fcalc ) 1.748 g
cm-3, F(000) ) 564 e, µ ) 52.86 cm-1, empirical absorption
correction via æ scan data (0.178 e T e 0.620), Z ) 2, triclinic,
space group P1h (No. 2), λ ) 0.71073 Å, T ) 223 K, ω/2θ scans,
analysis of compound 6b (code AUM_1830): formula C31H29
-
NO8W × (0.25 C4H10O), M ) 745.93, orange crystal 0.30 ×
0.25 × 0.10 mm, a ) 60.883(1) Å, b ) 11.033(1) Å, c ) 20.858(1)
Å, â ) 101.54(1)°, V ) 13727.6(14) Å3, Fcalc ) 1.444 g cm-3
,
F(000) ) 5928 e, µ ) 34.12 cm-1, absorption correction via
SORTAV (0.428 e T e 0.727), Z ) 16, monoclinic, space group
C2/c (No. 15), λ ) 0.71073 Å, T ) 198 K, ω and æ scans, 38 610
reflections collected ((h, (k, (l), [(sin θ)/λ] ) 0.66 Å 16183
(Rint ) 0.041) independent and 11 924 observed reflections [I
g 2σ(I)], 752 refined parameters, R ) 0.049, wR2 ) 0.138, max.
residual electron density 1.66 (-0.71) e Å-3 close to tungsten,
hydrogens calculated and refined as riding atoms, solvent
molecule refined with isotropic thermal displacement param-
eters.23
P en ta ca r bon yl{[3-(2,4,6-cycloh ep ta tr ien yl)-2-eth oxy-
4-p h en yl-1-cyclob u t en yl](d im et h yla m in o)m et h ylen e}-
tu n gsten [(3S*,4S*)-9c an d (3S*,4R*)-9c]. To N,N-Dimethyl-
3-phenylacrylamide (7a ) (263 mg, 1.50 mmol) in 2 mL of dry
4859 reflections collected (-h, (k, (l), [(sin θ)/λ] ) 0.62 Å-1
,
dichloromethane in
a 5 mL screw-top vessel was added
4446 (Rint ) 0.025) independent and 4035 observed reflections
[I g 2σ(I)], 272 refined parameters, R ) 0.050, wR2 ) 0.131,
max. residual electron density 3.36 (-3.94) e Å-3 close to
tungsten, hydrogens calculated and refined as riding atoms.23
phosphorus oxychloride (229 mg, 1.50 mmol) with stirring at
0 °C. To the pale yellow precipitate, which was formed within
ca. 30 min at 0 °C was added a mixture of pentacarbonyl[2-
(2,4,6-cycloheptatrienyl)-1-ethoxyethylidene]tungsten (1c) (486
mg, 1.00 mmol) and triethylamine (303 mg, 3.00 mmol) in 1
mL of dichloromethane. The mixture was brought to dryness
(20 °C, 2 kPa) after 16 h at 20 °C, and the residue was
dissolved in dichloromethane/diethyl ether (1:1) and separated
by chromatography on silica gel (column 25 × 2 cm). Elution
with n-pentane afforded colorless hexacarbonyltungsten, which
was discarded. Subsequent elution with n-pentane/dichloro-
methane (2:1) gave a yellow fraction containing compounds
(3S*,4S*)-9c and (3S*,4R*)-9c in a molar ratio 8:1 [553 mg,
86%, Rf ) 0.6 in 1:2 n-pentane/dichloromethane on silica gel,
(23) Data sets were collected with Nonius MACH3 and KappaCCD
diffractometers, equipped with a Nonius FR591 rotating anode genera-
tor. Programs used: data collection EXPRESS (Nonius B.V., 1994) and
COLLECT (Nonius B.V., 1998), data reduction MolEN (Fair, K. Enraf-
Nonius B.V., 1990) and Denzo-SMN (Otwinowski, Z., Minor, W.
Methods Enzymol. 1997, 276, 307-326), absorption correction for CCD
data SORTAV (Blessing, R. H. Acta Crystallogr. 1995, A51, 33-37.
Blessing, R. H. J . Appl. Crystallogr. 1997, 30, 421-426), structure
solution SHELXS-86 and SHELXS-97 (Sheldrick, G. M. Acta Crystal-
logr. 1990, A46, 467-473), structure refinement SHELXL-93 and
SHELXL-97 (Sheldrick, G. M. Universita¨t Go¨ttingen, 1997), graphics
DIAMOND (Brandenburg, K. Universita¨t Bonn, 1997).

Organic Syntheses via Transition Metal Complexes
Organometallics, Vol. 21, No. 8, 2002 1643
yellow crystals from 1:1 diethyl ether/n-pentane at - 20 °C,
mp 66 °C).
C3′), 48.6 (CH, C4′), 45.9 (NCH3 broad), 40.8 (CH, C1′′ C7H7),
15.5 (OCH2CH3).
P en ta ca r bon yl{[3-(2,4,6-cycloh ep ta tr ien yl)-2-eth oxy-
4-p h en yl-1-cyclob u t en yl]p yr r olid in om et h ylen e}t u n g-
st en [(3S*,4S*)-9d a n d (3S*,4R*)-9d ]. 3-Phenyl-1-pyrroli-
dinoprop-2-en-1-one (7b) (302 mg, 1.50 mmol) and phosphorus
oxychloride (230 mg, 1.50 mmol) were reacted with pentacar-
bonyl[2-(2,4,6-cycloheptatrienyl)-1-ethoxyethylidene]tung-
sten (1c) (486 mg, 1.00 mmol) and triethylamine (303 mg, 3.00
mmol) as described above to give a 3:1 mixture of compounds
(3S*,4S*)-9d and (3S*,4R*)-9d [440 mg, 66%, Rf ) 0.6 in 1:2
n-pentane/dichloromethane, on silica gel, yellow oil].
