An efficient one-pot method for the synthesis of mono- and biscyclopentenones via zirconium-catalyzed cycloalumination of cyclic alkynes and diynes

Article abstract of DOI:10.1016/j.tetlet.2010.08.120

Mono- and bisaluminacyclopentenes obtained via zirconium-catalyzed cycloalumination with Et₃Al and cyclic alkynes or diynes can be converted into the corresponding mono- and biscyclopentenones by treatment with CO₂, ClCOOEt, or CO(OE

Full text of DOI:10.1016/j.tetlet.2010.08.120

Tetrahedron Letters 51 (2010) 5886–5888
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Tetrahedron Letters
journal homepage: www.elsevier.com/locate/tetlet
An efficient one-pot method for the synthesis of mono- and biscyclopentenones
via zirconium-catalyzed cycloalumination of cyclic alkynes and diynes
⇑
Vladimir A. D’yakonov , Regina A. Tuktarova, Usein M. Dzhemilev
Institute of Petrochemistry and Catalysis, Russian Academy of Sciences, 141 Prospekt Oktyabrya, Ufa 450075, Russia
a r t i c l e i n f o
a b s t r a c t
Article history:
Mono- and bisaluminacyclopentenes obtained via zirconium-catalyzed cycloalumination with Et Al and
3
Received 13 July 2010
Revised 2 August 2010
Accepted 31 August 2010
Available online 8 September 2010
cyclic alkynes or diynes can be converted into the corresponding mono- and biscyclopentenones by treat-
ment with CO
2
, ClCOOEt, or CO(OEt)
2
in yields of 34À73%.
Ó 2010 Elsevier Ltd. All rights reserved.
Keywords:
Homogeneous catalysis
Organoaluminium compounds
Cycloalkynes
Cycloalumination
Dzhemilev reaction
Cyclic diynes
Cyclopentenones
Zirconocene dichloride
Cyclopentenones have attracted the attention of organic chem-
ists due to their wide use as building blocks in organic synthesis.
In addition, they are often encountered in drugs and flavoring
2 2
10:30, 5 mol % Cp ZrCl , 4 h, hexane) gave organoaluminium com-
pounds (OAC) 3 and 4, which after deuterolysis gave 2-deutero-1-
deuteroethylcyclododecene or 2-deutero-1-deuteroethylcyclot-
ridecene (>95% D in both positions) in 91À94% yields (Scheme 1).
1
compounds.
Efficient and widely used procedures for preparing cyclopente-
nones include the Nazarov cyclization, the Pauson-Khand reaction,
and methods based on intramolecular cyclization of dienes, eny-
2
Treatment of OACs 3 or 4 with 3 equiv of CO , ClCOOEt, or
2
CO(OEt) produced the desired bicyclo[10.3.0]pentadec-1(12)-en-
13-one (5) and bicyclo[11.3.0]hexadec-1(13)-en-14-one (6)8 in
7
2
nes, and diynes catalyzed by Ru, Ir, Rh, Au, Pd, or Ni complexes.
the yields indicated in Table 1.
Another method for the synthesis of cyclopentenones includes
intramolecular carbocyclization of aluminacyclopentenes gener-
Taking into account the experimental data obtained from the
catalytic cycloalumination of cyclic acetylenes on the example of
cyclotetradeca-1,8-diyne (8), we elaborated the reaction condi-
3
ated in situ in Zr-catalyzed cycloalumination reactions of alkynes
and Et
with CO
We have investigated, for the first time, the activity of cyclic
mono- and diynes in catalytic cycloaluminations with Et Al and also
their ability to give the corresponding aluminacyclopentenes in the
presence of Cp ZrCl as the catalyst. This confirms the high activity
3
Al (Dzhemilev reaction),4 and their subsequent treatment
tions (cycloalkadiyne:Et
The cycloalkadiyne underwent cycloalumination with Et
the presence of 10 mol % Cp ZrCl involving both triple bonds to
3
Al:[Zr] = 1:6:0.1, hexane, 20À22 °C, 6 h).
2
, ClCOOEt, or CO(OEt)
2
.
3
Al in
2
2
3
form the regioisomeric tricyclic bisaluminacyclopentenes 12a
and 12b in 87% yield (Scheme 2).
2
2
2
Carbocyclization of OACs 12a,b using 6 equiv of CO or ClCOOEt
5
1,17 7,11
and selectivity in cycloaluminations of unsaturated compounds.
Cycloalkynes [cyclododecyne (1), cyclotridecyne (2)]6a and cyc-
lic diynes [cyclododeca-1,7-diyne (7), cyclotetradeca-1,8-diyne (8),
cyclooctadeca-1,10-diyne (9), cyclodocosa-1,12-diyne (10)]6 were
selected for investigation.
gave rise to 8,20-dioxotricyclo[15.3.0 .0 ]icosa-1(17),7(11)-
7,11
diene 16a and 8,18-dioxotricyclo[15.3.01,17.0 ]icosa-1(17),
7(11)-diene 16b, respectively, a 1:1 ratio (as determined by NMR
spectroscopic experiments) in 59À68% overall yields (Table 1).
Other cyclic diynes (Table 1) participated in this reaction to
afford the corresponding doublytethered biscyclopentenones
b
We established that the reaction of cycloalkynes 1 and 2 with
2
j,2k
Et
3
Al (excess) under the developed conditions (cycloalkyne:Et
3
Al =
15À18
in high yields (50:50 mixture of regioisomers in all
cases).
⇑
Corresponding author. Tel./fax: +7 347 2842750.
E-mail address: DyakonovVA@rambler.ru (V.A. D’yakonov).
It is interesting to note that cyclopentenone 5 has been successfully
used in the synthesis of exaltone, muscone, and bicyclo[10.3.0]pentad-
0
040-4039/$ - see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tetlet.2010.08.120

