Gold(I)-catalyzed cycloisomerization of nitrogen- and oxygen-tethered alkylidenecyclopropanes to tricyclic compounds

Article abstract of DOI:10.1002/chem.201200978

A new construction of tricyclic compounds has been developed from a gold-catalyzed cycloisomerization of alkylidenecyclopropanes tethered by alkynes, giving the corresponding nitrogen- and oxygen-containing six-membered heterocyclic compounds in high yields under very mild conditions (see scheme; Ts=4-toluenesulfonyl, Ns=4-nitrobenzenesulfonyl, Bs=4-bromobenzenesulfonyl).

Full text of DOI:10.1002/chem.201200978

COMMUNICATION
DOI: 10.1002/chem.201200978
Gold(I)-Catalyzed Cycloisomerization of Nitrogen and Oxygen-Tethered
Alkylidenecyclopropanes to Tricyclic Compounds
Di-Han Zhang, Yin Wei,* and Min Shi*[a]
Homogeneous catalysis by gold complexes has received
considerable attention in recent years.[1] Among these inter-
esting reactions, gold-catalyzed cycloisomerization of 1,6-
enynes is one of the most important strategies for the con-
struction of functionalized cyclic structures.[2] Nitrogen- and
oxygen-bridged enynes are useful starting materials for the
preparation of heterocyclic building blocks. Since Blum
et al. first reported the PtCl4-catalyzed cyclorearrangement
of allyl propynyl ether to 3-oxabicycloACTHNUTRGNE[NUG 4.1.0]heptenes in
1995,[3a] this type of 6-endo-dig cycloisomerization has been
developed by the use of transition-metal catalysts, such as
platinum,[3] rhodium,[4] gold[5] and iridium.[6] For example,
Chung and co-workers reported the gold-catalyzed cycliza-
tion of enynes containing an olefinic cycle to give
Scheme 1. Gold-catalyzed cycloisomerization of alkylidenecyclopropanes
tethered by alkynes.
azabicycloACHTUNGTRENNUNG
[4.1.0]heptenes under mild conditions.[5c] Similar
oxygen heterocycles with high diastereoselectivities have
been reported by Micheletꢀs and Chenꢀs groups.[5f,h]
Table 1. Optimization of the reaction conditions for gold(I)-catalyzed in-
tramolecular cyclization.
Alkylidenecyclopropanes (ACPs) containing a coordinat-
ing double bond and a strained carbocycle can undergo
a number of interesting metal-assisted cycloadditions when
tethered by alkenes or alkynes.[7] In this aspect, Tosteꢀs
group reported a new gold-catalyzed ring-expanding enyne
cycloisomerization reaction that allows for rapid preparation
of complex polycyclic ring systems (Scheme 1a).[2j] Herein,
we report a new construction of tricyclic compounds along
with cycloisomerization from alkylidenecyclopropanes
toward six-membered heterocyclic rings (Scheme 1b).
Initial studies by using alkylidenecyclopropane 1a
(0.2 mmol) as the substrate were aimed to determine the re-
action outcome and subsequently optimize the reaction con-
ditions. The results are summarized in Table 1. We found
that an interesting tricyclic product 2a was formed in 69%
yield by using [(PPh3)AuCl]/AgOTf as the catalyst
Entry[a] Catalyst [x mol%]
Solvent
Yield [%],[b] 2a
1
N
DCE
DCE
DCE
DCM
DCM
toluene
MeCN
69
45
Complex
NR
NR
20
2[c]
3[c]
4
5
6
7
NR
8
N
1,4-dioxane 37
9
C
CHCl3
DCM
DCM
DCM
DCM
DCM
DCM
DCM
DCM
87
90
44
42
39
47
90
3
10
11
12
13
14
15
16
17
18
[a] D.-H. Zhang, Dr. Y. Wei, Prof. Dr. M. Shi
State Key Laboratory of Organometallic Chemistry
Shanghai Institute of Organic Chemistry
Chinese Academy of Sciences
58
94
ACHTUNGTREN(NGNU NCMe)]SbF6 (5) DCM
345 Lingling Road, Shanghai 200032 (P.R. China)
Fax : (+86)21-64166128
E-mail: Mshi@mail.sioc.ac.cn
[a] All reactions were carried out by using 1a (0.2 mmol) in the presence
of catalyst (x mol%) in various solvents (2.0 mL) unless otherwise speci-
fied. [b] Yield of isolated product. [c] At 808C. NR =no reaction.