(3S*,4S*)-9d : 1H NMR (CDCl3, 25 °C) δ 7.19 (3 H, m, Ph),
7.07 (2 H, “d”, Ph), 6.46 (2 H, m, 4′′-H and 5′′-H C7H7), 6.03
and 5.82 (1 H each, m each, 3′′-H and 6′′-H C7H7), 5.24 and
(3S*,4S*)-9c: 1H NMR (CDCl3, 25 °C) δ 7.17 (3 H, m, Ph),
7.04 (2 H, “d”, Ph), 6.42 (2 H, m, 4′′-H and 5′′-H C7H7), 6.04
and 5.80 (1 H each, m each, 3′′-H and 6′′-H C7H7), 5.23 and
3
4.72 (1 H each, m each, 2′′-H and 7′′-H C7H7), 4.63 (1 H, d, J
3
4.72 (1 H each, m each, 2′′-H and 7′′-H C7H7), 4.70 (1 H, d, J
) 4.9 Hz, 4′-H), 4.06 and 4.00 (2:4, m each, 2 NCH2 and
3
) 4.8 Hz, 4′-H), 3.94 (2 H, m, diastereotopic OCH2), 3.78 (3 H,
diastereotopic OCH2), 3.72 (1 H, dd, J ) 9.2 and 4.9 Hz, 3′-
3
s, NCH3), 3.73 (1 H, dd, J ) 9.5 and 4.8 Hz, 3′-H), 3.60 (3 H,
H), 2.15 (4 H, m, 2 NCH2CH2), 1.62 (1 H, m, 1′′-H C7H7), 1.35
(3 H, t, OCH2CH3); 13C NMR (CDCl3, 25 °C)26 δ 237.4 (WdC),
203.1 and 199.0 [1:4, trans- and cis-CO, W(CO)5], 142.1 (Cq,
C2′), 139.3 (Cq, i-C Ph), 130.7 and 130.2 (1:1, CH each, C4′′
and C5′′ C7H7), 128.9 (2 CH, Ph), 128.8 (Cq, C1′), 127.8 and
126.7 (2:1, CH each, Ph), 124.7 and 124.2 (1:1, CH each, C3′′
and C6′′ C7H7); 122.5 and 122.1 (1:1, CH each, C2′′ and C7′′
C7H7), 66.3 (OCH2), 61.9 and 55.5 (NCH2 each), 48.6 (CH, C3′),
48.0 (CH, C4′), 39.1 (CH, C1′′ C7H7), 25.7 and 24.9 (NCH2CH2
each), 15.6 (OCH2CH3); IR (diffuse reflection), cm-1 (%) 2065.8
(33), 1942.2 (88), 1900.6 (100) [ν(CtO)]; MS (70 eV), 184W, m/e
(%) 669 (6) [M+], 641 (11) [M+ - CO], 613 (0) [M+ - 2 CO],
s, NCH3), 1.53 (1 H, m, 1′′-H C7H7), 1.31 (3 H, t, OCH2CH3);
13C NMR (CDCl3, 25 °C)26 δ 243.7 (WdC), 203.1 and 198.5 [1:4,
trans- and cis-CO, W(CO)5], 143.5 (Cq, C2′), 139.3 (Cq, i-C Ph),
130.8 and 130.3 (1:1, CH each, C4′′ and C5′′ C7H7), 129.0, 127.9
(2:2, CH each, Ph), 127.2 (Cq, C1′), 126.8 (p-CH Ph), 124.7 and
124.2 (1:1, CH each, C3′′ and C6′′ C7H7), 122.7 and 122.5 (1:1,
CH each, C2′′ and C7′′ C7H7), 66.1 (OCH2), 53.7 (NCH3 broad),
48.7 (CH, C3′), 48.2 (CH, C4′), 45.5 (NCH3 broad), 39.2 (CH,
C1′′ C7H7), 15.7 (OCH2CH3); IR (diffuse reflection), cm-1 (%)
2066.3 (43), 1942.0 (88), 1901.6 (100) [ν(CtO)]; MS (70 eV),
184W, m/e (%) 643 (5) [M+], 615 (12) [M+ - CO], 587 (1) [M+
2 CO], 559 (28) [M+ - 3 CO], 531 (8) [M+ - 4 CO], 503 (100)
[M+ - 5 CO], 319 (16) [M+ - W(CO)5]. Anal. Calcd for C27H25
-
585 (32) [M+ - 3 CO], 557 (7) [M+ - 4 CO], 529 (100) [M+
-
5 CO], 345 (12) [M+ - W(CO)5]. Anal. Calcd for C29H27NO6W
(669.4): C, 52.04; H, 4.07; N, 2.09. Found: C, 52.45; H, 4.27;
N, 1.98.