V. A. D’yakonov et al. / Tetrahedron Letters 51 (2010) 5886–5888
5887
a
b
(
CH )n
(CH )n
(CH2)
n
2
2
Al
Et
O
1
2
(n = 4)
(n = 5)
3 (n = 4)
4 (n = 5)
5 (n = 4)
6 (n = 5)
n = 4, 5. (a): Et Al, [Zr], (b): CO , ClCOOEt or CO(OEt)
2
3
2
Scheme 1.
(
(
CH2)n
(CH2)n
Al
CH2)
n
Al
Et
(CH2)
n
(
(
CH2)
n
a
b
Et 11a-14a
O
O
15a-18a
15b-18b
O
O
+
+
Et
CH2)n
-10
Al
(CH2)n
(CH2)n
(
CH2)n
CH2)n
7
(
Al
Et
1
1b-14b
n = 2, 3, 5, 7. (a): Et Al, [Zr], (b): CO , ClCOOEt or CO(OEt)
2
3
2
[
Zr] = Cp ZrCl ; (n = 2) 7, 11, 15; (n = 3) 8, 12, 16; (n = 5) 9, 13, 17; (n = 7) 10, 14, 18
2
2
Scheme 2.
(
(
CH2)3
(CH2)3
(CH2)3
(CH2)3
(CH2)3
a
b
7
5%
78%
CH2)3
Al
Et
8
19
20
O
[
Zr] = Cp ZrCl ; (a): Et Al, [Zr], (b): CO
2 2 3 2
Scheme 3.
In conclusion, this catalytic cyclometallation reaction repre-
sents an efficient methodology, which allows the preparation of
mono- and bis(cyclopentenones) from the cyclic acetylenes via
the in situ generation of aluminacyclopentene intermediates in
yields greater than 80% and their carbocyclization with the aid of
Table 1
Synthesis of mono- (5,6) and biscyclopentenones (15À18) via cycloalumination of
cyclic mono- and diynes
Entry Cyclic alkyne or diyne
Cyclopentenone Isolated yield (%)
a
b
c
1
2
3
4
5
6
Cyclododecyne (1)
Cyclotridecyne (2)
Cyclododeca-1,7-diyne (7)
Cyclotetradeca-1,8-diyne (8)
5
6
15
16
71 , 62 , 34
a
b
b
b
b
b
2 2
CO , ClCOOEt or CO(OEt) .
73 , 63
a
59 , 48
a
68 , 59
Acknowledgment
a
Cyclooctadeca-1,10-diyne (9) 17
Cyclodocosa-1,12-diyne (10) 18
70 , 63
a
72 , 62
This work was supported financially by the Russian Foundation
for Basic Research (Grant No. 10-03-00046) and by the Russian Sci-
ence Support Foundation.
a
b
c
Reaction of OAC with CO
Reaction of OAC with ClCOOEt.
Reaction of OAC with CO(OEt)
2
.
2
.
References and notes
7
ecan-13-one—substances having a musk-like odor, and biscyclopen-
tenones 15À18 have been employed as starting materials for ansa-
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9
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2.
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11
For example, we found that cyclotetradeca-1,8-diyne (8) reacted
with Et
presence of Cp
lated aluminacyclopentene fragment. Subsequent reaction between
3 3
Al (cycloalkadiyne:Et Al = 1:3, hexane, 20–22 °C, 3 h) in the
2
ZrCl (5 mol %) to give cycloalkyne 19 with an annu-
2
2009, 74, 370.
produced bicyclo[12.3.01 ]heptadec-1(14)-
,14
OAC 19 and CO
en-7(8)-yn-15-one (20) in 59% overall yield (Scheme 3).
2
3.
Negishi, E.; Montchamp, J.-L.; Anastasia, L.; Elizarov, A.; Choueiry, D.
12
Tetrahedron Lett. 1998, 39, 2503.