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/chem.201200978. Experimental proce-
dures and spectral data for all new compounds. X-ray crystal struc-
tures and data for 2a, 3p and 4n. This material is available free of
charge via the Internet at http://onlinelibrary.wiley.com/journal/
(5 mol%) in 1,2-dichloroethane (DCE) at room tempera-
10.1002/
G
ture (208C) (Table 1, entry 1). The structure of compound
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Table 2. Substrate scope of the gold(I)-catalyzed cycloisomerization.
2a was confirmed by NMR spectroscopic data and X-ray
diffraction analysis (see the Supporting Information).[8] Car-
rying out the reaction in the presence of PtCl2 or
[RhCl(CO)ACHTUNGTRENNUNG(PPh3)2]/ACHTUNGTRENNUNG[AgSbF6] (5 mol%), which were effec-
tive catalysts in other similar reactions, afforded the desired
product 2a in lower yield or complex product mixtures, re-
spectively (Table 1, entries 2 and 3).[3b–h,j,m,4d] Control experi-
ments indicated that by using [(PPh3)AuCl] or AgOTf alone
as the catalyst did not promote the reaction (Table 1, en-
tries 4 and 5). Further examination of solvent effects re-
vealed that dichloromethane (DCM) was the solvent of
choice, and 2a was formed in lower yield in other organic
solvents, such as toluene, MeCN, 1,4-dioxane, or CHCl3
(Table 1, entries 6–10). Moreover, adding [(PPh3)AuCl]/
AgOTf (10 mol%) afforded 2a in 44% yield (Table 1,
entry 11). Changing silver salt to AgSbF6 or AgBF4 did not
improve the reaction outcomes (Table 1, entries 12 and 13).
By using [(PMe3)AuCl] or [(tBu3P)AuCl] instead of
[(PPh3)AuCl] as the gold catalyst gave 2a in 47 and 90%
yields, respectively, and [(IPr)AuCl] (IPr=1,3-bis(2,6-diiso-
propylphenyl)imidazol-2-ylidene) as well as AuCl3 were not
effective gold catalysts in this reaction (Table 1, entries 14–
Entry[a]
1
X
R
Yield [%],[b]
2
1
2
3
4
5
6
7
8
1b
1c
1d
1e
1 f
1g
1h
1i
NTs
NTs
NTs
NTs
NTs
NTs
NTs
NTs
NNs
NBs
O
4-MeOPh
4-MePh
3-MePh
2-BrPh
4-ClPh
1-naphthyl
Me
Et
Ph
Ph
Ph
2b, 87
2c, 95
2d, 90
2e, 98
2 f, 99
2g, 99
2h, 73
2i, 87
2j, 88
2k, 99
2l, 71
2m,80
9
1j
1k
1l
10
11
12
1m
O
4-ClPh
13[c]
1n
1o
1p
2n, 94
NR
14
15
3p, 71
17). In the presence of [(tBuXPhos)AuACTHNUTRGEN(UNG NCMe)]SbF6
(Figure 1, cat. 1), 2a could be
obtained in 94% yield under
otherwise identical conditions
(Table 1, entry 18). Therefore,
the optimal reaction conditions
have been identified to carry
of out the reaction in DCM at
room temperature by using
[a] All reactions were carried out by using 1 (0.2 mmol) in the presence
of cat. 1 (5 mol%) in DCM (2.0 mL) at RT for 15–30 h. [b] Yield of iso-
lated product. [c] Molecular sieves (4 ꢂ, 50 mg) was added. Ts=4-tolue-
nesulfonyl; Ns=4-nitrobenzenesulfonyl; Bs=4-bromobenzenesulfonyl;
NR=no reaction.