-
NO6W‚(1/2Et2O) (680.4): C, 51.19; H, 4.44; N, 2.06. Found:
C, 52.10; H, 4.84; N, 2.36. X-ray crystal structure analysis (code
AUM_849): formula C27H25NO6W × (1/2C4H10O), M ) 680.39,
yellow crystal, 0.40 × 0.30 × 0.20 mm, a ) 10.782(1) Å, b )
21.102(2) Å, c ) 12.936(1) Å, â ) 92.35(1)°, V ) 2940.7(5) Å3,
(3S*,4R*)-9d : 1H NMR (CDCl3, 25 °C) δ 7.31 (3 H, m, Ph),
7.21 (2 H, m, Ph), 6.69 (2 H, m, 4′′-H and 5′′-H C7H7), 6.29
and 6.22 (1 H each, m each, 3′′-H and 6′′-H C7H7), 5.45 and
5.32 (1 H each, m each, 2′′-H and 7′′-H C7H7), 3.99 and 3.79
(3:3, m each, diastereotopic OCH2 and 2 NCH2), 3.29 (1 H, dd,
3J ) 7.2 and 0.9 Hz, 3′-H), 2.12 and 1.93 (3:2, m each, 1′′-H
C7H7 and 2 NCH2CH2), 1.32 (3 H, t, OCH2CH3); 13C NMR
(CDCl3, 25 °C) (partial assignment only, due to overlapping
signals)26 δ 236.1 (WdC), 203.1 and 199.7 [1:4, trans- and cis-
CO, W(CO)5], 147.7 (Cq, C2′), 144.6 (Cq, i-C Ph), 131.1 (2 CH,
C4′′ and C5′′ C7H7), 128.7, 127.1, and 126.8 (2:2:1, CH each,
Ph), 125.9 (Cq, C1′); 125.8, 125.5, and 122.2 (2:2:2, CH each,
C7H7),25 66.1 (OCH2), 62.3 and 55.8 (NCH2 each), 53.5 (CH,
C3′), 48.6 (CH, C4′,), 40.2 (CH, C1′′ C7H7), 25.9 and 24.9
(NCH2NCH2 each), 15.3 (OCH2CH3).
F
calc ) 1.537 g cm-3, F(000) ) 1348 e, µ ) 39.69 cm-1, empirical
absorption correction via æ scan data (0.300 e T e 0.504), Z
) 4, monoclinic, space group P21/c (No. 14), λ ) 0.71073 Å, T
) 293 K, ω/2θ scans, 6302 reflections collected (-h, -k, (l),
[(sin θ)/λ] ) 0.62 Å-1, 5982 independent (Rint ) 0.030) and 3810
observed reflections [I g 2 σ(I)], 340 refined parameters, R )
0.032, wR2 ) 0.065, max. residual electron density 0.77 (-0.40)
e Å-3, disorder in the OEt group (67:33), half disordered ether
molecule in the asymmetric unit, hydrogens calculated and
refined as riding atoms.23
P en ta ca r bon yl{[3-(2,4,6-cycloh ep ta tr ien yl)-2-eth oxy-
4-p h en yl-1-cyclob u t en yl]m or p h olin om et h ylen e}t u n g-
sten [(3S*,4S*)-9e a n d (3S*,4R*)-9e]. 1-Morpholino-3-phen-
ylprop-2-en-1-one (7c) (326 mg, 1.50 mmol) and phosphorus
oxychloride (230 mg, 1.50 mmol) were reacted with pentacar-
bonyl[2-(2,4,6-cycloheptatrienyl)-1-ethoxyethylidene]tung-
sten (1c) (486 mg, 1.00 mmol) and triethylamine (303 mg, 3.00
mmol) as described above to give a 20:1 mixture of compounds
(3S*,4S*)-9e and (3S*,4R*)-9e (424 mg, 62%, Rf ) 0.4 in 1:2
n-pentane/dichloromethane, on silica gel, yellow crystals from
n-pentane, mp 46 °C).
(3S*,4R*)-9c: 1H NMR (CDCl3, 25 °C) δ 7.78 (3 H, m, Ph),
7.18 (2 H, m, Ph), 6.64 (2 H, m, 4′′-H and 5′′-H C7H7), 6.26
and 6.19 (1 H each, m each, 3′′-H and 6′′-H C7H7), 5.41 and
(3S*,4S*)-9e: 1H NMR (CDCl3, 25 °C) δ 7.19 (3 H, m, Ph),
7.05 (2 H, “d”, Ph), 6.45 (2 H, m, 4′′-H and 5′′-H C7H7), 6.06
and 5.80 (1 H each, m each, 3′′-H and 6′′-H C7H7), 5.22 and
3
5.35 (1 H each, m each, 2′′-H and 7′′-H C7H7), 4.07 (1 H, d, J
) ca. 2.3 Hz, 4′-H), 3.89 (2 H, m, diastereotopic OCH2), 3.75
and 3.41 (3 H each, s each, NCH3 each), 3.28 (1 H, dd, 3J )
8.0 and 2.3 Hz, 3′-H), 2.17 (1 H, m, 1′′-H C7H7), 1.29 (3 H, t,
OCH2CH3); 13C NMR (CDCl3, 25 °C) (partial assignment only,
due to overlapping signals)26 δ24? (CrdC) and [1:4, trans- and
cis-CO, Cr(CO)5], 146.8 (Cq, C2′), 142.0 (Cq, i-C Ph), 131.1 and
131.0 (1:1, CH each, C4′′ and C5′′ C7H7); 128.7, 127.2, and
126.8 (2:2:1, CH each, Ph), 125.7 (CH C7H7), 125.5 (Cq, C1′),
125.3 (CH, C7H7), 66.1 (OCH2), 53.9 (NCH3 broad), 53.1 (CH,
(24) Signal not observed due to dynamic line-broadening.
