1,1-Cycloaddition of oxalyl dichloride with dialkenylmetal compounds: Formation of cyclopentadienone derivatives by the reaction of 1,4,-dilithio-1,3-dienes or zirconacyclopentadienes with oxalyl chloride in the presence of CuCl

Article abstract of DOI:10.1021/ja0506713

1,4-Dilithio-1,3-dienes or zirconacyclopentadienes reacted with oxalyl chloride in the presence of CuCl in a 1,1-cycloaddition manner to give cyclopentadienone derivatives in high yields along with the elimination of CO. Copyright

Full text of DOI:10.1021/ja0506713

Published on Web 05/12/2005
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,1-Cycloaddition of Oxalyl Dichloride with Dialkenylmetal Compounds:
Formation of Cyclopentadienone Derivatives by the Reaction of
1
,4,-Dilithio-1,3-dienes or Zirconacyclopentadienes with Oxalyl Chloride in the
Presence of CuCl
Chao Chen, Chanjuan Xi,* Yanfeng Jiang, and Xiaoyin Hong
Department of Chemistry, Tsinghua UniVersity, Beijing, 100084, China
Received February 2, 2005; E-mail: cjxi@tsinghua.edu.cn
Oxalyl chloride, as carbonylated reagent, had been reported to
undergo substitution reaction with 2 equiv of monofunctional
organometallic compound, such as Grignard reagent, organolithium,
To extend the reaction of 1,4-dicopper-1,3-diene derivatives 2, we
tried various 1,4-dicopper-1,3-dienes that easily generated in situ
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from the corresponding zirconacyclopentadienes 4 and CuCl. For
and organocopper compound, to form 1,2-diorgano-1,2-dione (eq
example, the reaction of 1,4-dicopper-1,3-diene 2d with oxalyl
chloride in the presence of 2 equiv of DMPU (N,N′-dimethylpropyl-
1
1).
8
9
eneurea) at 0 °C for 1 h led to compound 3d in excellent yield
eq 4). Meanwhile, generated gas was collected and detected by
(
GC. Only CO gas was measured, and no carbon dioxide was
detected.
When dianionic reagents of these organometallic compounds were
used, however, the reaction frequently led to the formation of
complex, or inseparable, mixture owing to over-addition, polym-
erization, or decomposition. Therefore, cyclization reaction of
organodimetallic reagent (such as organodilithium, organodicopper,
or organodimagnesium reagent) with oxalyl chloride is rare,
although a successful cyclization of 1,4-dilithio-1,3-dienes with
dimethyl oxalates to afford o-benzoquinones has been reported.2
To the best of our knowledge, no 1,1-cycloaddition of oxalyl
chloride with dicarbanionic reagent has been reported in which
oxalyl chloride acts as one carbonyl donor. Herein we report the
first 1,1-cycloaddition of oxalyl chloride with 1,4-dilithio-1,3-dienes
or zirconcyclopentadienes to afford cyclopentadienone derivatives
in the presence of CuCl (eq 2), in which the carbon-carbon bond
of 1,2-dicarbonyl cleaved during nucleophilic addition.3
Listed in Table 1 are representative examples of cyclopentadi-
enone derivatives 3 obtained by the reaction with zirconacyclo-
pentadienes or 1,4-dilithio-1,3-dienes. Both could be symmetrically
and unsymmetrically substituted dienes bearing alkyl and aryl
groups.
It was noteworthy that 1,4-dicopper-1,3-dienes, which generated
from the corresponding zirconacyclopentadienes 4, did not react
with oxalyl chloride at 0 °C in the absence of DMPU. This is in
contrast to the reaction with 1,4-dicopper-1,3-dienes, which gener-
ated from the corresponding 1,4-dilithio-1,3-dienes 1. When the
reaction temperature was raised to 50 °C, the double bond
rearranged product 5 was obtained in 69% isolated yield (eq 5).
We propose that 5 formed via 3e. To obtain the direct evidence,
we treated 3e in THF in the presence of CuCl at 50 °C, and 5 was
obtained. These results indicated that in this reaction the DMPU
was necessary not only for increasing the solubility of 1,4-dicopper-
The initial experiment showed that reaction of organodilithium
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1a with oxalyl chloride led to the formation of complex, inseparable
1,3-dienes in THF but also for activating the C-Cu bond to afford
mixture. Nevertheless, a trace amount of cyclopentadienone 3a was
detected by GC-MS. This result may be explained by the high
reactivity of organodilithium and oxalyl chloride, which results in
the desired reaction to be minor. To avoid the high reactivity of
organodilithium compound, a proper tuning of the reactivity of
cyclopentadienone at low temperature.
4
organodimetallic reagents and oxalyl chloride is possible. There-
fore, we conducted the reaction of organodilithium 1a with oxalyl
chloride in the presence of CuCl, in which organodilithium
compound 1a transformed into organodicopper compound 2a that
In light of these results, we propose a possible mechanism for
this reaction (eq 6). First, the dialkenylithium compound 1 or the
5
was a softer nucleophile. The reaction smoothly proceeded, and
cyclopentadienone6 was obtained in high yield with CO gas
generated (eq 3).
zirconacyclopentadiene 4 undergoes transmetalation with CuCl to
2,5,8,10
form the dialkenylcopper compound.
Second, coordination of
one of the two carbonyl groups to copper metals of the alkenyl-
copper moieties affords seven-membered ring 6. One of the two
alkenylcopper moieties reacts with the chelated carbonyl group to
form 7. Then elimination of CuCl recovers coordinated CdO bond
to form 8, which then undergoes an intramolecular attack by the
remaining alkenylcopper moiety to give five-membered carbocycle
8024
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J. AM. CHEM. SOC. 2005, 127, 8024-8025
10.1021/ja0506713 CCC: $30.25 © 2005 American Chemical Society