Figure 1. Structure
[(tBuXPhos)Au(NCMe)]SbF6.
ACHTUNGTRENNUNG
strate 1n revealed that the azabicycloACTHNUTRGNEUNG[4.1.0]heptene deriva-
[(tBuXPhos)Au
(5 mol%) as the catalyst.
(NCMe)]SbF6
tive 2n could be obtained in 94% yield, when 4 ꢂ molecular
sieves was added (Table 2, entry 13). As for 1,7-enyne 1o,
no reaction occurred under the standard conditions (Table 2,
entry 14). When the terminal of alkyne moiety is a hydrogen
atom (substrate 1p), the corresponding 1,3-diene 3p could
be obtained in 71% yield rather than the tricyclic product
(Table 2, entry 15).[9] The product structures of 2b–n were
determined by NMR spectroscopic data, MS, and HRMS.
The structure of compound 3p was confirmed by NMR
spectroscopic data and X-ray diffraction analysis (see the
Supporting Information).[10]
We next examined the substrate generality of the reaction
under the optimized conditions, and the results are shown in
Table 2. As can be seen, for nitrogen-tethered substrates
1b–d with an electron-donating group on the benzene ring,
such as MeO and Me groups, the reactions proceeded
smoothly to give the desired products 2b–d in 87–99%
yields (Table 2, entries 1–3). When the electron-withdrawing
groups, Br or Cl, were introduced on the benzene ring (sub-
strates 1e and 1 f), the corresponding products 2e and 2 f
were obtained in 98 and 99% yields, respectively (Table 2,
entries 4 and 5). The aromatic group of 1 could also be
a naphthyl group (substrate 1g), giving the cycloisomerized
compound 2g in 99% yield (Table 2, entry 6). As for sub-
strates 1h (R=Me) and 1i (R=Et) with an alkyl group at
the terminal of alkyne moiety, tricyclic compounds 2h and
2i could be formed in 73 and 87% yields, respectively
(Table 2, entries 7 and 8). In the case of other N-sulfonated
amines (X=NNs or NBs), the reaction also proceeded
smoothly to give the desired products 2j and 2k in 88–99%
yields, indicating a broad substrate scope of this reaction
(Table 2, entries 9 and 10). For oxygen-tethered alkylidene-
cyclopropanes, such as substrates 1l and 1m, the reactions
produced 2l and 2m in 71 and 80% yields, respectively
(Table 2, entries 11 and 12). Further examination of sub-
On the other hand, in the case of 1,6-enyne 1n, under the
standard conditions, the reactions produced 2n, 4n, and
5n[11] in 49, 15, and 29% yields, respectively. Then, adding
molecular sieves (4 ꢂ, 50 mg) into the reaction system,
azabicycloACTHNUTRGNEUG[N 4.1.0]heptene derivative 2n could be obtained in
94% yield as the sole product. Alcohol derivative 5n was
formed in 77% yield along with a trace amount of 2,3-dihy-
drofuran derivative 4n, when H2O (10 equiv) was added,
suggesting that products 4n and 5n are derived from adven-
titious water (Scheme 2). The structure of compound 4n was
confirmed by NMR spectroscopic data and X-ray diffraction
analysis (see the Supporting Information).[12]
Plausible mechanisms for these reactions are outlined in
Scheme 3 on the basis of above results. Coordination of AuI
complex to the alkyne forms intermediate 1, which evolves
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Gold(I)-Catalyzed Cycloisomerization
COMMUNICATION
carbenoid E can undergo a rearrangement to give a spiro in-
termediate F.[4b,9a] Depending on the substitution pattern,
when R=H, the spiro intermediate F undergoes fragmenta-
tion to produce the carbocation G, followed by elimination
of AuI complex to give 1,3-diene 3 (blue arrow). As depicted
by black arrows, activation of the alkyne moiety by AuI
complex induces a nucleophilic attack of water to give inter-
mediate H. Skeletal reorganization of intermediate H pro-
duces enol I, followed by intramolecular proton transfer to
form the oxo-anion intermediate J. Intermediate J under-
goes intramolecular nucleophilic attack to produce tetrahy-
drofuran K, which can also further tautomerize to the corre-
sponding 2,3-dihydrofuran derivative 4.