(25) One signal missing probably due to overlap with signals of the
major isomer.
(26) The NMR data were derived from spectra of the mixture of
compounds (3S*,4S*)-9 and (3S*,4S*)-9, but they are listed separately
for each compound. The assignment of signals C3′ and C4′, and 3′-H
and 4′-H, respectively, is based on the pattern, which has been derived
from compound 9a by 1J (C,H) and 2,3J (C,H) correlation experiments.

1644 Organometallics, Vol. 21, No. 8, 2002
Aumann et al.
3
4.68 (1 H each, m each, 2′′-H and 7′′-H C7H7), 4.75 (1 H, d, J
) 4.9 Hz, 4′-H); 4.43, 4.32, 4.26, and 4.18 (1 H each, m each,
2 OCH2CH2N), 3.95 (6 H, m, diastereotopic OCH2CH3 and 2
NCH2), 3.79 (1 H, dd, 3J ) 9.3 and 4.9 Hz, 3′-H), 1.60 (1 H, m,
1′′-H C7H7), 1.30 (3 H, t, OCH2CH3); 13C NMR (CDCl3, 25 °C)26
δ 241.5 (WdC), 202.8 and 198.3 [1:4, trans- and cis-CO,
W(CO)5], 142.7 (Cq, C2′), 139.0 (Cq, i-C Ph), 130.9 and 130.1
(1:1, CH each, C4′′ and C5′′ C7H7), 128.9, 127.8 (2:2, CH each,
Ph), 127.1 (Cq, C1′), 126.9 (p-CH), 125.0 and 124.3 (1:1, CH
each, C3′′ and C6′′ C7H7), 122.1 and 121.8 (1:1, CH each, C2′′
and C7′′ C7H7), 67.8 and 67.6 (OCH2CH2N each), 66.3 (OCH2),
62.9 and 55.0 (NCH2 each), 48.5 (CH, C3′), 48.4 (CH, C4′), 39.0
(CH, C1′′ C7H7), 15.6 (OCH2CH3); IR (diffuse reflection), cm-1
(%) 2066.8 (33), 1940.1 (88), 1900.1 (100) [ν(CtO)]; MS (70
eV), 184W, m/e (%) 685 (2) [M+], 657 (8) [M+ - CO], 629 (0)
[M+ - 2 CO], 601 (34) [M+ - 3 CO], 573 (9) [M+ - 4 CO], 545
(100) [M+ - 5 CO], 361 (15) [M+ - W(CO)5]. Anal. Calcd for
(3S*,4S*)-9g and (3S*,4R*)-9g (184 mg, 68%, Rf ) 0.6 in 1:2
n-pentane/dichloromethane, on silica gel, yellow oil).
(3S*,4S*)-9g: 1H NMR (CDCl3, 25 °C) δ 7.18 (3 H, m, Ph),
7.05 (2 H, “d”, Ph), 6.45 (2 H, m, 4′′-H and 5′′-H C7H7), 6.04
and 5.80 (1 H each, m each, 3′′-H and 6′′-H C7H7), 5.26 and
3
4.71 (1 H each, m each, 2′′-H and 7′′-H C7H7), 4.68 (1 H, d, J
) 4.9 Hz, 4′-H), 4.16 and 4.08 (2:2, m each, 2 NCH2), 3.93 (2
H, m, diastereotopic OCH2), 3.69 (1 H, dd, 3J ) 9.3 and 4.9
Hz, 3′-H), 2.12 (4 H, m, 2 NCH2CH2), 1.57 (1 H, m, 1′′-H C7H7),
1.31 (3 H, t, OCH2CH3); 13C NMR (CDCl3, 25 °C)26 δ 256.5
(CrdC), 223.6 and 218.3 [1:4, trans- and cis-CO, Cr(CO)5],
142.4 (Cq, C2′), 139.7 (Cq, i-C Ph), 131.0 and 130.5 (1:1, CH
each, C4′′ and C5′′ C7H7), 129.2 (2 CH, Ph), 128.4 (Cq, C1′),
128.1 and 126.9 (2:1, CH each, Ph), 124.9 and 124.4 (1:1, CH
each, C3′′ and C6′′ C7H7), 123.1 and 122.9 (1:1, CH each, C2′′
and C7′′ C7H7), 66.5 (OCH2), 59.7 and 57.0 (NCH2 each), 49.0
(CH, C3′), 47.7 (CH, C4′), 39.3 (CH, C1′′ C7H7), 25.8 and 25.5
(NCH2CH2 each), 16.0 (OCH2CH3); IR (hexane), cm-1 (%)
2048.8 (15), 1923.9 (99) [ν(CtO)]; MS (70 eV), m/e (%) 537 (3)
[M+], 509 (11) [M+ - CO], 481 (0) [M+ - 2 CO], 453 (30) [M+
- 3 CO], 425 (6) [M+ - 4 CO], 397 (97) [M+ - 5 CO], 345 (21)
[M+ - Cr(CO)5], 275 (23), 262 (25), 238 (25), 115 (52), 103 (21),
91 (92), 52 (100). Anal. Calcd for C29H27NO6Cr (537.5): C, 64.80;
H, 5.06; N, 2.61. Found: C, 65.02; H, 5.17; N, 2.51.
C
29H27NO7W (685.4): C, 50.82; H, 3.97; N, 2.04. Found: C,
50.76; H, 3.93; N, 1.80.
(3S*,4R*)-9e: spectroscopic data were not collected.
