Gold-catalyzed cycloisomerization of yne-vinylidenecyclopropanes: A three-carbon synthon for [3+2] cycloadditions

Article abstract of DOI:10.1002/chem.201304579

A novel type of yne-vinylidenecyclopropanes (VDCPs) has been synthesized and applied in gold-catalyzed cycloisomerization reactions. It was found that these compounds can undergo an intramolecular cycloisomerization and perform as a three-carbon synthon for [3+2] cycloaddition under gold catalysis to give fused [4.3.0] and [5.3.0] bicyclic derivatives and VDCP rearranged products in moderated to good yields under mild conditions. The substrate scope of these novel transformations has been explored and plausible reaction mechanisms have been presented on the basis of deuterium labeling experiments and DFT calculations. Gold cats: A novel type of yne-vinylidenecyclopropanes (VDCPs) has been synthesized. These compounds can undergo an intramolecular cycloisomerization and perform as a three-carbon synthon for [3+2] cycloadditions under gold catalysis to give fused [4.3.0] and [5.3.0] bicyclic derivatives and VDCP-rearranged products in moderated to good yields under mild conditions (see scheme).

Full text of DOI:10.1002/chem.201304579

DOI: 10.1002/chem.201304579
Full Paper
&
Gold Catalysis
Gold-Catalyzed Cycloisomerization of Yne-
Vinylidenecyclopropanes: A Three-Carbon Synthon for [3+2]
Cycloadditions
Wei Yuan, Xiangying Tang, Yin Wei,* and Min Shi*[a]
Abstract:
A
novel type of yne-vinylidenecyclopropanes
cyclic derivatives and VDCP rearranged products in moderat-
ed to good yields under mild conditions. The substrate
scope of these novel transformations has been explored and
plausible reaction mechanisms have been presented on the
basis of deuterium labeling experiments and DFT
calculations.
(VDCPs) has been synthesized and applied in gold-catalyzed
cycloisomerization reactions. It was found that these com-
pounds can undergo an intramolecular cycloisomerization
and perform as a three-carbon synthon for [3+2] cycloaddi-
tion under gold catalysis to give fused [4.3.0] and [5.3.0] bi-
Introduction
Homogeneous gold catalysis
based on activating alkenes, al-
kynes, and allenes has witnessed
significant developments in
many organic transformations
within the past decade.[1,2] Many
of these fascinating transforma-
tions have been applied in the
synthesis of intermediates or
functional blocks of natural
products.[3] Enynes[4,5,1i,6] and al-
leneynes[2,7] feature as easily
available substrates that have
unique versatility in reactions
catalyzed by gold catalysts and
have been the focus of much
recent research.
Scheme 1. Cycloisomerization of alleneynes, yne-alkylidecyclopropanes 1, and yne-VPCPs 2 catalyzed by gold(I)
complexes.
Vinylidenecyclopropanes
(VDCPs) bearing an allene
moiety connected to a highly
strained cyclopropane group are fascinating building blocks in
organic synthesis and have attracted much interest from or-
ganic chemists. To date, numerous useful and unique transfor-
mations of VDCPs have been discovered by us and other re-
search groups.[8,9] Referring to the previous work, a number of
examples of gold-catalyzed reactions of allenyene substrates
have been reported (Scheme 1a and b),[10] and reactions of
yne-alkylidecyclopropane substrates 1 (Scheme 1c)[11] catalyzed
by gold complexes have been extensively explored. However,
yne-VDCPs 2 (Scheme 1d) have, to the best of our knowledge,
never been synthesized and, consequently, the reactivities of
these novel VDCP substrates in the presence of gold catalysts
have never been explored. Because VDCPs bearing an allene
moiety and a highly strained cyclopropane group are rather
electron-rich substrates, we envisaged that they could react
with terminal alkynes activated by gold catalysts in either an
intramolecular or intermolecular manner, thus providing novel
transformations through further CÀC bond cleavage or ring en-
[a] W. Yuan, X. Tang, Y. Wei, M. Shi
State Key Laboratory of Organometallic Chemistry
Shanghai Institute of Organic Chemistry
Chinese Academy of Sciences
354 Fenglin Lu, Shanghai, 200032 (P. R. China)
Fax: (+86)21-64166128
E-mail: Mshi@mail.sioc.ac.cn
Supporting information for this article is available on the WWW under
http://dx.doi.org/10.1002/chem.201304579. It contains spectroscopic charts
of the compounds shown in Tables 2 and 3, X-ray crystal data of 3h’, and
experimental procedures.