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V. A. D’yakonov et al. / Tetrahedron Letters 51 (2010) 5886–5888
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.
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Commun. 2008, 18, 1; (d) Dzhemilev, U. M.; Ibragimov, A. G. J. Organomet. Chem.
(haxane and then 5:1 hexane-EtOAc) afforded the target products 5, 6, or
2k,2j
15À18.
Bicyclo[11.3.0]hexadec-1(13)-en-14-one (6):
R
f
= 0.56 (hexane–
H NMR (400 MHz, CDCl ): d
1.91À2.62 (m, 8H), 0.89À1.93 (m, 18H); C NMR (100 MHz, CDCl ): d 20.6,
21.9, 22.8, 23.5, 24.6, 24.8, 25.2, 25.4, 25.6, 27.9, 28.8, 29.1, 34.5, 140.0, 174.6,
À1
1
EtOAc, 5:1). IR: 1635 (C@O), 1691 (C@O) cm
.
3
13
2
010, 695, 1085; (e) D’yakonov, V. A. Dzhemilev Reaction in Organic and
3
Organometallic Synthesis; NOVA Sci. Publ.: New York, 2010. p 96.
+
5
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81.78; H, 11.16.
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3
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6
.
(a) Brandsma, L.; Verkruijsse, H. D. Synthesis 1978, 290; (b) Gleiter, R.; Merger,
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7
8
.
.
Zr-Catalyzed cycloalumination of cycloalkynes and diynes with Et
treatment with CO , ClCOOEt, or CO(OEt) (general procedure). A glass reactor
under a dry argon atmosphere at ambient temperature was charged under
stirring with 10 ml of hexane, Cp ZrCl (1 mmol), cycloalkyne (10 mmol) or
cyclic diyne (5 mmol), and Et Al (30 or 60 mmol). The mixture was stirred for
À6 h. Analysis of an aliquot by GLC indicated the formation of 3, 4, or 11À14
in 34À73% yields. After cooling the reaction mixture to 0 °C, CO was slowly
bubbled through via a gauge needle or ClCOOEt(CO(OEt) ) (36 or 72 mmol) was
added at À78 °C and the mixture stirred overnight at ambient temperature. The
reaction mixture was diluted with CH Cl (15 ml) and quenched with 5%
aqueous HCl (5 ml). The organic layer was washed with aqueous NaHCO
3
Al followed by
2
2
Makarov, A. A.; Dzhemilev, U. M. Tetrahedron 2010, 66, 6885.
12. Bicyclo[12.3.01 ]heptadec-1(14)-en-7(8)-yn-15-one (20): Yield 59%. R
,14
= 0.52
2
2
f
3
(hexane–EtOAc, 5:1). IR: 771, 921, 1437, 1464, 1625 (C@O), 1674 (C@O), 1755
1
À1
4
(C@O), 2846, 2960 cm
C@), 2.45 (t, 2H, J = 7.2 Hz, CH
(m, 6H, 3CH
), 1.67À1.69 (m, 2H, CH
(100 MHz, CDCl ): d 17.9, 18.4, 23.2, 26.3, 26.6, 27.1, 27.3, 28.3, 28.3, 29.1, 34.2,
.
H NMR (400 MHz, CDCl
–C@), 2.37À2.41 (m, 2H, CH
), 1.39À1.62 (m, 10H, 5CH
3
): d 2.49À2.51 (m, 2H, CH
2
–
2
2
2
–C@O), 2.16À2.26
13
2
2
2
2
); C NMR
3
+
2
2
80.2, 81.3, 140.3, 174.1, 210.4. MS, m/z: 244 (M ). Anal. Calcd for C17H24O: C,
3
83.55; H, 9.90. Found: C, 83.35; H, 9.88.