P en ta ca r bon yl{[3-(2,4,6-cycloh ep ta tr ien yl)-2-eth oxy-
4-p h en yl-1-cyclob u t en yl](d im et h yla m in o)m et h ylen e}-
ch r om iu m [(3S*,4S*)-9f a n d (3S*,4R*)-9f]. N,N-Dimethyl-
3-phenylacrylamide (7a ) (175 mg, 1.00 mmol) and oxalyldi-
chloride (140 mg, 1.10 mmol) were reacted with pentacarbonyl-
[2-(2,4,6-cycloheptatrienyl)-1-ethoxyethylidene]chromium (1d )
(177 mg, 0.50 mmol) and triethylamine (202 mg, 2.00 mmol)
to give a 5:2 mixture of compounds (3S*,4S*)-9f and (3S*,4R*)-
9f (184 mg, 72%, Rf ) 0.6 in 1:2 n-pentane/dichloromethane,
on silica gel, yellow oil).
(3S*,4R*)-9g: 1H NMR (CDCl3, 25 °C) δ 7.28 (3 H, m, Ph),
7.19 (2 H, m, Ph), 6.67 (2 H, m, 4′′-H/5′′-H C7H7), 6.28 and
6.20 (1 H each, m each, 3′′-H/6′′-H C7H7), 5.41 and 5.32 (1 H
3
each, m each, 2′′-H/7′′-H C7H7), 4.02 (1 H, d, J ) ca. 0.9 Hz,
4′-H), 3.92 (2 H, m, diastereotopic OCH2), 3.88 and 3.68 (3:1,
m each, 2 NCH2), 3.26 (1 H, dd, 3J ) 7.3 and 0.9 Hz, 3′-H),
2.07 and 1.94 (3:2, m each, 1′′-H C7H7 and 2 NCH2CH2), 1.32
(3 H, t, OCH2CH3); 13C NMR (CDCl3, 25 °C)26 δ 258.0 (CrdC),
223.7 and 218.6 [1:4, trans- and cis-CO, Cr(CO)5], 147.5 (Cq,
C2′), 142.4 (Cq, i-C Ph), 131.4 and 131.3 (1:1, CH each, C4′′
and C5′′ C7H7), 128.9, 127.4, and 126.9 (2:2:1, CH each, Ph),
126.2 (Cq, C1′), 126.0, 125.5, 124.6, and 122.8 (1:1:1:1, CH each,
C7H7), 66.3 (OCH2), 60.1 and 57.3 (NCH2 each), 53.8 (CH, C3′),
48.6 (CH, C4′), 40.8 (CH, C1′′ C7H7), 25.9 and 25.5 (NCH2NCH2
each), 14.4 (OCH2CH3).
(3S*,4S*)-9f: 1H NMR (CDCl3, 25 °C) δ 7.18 (3 H, m, Ph),
7.04 (2 H, “d”, Ph), 6.44 (2 H, m, 4′′-H/5′′-H C7H7), 6.06 and
5.80 (1 H each, m each, 3′′-H/6′′-H C7H7), 5.26 and 4.73 (1 H
3
each, m each, 2′′-H/7′′-H C7H7), 4.73 (1 H, d, J ) 4.8 Hz, 4′-
H), 3.92 (2 H, m, diastereotopic OCH2), 3.86 (3 H, s, NCH3),
3
3.69 (1 H, dd, J ) 9.5 and 4.8 Hz, 3′-H), 3.64 (3 H, s, NCH3),
1.54 (1 H, m, 1′′-H C7H7), 1.31 (3 H, t, OCH2CH3); 13C NMR
(CDCl3, 25 °C)26 δ 262.1 (CrdC), 223.3 and 217.6 [1:4, trans-
and cis-CO, Cr(CO)5], 141.9 (Cq, C2′), 139.2 (Cq, i-C Ph), 130.7
and 130.2 (1:1, CH each, C4′′ and C5′′ C7H7); 128.8, 127.7, and
126.6 (2:2:1, CH each, Ph), 126.5 (Cq, C1′), 124.6 and 124.1
(1:1, CH each, C3′′ and C6′′ C7H7), 122.8 and 122.6 (1:1, CH
each, C2′′ and C7′′ C7H7), 65.9 (OCH2), 51.0 (NCH3 broad), 48.8
(CH, C3′), 47.5 (CH, C4′), 46.7 (NCH3 broad), 39.0 (CH, C1′′
C7H7), 15.6 (OCH2CH3); IR (hexane), cm-1 (%) 2051.0 (10),
1926.0 (99) [ν(CtO)]; MS (70 eV), m/e (%) 511 (5) [M+], 483
(12) [M+ - CO], 455 (1) [M+ - 2 CO], 427 (28) [M+ - 3 CO],
P en ta ca r bon yl{[3-(2,4,6-cycloh ep ta tr ien yl)-2-eth oxy-
4-p h en yl-1-cyclob u t en yl]-m or p h olin om et h ylen e}ch r o-
m iu m [(3S*,4S*)-9h a n d (3S*,4R*)-9h ]. 1-Morpholino-3-
phenylprop-2-en-1-one (7c) (217 mg, 1.00 mmol) and oxalyl-
dichloride (140 mg, 1.10 mmol) were reacted with penta-
carbonyl[2-(2,4,6-cycloheptatrienyl)-1-ethoxyethylidene]chro-
mium (1d ) (177 mg, 0.50 mmol) and triethylamine (202 mg,
2.00 mmol) as described above to give a 9:1 mixture of
compounds (3S*,4S*)-9h and (3R*,4S*)-9h (144 mg, 52%, Rf
) 0.4 in 1:2 n-pentane/dichloromethane, on silica gel, yellow
crystal from n-pentane, mp 72 °C).