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largement of cyclopropane. Recently, we discovered
several unprecedented transformations of VDCPs
catalyzed by gold complexes.[9d,j,m,o] Herein, we wish
to present a novel cycloisomerization of newly syn-
thesized yne-VDCPs catalyzed by an AuI complex
that efficiently affords fused [4.3.0] or [5.3.0] bicyclic
derivatives as well as unexpected VDCP-rearranged
products in moderate to good yields under mild
conditions.
Table 1. Substrate scope of the gold-catalyzed cycloisomerization of yne-VDCPs 2.[a]
2
3, yield
[%][b]
2
3, yield [%][b]
1
2
8[c]
Results and Discussion
Yne-VDCP substrate 2a was first synthesized (see
the Supporting Information for details) and then re-
acted under gold catalysis. Through screening of
the reaction conditions, it was found that the corre-
sponding bicyclic derivative 3a[12] could be afforded
in 80% yield when 5 mol% cat. I was used as cata-
lyst and the reaction was carried out at room tem-
perature within 0.5 h in 1,2-dichloroethane (DCE)
under argon (see Table SI-1 in the Supporting Infor-
mation for details). Through this transformation, it
is clear that the VDCP moiety can also act as
a three-carbon synthon for [3+2] cycloaddition.
The substrate scope of this novel transformation
was explored under the optimized reaction condi-
tions, and the results are summarized in Table 1. For
yne-VDCPs 2b–g, in which R can be various primary
or secondary alkyl groups with X as TsN (Ts=4-
methylbenzenesulfonyl) or BsN anchor (Bs=4-bro-
mobenzenesulfonyl), the desired products 3b–g
were obtained in moderate to good yields ranging
from 43 to 85% (Table 1, entries 2–7). When yne-
VDCPs 2h–j were employed as substrates, in which
R was benzyl (Bn) or 4-methylbenzyl group with
X=TsN or BsN as an anchor, the corresponding
products 3h–j could also be afforded in 56–74%
yield (Table 1, entries 8–10). By using yne-VDCP 2k
(X=CH2, R=Bn) or 2l (X=4-phenylbenzenesulfony-
9
3
10
4
5
6
7
11
12
13
14
complex
complex
[a] Reaction conditions: 2 (0.1 mmol), gold complex I (5 mol%), DCE, RT, 0.5 h. [b] Isolat-
ed yield. [c] By-product 3h’ was obtained in 14% yield.
lamino group, R=Me) as substrate, the corresponding reaction
took place smoothly, affording the desired product 3k or 3l in
25 or 54% yield, respectively (Table 1, entries 11 and 12). How-
ever, when yne-VPCP 2m (X=O, R=Bn) or 2n (X=NTs, R=
Me, and the yne moiety is an internal alkyne) was used as the
substrate, the reactions gave complex product mixtures
(Table 1, entries 13 and 14). For substrate 2m, the reasons for
the formation of the complex product mixture are not yet
clear. For substrate 2n, the desired product could not be ob-
tained and we believed that the reason is more related to the
generation of higher energy barriers for the desired reactions
when the employed alkyne is substituted. More interestingly,
an unexpected VDCP rearranged product 3h’ was also isolated
in 14% yield under the optimal reaction conditions when 2h
was used as substrate (Table 1, entry 8). The structure of 3h’
was unambiguously assigned by X-ray diffraction analysis, and
its ORTEP drawing and the CIF data are presented in the Sup-
porting Information.[13] Similar byproducts could be also ob-
tained, albeit in trace amounts (<5% yield), when 2i or 2j
were employed as reactant, perhaps due to the electronic
properties of the benzyl group.