C O M M U N I C A T I O N S
Table 1. Reaction of Dianionic Reagents with Oxalyl Chloride
intermediate 6 is the most likely intermediate. This can prevent
intermolecular reactions that give a complex mixture. Moreover,
when the reaction was treated with dimethyl oxalate under the same
reaction conditions, it did not proceed, and starting material
remained. When the reaction was treated with methyl(chloro-
carbonyl)formate 10 under the same reaction conditions, product
11 was obtained in 46% isolated yield after normal workup (eq 7).
In this case, elimination of CuOMe and CO did not occur, whereas
further reaction with the second molecule of 10 occurred. These
results suggest that the intermediate 9 with chlorine is the most
possible intermediate to afford cyclopentadienone.
In summary, 1,4-dilithio-1,3-dienes or zirconcyclopentadienes
unprecedentedly reacted with oxalyl chloride in the presence of
CuCl, resulting in the formation of cyclopentadienones as 1,1-
cycloaddition products. The investigation for the mechanism and
scope are being undertaken in this laboratory.
Acknowledgment. We thank the National Natural Science
Foundation of China (20172032) (20372041) for supporting this
work.
Supporting Information Available: Experimental procedure and
spectroscopic data for new products. This material is available free of
charge via the Internet at http://pubs.acs.org.
References
a
b
GC yields and isolated yields are given in parentheses. 16.3 mL of
c
CO gas was observed. 16.5 mL of CO was observed. The yield of CO
gas was comparable with the yield of cyclopentadienone.
(1) (a) Larock, R. C. ComprehensiVe Organic Transformations; VCH: New
York, 1989. (b) O’Niel, B. T. In ComprehensiVe Organic Synthesis; Trost,
B. M., Fleming, I., Eds.; Pergamon Press: New York, 1991; Vol. 1, p
397. (c) Shirley, D. A. Org. React. 1954, 8, 28. (d) Jorgenson, M. J. Org.
9
. Finally, elimination of the other CuCl accompanying decar-
React. 1970, 18, 1. (e) Faust, R.; Weber, C.; Fiandanese, V.; Marchese,
G.; Punzi, A. Tetrahedron 1997, 53, 14655. (f) Faust, R.; Weber, C. J.
Org. Chem. 1999, 64, 2571.
bonylation gives product 3. This result is in sharp contrast to the
case of other dianionic reagent reactions with oxalyl chloride, which
usually gives complex and inseparable products. The chelating effect
of the alkenylcopper moieties and the formation of cyclopentadi-
enone derivatives and CO gas were assumed to be the driving force
in this reaction.