399 (8) [M+ - 4 CO], 371 (100) [M+ - 5 CO], 319 (20) [M+
Cr(CO)5], 275 (21), 236 (41), 115 (48), 91 (100), 52 (90).
-
(3S*,4R*)-9f: 1H NMR (CDCl3, 25 °C) δ 7.29 (3 H, m, Ph),
7.19 (2 H, m, Ph), 6.66 (2 H, m, 4′′-H and 5′′-H C7H7), 6.28
and 6.21 (1 H each, m each, 3′′-H and 6′′-H C7H7), 5.41 and
(3S*,4S*)-9h : 1H NMR (CDCl3, 25 °C) δ 7.19 (3 H, m, Ph),
7.04 (2 H, “d”, Ph), 6.46 (2 H, m, 4′′-H and 5′′-H C7H7), 6.09
and 5.83 (1 H each, m each, 3′′-H and 6′′-H C7H7), 5.22 and
3
5.36 (1 H each, m each, 2′′-H and 7′′-H C7H7), 4.11 (1 H, d, J
3
) ca. 0.7 Hz, 4′-H), 3.90 (2 H, m, diastereotopic OCH2), 3.78
and 3.46 (3 H each, s each, NCH3 each), 3.22 (1 H, dd, 3J )
8.3 and 0.7 Hz, 3′-H), 2.19 (1 H, m, 1′′-H C7H7), 1.29 (3 H, t,
OCH2CH3); 13C NMR (CDCl3, 25 °C)26 δ 263.4 (CrdC), 223.3
and 217.8 [1:4, trans- and cis-CO, Cr(CO)5], 144.4 (Cq, C2′),
141.9 (Cq, i-C Ph), 131.0 and 130.9 (1:1, CH each, C4′′ and
C5′′ C7H7); 128.5, 127.1, and 126.6 (2:2:1, CH each, Ph), 125.6
and 125.1 (1:1, CH each, C7H7), 124.3 and 122.8 (CH C7H7),
65.9 (OCH2), 53.1 (CH, C3′), 51.2 (NCH3 broad), 48.3 (CH, C4′),
47.0 (NCH3 broad), 40.8 (CH, C1′′ C7H7), 15.4 (OCH2CH3).
P en ta ca r bon yl{[3-(2,4,6-cycloh ep ta tr ien yl)-2-eth oxy-
4-p h en yl-1-cyclob u t en yl]p yr r olid in om et h ylen e }ch r o-
m iu m [(3S*,4S*)-9g a n d (3S*,4R*)-9g]. 3-Phenyl-1-pyrroli-
dinoprop-2-en-1-one (7b) (201 mg, 1.00 mmol) and oxalyldi-
chloride (140 mg, 1.10 mmol) were reacted with pentacarbonyl-
[2-(2,4,6-cycloheptatrienyl)-1-ethoxyethylidene]chromium (1d )
(177 mg, 0.50 mmol) and triethylamine (202 mg, 2.00 mmol)
as described above to give a 2:1 mixture of compounds
4.68 (1 H each, m each, 2′′-H and 7′′-H C7H7), 4.78 (1 H, d, J
) 4.9 Hz, 4′-H); 4.52, 4.41, 4.28, and 4.19 (1 H each, m each,
2 OCH2CH2N), 3.93 (6 H, m, diastereotopic OCH2CH3 and 2
NCH2), 3.76 (1 H, dd, 3J ) 9.3 and 4.9 Hz, 3′-H), 1.62 (1 H, m,
1′′-H C7H7), 1.32 (3 H, t, OCH2CH3); 13C NMR (CDCl3, 25 °C)26
δ 259.9 (CrdC), 223.0 and 217.4 [1:4, trans- and cis-CO,
Cr(CO)5], 140.9 (Cq, C2′), 139.0 (Cq, i-C Ph), 130.8 and 130.0
(1:1, CH each, C4′′ and C5′′ C7H7); 128.8, 127.8, and 126.8 (2:
2:1, CH each, Ph), 126.4 (Cq, C1′), 124.9 and 124.2 (1:1, CH
each, C3′′ and C6′′ C7H7), 122.2 and 121.9 (1:1, CH each, C2′′
and C7′′ C7H7), 67.8 and 67.6 (OCH2CH2N each), 66.1 (OCH2),
60.5 and 55.9 (NCH2 each), 48.5 (CH, C3′), 47.7 (CH, C4′), 38.8
(CH, C1′′ C7H7), 15.6 (OCH2CH3); IR (hexane), cm-1 (%) 2050.9
(12), 1926.7 (100) [ν(CtO)]; MS (70 eV), m/e (%) 553 (2) [M+],
525 (4) [M+ - CO], 497 (0) [M+ - 2 CO], 469 (13) [M+ - 3
CO], 441 (4) [M+ - 4 CO], 413 (47) [M+ - 5 CO], 385 (1) [M+
- Cr(CO)5], 275 (11), 193 (25), 115 (36), 103 (16), 91 (100), 52
(54).