The observed formation of VDCP rearranged product 3h’ in-
spired us to further explore the reaction scope of this interest-
ing transformation. We found that yne-VDCPs 4, in which one
carbon chain has been extended by a CH2CH2 moiety, could
produce the desired VDCP rearranged product 5 in moderate
yields in the presence of cat. I under slightly modified optimal
conditions (reaction time being extended to 1 h); the results
are summarized in Table 2. All the reactions proceeded
smoothly to give the desired VDCP rearranged products 5 as
the major species. For yne-VDCPs 4a–g, in which R was various
primary or secondary alkyl groups with X as TsN or BsN anchor,
the rearranged VDCP products 5a–g were obtained in moder-
ate yields ranging from 28 to 56% (Table 2, entries 1–7) along
with the corresponding cycloisomerization products 6b–g in
11–25% yield (Table 2, entries 2–7). When yne-VDCP 4h or 4i
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outcome by using deuterated [D]-2a
(D content=99%) as the reactant
Table 2. Substrate scope of the gold-catalyzed cycloisomerization/rearrangement of yne-VDCPs 4.[a]
under
the
standard
conditions
(Scheme 3; see the Supporting Infor-
mation). It was found that product [D]-
3a could be obtained in 87% yield and
99% D content, which clearly suggest-
ed an intramolecular cycloisomerization
process. Furthermore, by using deuter-
ated substrate [D]-4a (D content>
80%) in the reaction, the correspond-
ing product [D]-5a was afforded in
53% yield and 80% D content under
the standard conditions (Scheme 3; see
the Supporting Information), which
also suggests an intramolecular re-
arrangement process.
4
Yield [%][b]
4
Yield [%][b]
5
6
5
6
1
2
3
4
trace
6
7
8
9
Plausible mechanisms for the cyclo-
isomerization/rearrangement of yne-
–
–
VPCPs
2 and 4 are presented in
Scheme 4 on the basis of isotope label-
ing experiments and on previous re-
ports.[9k,14] In path a, the coordination
of terminal alkyne in VDCP 2 (n=1)
with AuI catalyst initially generates
gold species A, which cyclizes with the
C-2 carbon in the tethered VDCP to
give a pair of equilibrated intermedi-
ates B and C in a 6-exo-dig manner. In-
termediate C then undergoes intramo-
lecular cyclization of the nucleophilic
vinylgold moiety[15,16] to produce the
corresponding product 3 with release
5
10
complex
[a] Reaction conditions: substrate 4, cat. I (10 mol%), DCE (0.1m), under argon, RT, 1 h. [b] Isolated
yield.
was employed as substrate, in which R was a benzyl group
with X as TsN or BsN anchor, the corresponding products 5h
or 5i could be produced exclusively in 62 or 76% yields, re-
spectively (Table 2, entries 8 and 9). When yne-VDCP 4k (X=
CH2, R=Bn) was employed as substrate, the reaction only gave
complex product mixtures (Table 2, entry 10). With yne-VDCP
4k as substrate (one carbon chain being extended by
a CH2CH2CH2 moiety), no reaction occurred under the standard
conditions (Scheme 2).
Concerning the substitution requirement of the allene, we
realized that a benzyl group on the allene moiety favored the
formation of VDCP rearranged products, perhaps as a result of
Scheme 3. Isotope-labeling experiments.
electronic effects.
To gain more mechanistic insights into the reaction, we con-
ducted isotope labeling experiments to examine the reaction
of the AuI catalyst, which is free to engage in the next catalytic
cycle. This is a main process for VDCP 2. On the other hand, in
path b, coordination of the terminal alkyne in VDCP 2 with the
AuI catalyst also initially generates gold species A, which cycliz-
es with the C-1 carbon in the tethered VDCP to give vinylgold
species D in a 5-exo-dig manner. Intermediate D then under-
goes intramolecular cyclization of the nucleophilic vinylgold
moiety to produce a cyclobutene-containing bicyclic inter-
mediate E. The latter intermediate produces the corresponding
Scheme 2. The cycloisomerization reaction with yne-VDCP 4k as substrate
by using catalyst I.
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tion mechanisms to those described in previous re-
ports on alleneynes, it should be noted that the for-
mation of VDCP rearranged products is very similar
to that of cycloisomerization of alleneyne substrates
catalyzed by Ga or Hg.[17] However, the formation of
3 and 6 suggests the existence of different mechanis-
tic possibilities.