Scheme 2. Gold(I)-catalyzed cycloisomerization of 1n by using different
conditions.
In conclusion, we have developed a new gold(I)-catalyzed
cycloisomerization of nitrogen and oxygen-tethered alkyli-
denecyclopropanes to provide an easy access to tricyclic
compounds or bicycloACHTNUGRTENUNG[4.1.0]heptene derivatives in high
yields under very mild conditions. Further applications of
this air- or moisture-tolerant reaction of a gold-catalyzed
tandem system and more detailed mechanistic investigation
are underway in our laboratory.
Experimental Section
General procedure for gold(I)-catalyzed cycloisomerization of alkylide-
necyclopropanes under the standard reaction conditions: Under ambient
atmosphere, an alkylidenecyclopropanes 1 (0.2 mmol, 1.0 equiv) was dis-
solved in DCM (2.0 mL) in an Schlenk tube, and [(tBuXPhos)Au-
AHCTUNGTRE(GNUNN NCMe)]SbF6 (5 mol%) was added. Then, the reaction mixture was
stirred at RT until the reaction was completed. The solvent was removed
under reduced pressure, and the residue was purified by a flash-column
chromatography (SiO2) to give the corresponding product 2 in moderate-
to-excellent yields.
Acknowledgement
We thank the Shanghai Municipal Committee of Science and Technology
(11JC1402600), National Basic Research Program of China ACHTUNGTRENNUNG(973)-
2009CB825300, and the National Natural Science Foundation of China
for financial support (20872162, 21072206, 20672127, 21121062 and
20732008).
Scheme 3. A plausible reaction mechanism.
Keywords: cyclization · cyclotrimerization · homogeneous
catalysis · heterocycles · gold
to give the cyclopropyl Au–carbene intermediate A (via 6-
endo-dig cyclization) or E (via 5-exo-dig cyclization), which
are often observed in gold-catalyzed cycloisomerizations of
1,6-enynes. It should be also mentioned here that we did not
observe any product via 6-exo-dig cyclization as reported by
Toste and co-workers.[2j] There might be an equilibrium be-
tween the intermediates A and B, intermediate B is expect-
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mediate C, followed by elimination of AuI complex to give
product 2 (orange arrow).[5f] Alternatively, nucleophilic
attack of water on the cyclopropyl moiety of intermediate A
gives intermediate D, which undergoes hydrolysis to pro-
duce alcohol derivative 5 (red arrow).[5b] On the other hand,
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Received: March 22, 2012
Published online: && &&, 2012
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ꢁ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 0000, 00, 0 – 0
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These are not the final page numbers!

Gold(I)-Catalyzed Cycloisomerization
COMMUNICATION
Hererocycles
D.-H. Zhang, Y. Wei,*
M. Shi* ......................... &&&& — &&&&
Gold(I)-Catalyzed Cycloisomerization
of Nitrogen and Oxygen-Tethered
Alkylidenecyclopropanes to Tricyclic
Compounds
A new construction of tricyclic com-
pounds has been developed from
a gold-catalyzed cycloisomerization of
alkylidenecyclopropanes tethered by
alkynes, giving the corresponding
nitrogen- and oxygen-containing six-
membered heterocyclic compounds in
high yields under very mild conditions
(see scheme; Ts=4-toluenesulfonyl,
Ns=4-nitrobenzenesulfonyl, Bs=4-
bromobenzenesulfonyl).
Chem. Eur. J. 2012, 00, 0 – 0
ꢁ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
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These are not the final page numbers!