Organic Syntheses via Transition Metal Complexes
Organometallics, Vol. 21, No. 8, 2002 1645
(3S*,4R*)-9h : 1H NMR (CDCl3, 25 °C) δ 7.20 (5 H, m, Ph),
6.65 (2 H, m, 4′′-H and 5′′-H C7H7), 6.23 (2 H, m, 3′′-H and
6′′-H C7H7), 5.39 (2 H, m, 2′′-H and 7′′-H C7H7), 4.19 (4 H, m,
2 OCH2CH2N), 3.95 (7 H, m, 4′-H and OCH2CH3 and 2 NCH2),
mg, 1.00 mmol) and phosphorus oxychloride (153 mg, 1.50
mmol) were reacted with pentacarbonyl(1-ethoxybutylidene]-
tungsten (1e) (219 mg, 0.50 mmol) and triethylamine (202 mg,
2.00 mmol) as described above to afford a 5:1 mixture of
compounds (3S*,4S*)-9j and (3S*,4R*)-9j (134 mg, 43%, Rf )
0.6 in 1:2 n-pentane/dichloromethane, on silica gel, yellow oil).
(3S*,4S*)-9j:27 1H NMR (CDCl3, 25 °C) δ 7.26 (3H, m, Ph),
3
3.29 (1 H, dd, J ) 7.3 and 0.9 Hz, 3′-H), 2.20 (1 H, m, 1′′-H
C7H7), 1.30 (3 H, t, OCH2CH3); 13C NMR (CDCl3, 25 °C) (partial
assignment only, due to overlapping signals)26 24 (CrdC) and
δ
[1:4, trans- and cis-CO, Cr(CO)5],24 (Cq, C2′), 141.4 (Cq, i-C Ph),
131.0 and 130.8 (1:1, CH each, C4′′ and C5′′ C7H7), 128.6 and
127.1 (2:2, CH each, Ph), 125.6 (Cq, C1′), 125.1 and 122.8 (1:1,
CH each, C7H7), 67.7 and 67.3 (OCH2CH2N each), 65.8 (OCH2),
60.3 and 56.2 (NCH2 each), 52.2 (CH, C3′), 48.0 (CH, C4′), 40.9
(CH, C1′′ C7H7), 15.2 (OCH2CH3).
7.09 (2 H, “d”, Ph), 4.51 (1 H, d, J ) 4.9 Hz, 4′-H), 4.05 (2 H,
3
m, diastereotopic OCH2), 3.98 (4 H, m, 2 NCH2), 3.37 (1 H, m,
3′-H), 2.07 (4 H, m, 2 NCH2CH2), 1.34 (3 H, t, OCH2CH3), 1.00
(4 H, m, CH2CH2CH3), 0.60 (3 H, t, CH2CH2CH3); 13C NMR
(CDCl3, 25 °C) δ 234.3 (WdC), 203.5 and 199.4 [1:4, trans-
and cis-CO, W(CO)5], 149.3 (Cq, C2′), 140.0 (Cq, i-C Ph), 128.8,
127.9, and 126.5 (2:2:1, CH each, Ph), 126.0 (Cq, C1′), 65.4
(OCH2), 62.1 and 55.3 (NCH2 each), 48.8 (CH, C4′), 46.2 (CH,
C3′), 31.1 (CH2CH2CH3), 25.9 and 24.9 (NCH2CH2 each), 20.1
(CH2CH2CH3), 15.5 (OCH2CH3), 14.0 (CH2CH2CH3); IR (diffuse
reflection), cm-1 (%) 2064.8 (35), 1901.6 (100) [ν(CtO)]; MS
(70 eV), 184W, m/e (%) 621 (4) [M+], 593 (9) [M+ - CO], 565
(0) [M+ - 2 CO], 537 (32) [M+ - 3 CO], 509 (9) [M+ - 4 CO],
481 (100) [M+ - 5 CO], 297 (16) [M+ - W(CO)5]. Anal. Calcd
for C25H27NO6W (621.3): C, 48.33; H, 4.38; N, 2.25. Found: C,
49.18; H, 4.56; N, 2.11.
P en ta ca r bon yl[(2-eth oxy-4-p h en yl-3-p r op yl-1-cyclobu -
ten yl)(d im eth yla m in o)m eth ylen e]tu n gsten [(3S*,4S*)-9i
a n d (3S*,4R*)-9i]. N,N-Dimethyl-3-phenylacrylamide (7a )
(175 mg, 1.00 mmol) and phosphorus oxychloride (153 mg, 1.00
mmol) were reacted with pentacarbonyl(1-ethoxybutylidene]-
tungsten (1e) (219 mg, 0.50 mmol) and triethylamine (202 mg,
2.00 mmol) to give a 7:1 mixture of compounds (3S*,4S*)-9i
and (3S*,4R*)-9i (158 mg, 53%, Rf ) 0.6 in 1:2 n-pentane/
dichloromethane, on silica gel, yellow crystals from n-pentane,
mp 39 °C).
(3S*,4R*)-9j: 13C NMR (CDCl3, 25 °C) (partial assignment
only, due to overlapping signals) 149.9, 142.9, 128.4, 126.8,
126.4, 55.6, 52.1, 50.8, 34.6, 29.0, 22.6, 21.4, 14.3, 14.0.
P en ta ca r bon yl[(2-eth oxy-4-p h en yl-3-p r op yl-1-cyclobu -
t en yl)m or p h olin om et h ylen e]t u n gst en [(3S*,4S*)- a n d
(3S*,4R*)-9k]. 1-Morpholino-3-phenylprop-2-en-1-one (7c) (217
mg, 1.00 mmol) and phosphorus oxychloride (153 mg, 1.50
mmol) were reacted with pentacarbonyl(1-ethoxybutylidene]-
tungsten (1e) (219 mg, 0.50 mmol) and triethylamine (202 mg,
2.00 mmol) as described above to give a 20:1 mixture of
compounds (3S*,4S*)-9k and (3S*,4R*)-9k (153 mg, 48%, Rf
) 0.5 in 1:2 n-pentane/dichloromethane, on silica gel, yellow
crystals from n-pentane, mp 51 °C).