(2) Mao, G.; Lu, J.; Xi, Z. Tetrahedron Lett. 2004, 45, 8095.
(
3) For the cleavage of carbon-carbon bond of oxalyl chloride with hetero-
element, see: (a) Adams, R.; Weeks, L. F. J. Am. Chem. Soc. 1916, 38,
2514. (b) Iida, T.; Itaya, T. Tetrahedron 1993, 49, 10551. (c) Tanner, D.
D.; Das, N. C. J. Org. Chem. 1970, 35, 3972.
(4) Langer, P.; Freiberg, W. Chem. ReV. 2004, 104, 4125.
(
5) (a) Rausch, M. D.; Klemann, L. P.; Boon, W. H. Synth. React. Inorg.
Met.-Org. Chem. 1985, 15, 923. (b) Buchwald, S. L.; Nielsen, R. B. J.
Am. Chem. Soc. 1989, 111, 2870. (c) Negishi, E.; Holmes, S. J.; Tour, J.
M.; Miller, J. A.; Cederbaum, F. E.; Swanson, D. R.; Takahashi, T. J.
Am. Chem. Soc. 1989, 111, 3336. (d) Xi, C.; Huo, S.; Afifi, T. H.; Hara,
R.; Takahashi, T. Tetrahedron Lett. 1997, 38, 4099.
(6) Xi, Z.; Song, Q. J. Org. Chem. 2000, 65, 9157.
(
7) (a) Negishi, E.; Cederbaum, F. E.; Takahashi, T. Tetrahedron Lett. 1986,
2
7, 2829. (b) Takahashi, T.; Kotora, M.; Kasai, K.; Suzuki, N.; Nakajima,
N. Organometallics 1994, 13, 4183. (c) Hara, R.; Liu, Y.; Sun, W.-H.;
Takahashi, T. Tetrahedron Lett. 1997, 38, 4104. (d) Kotora, M.; Umeda,
C.; Ishida, T.; Takahashi, T. Tetradedron Lett. 1997, 38, 8355. (e)
Takahashi, T.; Hara, R.; Nishihara, Y.; Kotora, M. J. Am. Chem. Soc.
1
1
996, 118, 5154. (f) Kotora, M.; Xi, C.; Takahashi, T. Tetrahedron Lett.
998, 39, 4321.
(
8) DMPU was added to dissolve a plausible dialkenylcopper species that
was precipitated from the THF solution. See: (a) Takahashi, T.; Kotora,
M.; Xi, Z. J. Chem. Soc., Chem. Commun. 1995, 36. (b) Takahashi, T.;
Hara, R.; Nishihara, Y.; Kotora, M. J. Am. Chem. Soc. 1996, 118, 5154.
(c) Hara, R.; Liu, Y.; Sun, W.-H.; Takahashi, T. Tetrahedron Lett. 1997,
To further confirm the reaction mechanism, we carried out the
reaction of 1-copper-1,4-diene, which generated in situ from the
corresponding 1-lithium-1,4-diene and CuCl, with oxalyl chloride
at 0 °C, in which there is no possibility to form a chelated
intermediate. The starting material was completely consumed,
however, and no 1,2-dione derivative was obtained. Instead, a
complex mixture was obtained. This result indicates that the chelated
3
8, 4103.
9) Takahashi, T.; Tsai, F.-Y.; Li, Y.; Nakajima, K. Organometallics 2001,
0, 4122.
(
2
(
10) (a) Takahashi, T.; Sun, W.-H.; Xi, C.; Ubayama, H.; Xi, Z. Tetrahedron
1998, 54, 715. (b) Takahashi, T.; Sun, W.-H.; Liu, Y.; Kiyohiko, N.;
Kotora, M. Organometallics 1998, 17, 3841.
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