(3S*,4S*)-9i:27 1H NMR (CDCl3, 25 °C) δ 7.25 (3 H, m, Ph),
7.08 (2 H, “d”, Ph), 4.59 (1 H, d, J ) 4.9 Hz, 4′-H), 4.01 (2 H,
3
m, diastereotopic OCH2), 3.79 (3 H, s, NCH3), 3.56 (3 H, s,
NCH3), 3.37 (1 H, m, 3′-H), 1.32 (3 H, t, OCH2CH3), 1.00 (4 H,
m, 3′-CH2CH2), 0.56 (3 H, t, CH2CH2CH3); 13C NMR (CDCl3,
25 °C) δ 241.2 (WdC), 203.0 and 198.8 [1:4, trans- and cis-
CO, W(CO)5], 146.4 (Cq, C2′), 140.0 (Cq, i-C Ph); 128.8, 127.9,
and 126.6 (2:2:1, CH each, Ph), 125.5 (Cq, C1′), 65.3 (OCH2),
53.9 (NCH3 broad), 48.7 (CH, C4′), 46.1 (CH, C3′), 45.3 (NCH3
broad), 31.2 (CH2CH2CH3), 20.2 (CH2CH2CH3), 15.6 (OCH2CH3),
14.1 (CH2CH2CH3); IR (diffuse reflection), cm-1 (%) 2065.8 (38),
1941.8 (86), 1901.8 (100) [ν(CtO)]; MS (70 eV), 184W, m/e (%)
595 (2) [M+], 567 (11) [M+ - CO], 539 (0) [M+ - 2 CO], 511
(32) [M+ - 3 CO], 483 (7) [M+ - 4 CO], 455 (100) [M+ - 5
CO], 271 (22) [M+ - W(CO)5]. Anal. Calcd for C23H25NO6W
(595.3): C, 46.41; H, 4.23; N, 2.35. Found: C, 46.45; H, 4.33;
N, 2.28.
(3S*,4S*)-9k :27 1H NMR (CDCl3, 25 °C) δ 7.29 (3 H, m, Ph),
3
7.07 (2 H, “d”, Ph), 4.68 (1 H, d, J ) 4.9 Hz, 4′-H), 4.52 and
4.25 (1:2, m each, OCH2CH2N), 4.03 and 3.84 (5:2, m each,
diastereotopic OCH2CH3 and OCH2CH2N), 3.42 (1 H, m, 3′-
H), 1.32 (3 H, t, OCH2CH3), 1.01 (4 H, m, CH2CH2CH3), 0.59
(3 H, t, CH2CH2CH3); 13C NMR (CDCl3, 25 °C) δ 239.6 (WdC),
203.0 and 198.4 [1:4, trans- and cis-CO, W(CO)5], 144.7 (Cq,
C2′), 139.7 (Cq, i-C Ph), 128.7, 128.0, and 126.7 (2:2:1, CH each,
Ph), 124.7 (Cq, C1′), 67.9 and 67.7 (OCH2CH2N each), 65.3
(OCH2), 63.0 and 54.7 (NCH2 each), 48.9 (CH, C4′), 46.1 (CH,
C3′), 31.1 (CH2CH2CH3), 20.2 (CH2CH2CH3), 15.6 (OCH2CH3),
14.0 (CH2CH2CH3); IR (diffuse reflection), cm-1 (%) 2066.8 (33),
1940.1 (88), 1900.1 (100) [ν(CtO)]; MS (70 eV), 184W, m/e (%)
637 (2) [M+], 609 (8) [M+ - CO], 581 (0) [M+ - 2 CO], 553 (34)
[M+ - 3 CO], 525 (9) [M+ - 4 CO], 497 (100) [M+ - 5 CO], 313
(15) [M+ - W(CO)5]. Anal. Calcd for C25H27NO7W (637.3): C,
47.11; H, 4.27; N, 2.20. Found: C, 46.92; H, 4.24; N, 2.23.
(3S*,4R*)-9k : spectroscopic data were not collected.
Ack n ow led gm en t. This work was supported by the
Deutsche Forschungsgemeinschaft and the Fonds der
Chemischen Industrie.
(3S*,4R*)-9i: 13C NMR (CDCl3, 25 °C) (partial assignment
only, due to overlapping signals) δ 128.4, 126.9, 52.1, 50.6, 45.7,
34.5, 21.8, 14.3.
P en ta ca r bon yl[(2-eth oxy-4-p h en yl-3-p r op yl-1-cyclobu -
t en yl)p yr r olid in om et h ylen e]t u n gst en [(3S*,4S*)- a n d
(3S*,4R*)-9j]. 3-Phenyl-1-pyrrolidinoprop-2-en-1-one (7b) (201
Su p p or tin g In for m a tion Ava ila ble: Details of the X-ray
crystal structure analyses, including bond distances and angles
for compounds 9c, 6b, and (3E)-2b. This material is available
free of charge via the Internet at http://pubs.acs.org.
(27) The configurational assignment is based on the coupling
constant 3J (3′H,4′-H) ) 4.9 Hz.
OM0108604