To understand in detail the mechanism for the for-
mation of main product 3h and side product 3h’, we
also investigated the reaction pathway theoretically.
All calculations were performed at the B3LYP level
with the Gaussian 09 program.[10,18,19] The SDD basis
set and pseudopotential were used for the gold
atom[20] and the 6-31G(d) basis set was used for
other atoms. The relative energies of all intermedi-
ates and transitional states along the reaction path-
ways are shown in Scheme 5. Initially, coordination of
terminal alkyne in VDCP 2 with AuI catalyst generates
Scheme 4. Plausible mechanisms for the cycloisomerization of yne-vinylidenecyclopro-
panes.
product 3h’ through ring-opening of the cyclobutene together
with release of the gold catalyst. This is a minor process for
VDCP 2. When VDCP 4 (n=2) is used as the substrate, the re-
action probably also proceeds through both pathways (7-exo-
dig and 6-exo-dig). In this case, path b is the main process,
giving rearranged VDCP 5 as the major product and bicyclic
compound 6 as the minor product. Comparing the above reac-
gold complex 7. In path a, the gold complex 7 undergoes a 6-
exo-dig cyclization to give intermediate 8 via transition state
TS1 with an energy barrier of 8.1 kcalmolÀ1. Subsequently, in-
termediate 8 passes through transition state TS2 with an
energy barrier of 14.3 kcalmolÀ1, producing another carbocat-
ionic intermediate 10. The latter intermediate undergoes intra-
molecular cyclization via TS3 with an energy barrier of 1.9 kcal
Scheme 5. Theoretical investigations on the reaction pathways for the formation of product 3.
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molÀ1, leading to the product complex 12, which is cleaved to
give the major product 3h. On the other hand, in path b, gold
complex 7 undergoes a 5-exo-dig cyclization to give intermedi-
ate 9 via transition state TS1’ with an energy barrier of
11.5 kcalmolÀ1. Subsequently, intermediate 9 undergoes an in-
tramolecular cyclization through transition state TS2’ with an
energy barrier of 13.4 kcalmolÀ1, producing another carbocat-
ionic intermediate 11. In addition, as shown in Scheme 5, a pos-
sible cyclopropyl gold carbene intermediate I was also investi-
gated. However, when we looked for this intermediate, it was
found to be much higher than intermediate 11 by
31.8 kcalmolÀ1. Intermediate 11 passes through transition state
TS3’ with an energy barrier of 10.3 kcalmolÀ1, leading to the
product complex 13, which is cleaved to give the minor prod-
uct 3h’. The results of the calculations show that all intermedi-
ates along path a are thermodynamically more stable than
those along path b, and that path a is also kinetically favorable,
indicating that the bicyclic product 3h is the major product.
These results are consistent with the experimental results
shown in Table 1, which show that bicyclic product 3 was ob-
tained as the major product.
carbocationic intermediate 17. The latter intermediate under-
goes intramolecular cyclization via TS6 with an energy barrier
of 24.9 kcalmolÀ1, leading to the product complex 19, which is
cleaved to give product 6. On the other hand, in path b, gold
complex 14 undergoes 6-exo-dig cyclization to give intermedi-
ate 16 via transition state TS4’ with an energy barrier of
10.6 kcalmolÀ1. Subsequently, intermediate 16 undergoes intra-
molecular cyclization through transition state TS5’ with an
energy barrier of 8.9 kcalmolÀ1, producing another carbocat-
ionic intermediate 18. The latter intermediate passes through
transition state TS6’ with an energy barrier of 12.5 kcalmolÀ1
,
leading to the product complex 20, which is cleaved to give
product 5. The energy barriers along path b are all lower than
those along path a, suggesting that the formation of product
5 is kinetically favorable and that this is a kinetically controlled
reaction. These results are in line with the experimental obser-
vations (Table 2), which show that 5 is obtained as the major
product when yne-VDCPs 4 is used as the substrate.
Conclusion
We further investigated the reaction energy profiles for the
reaction of yne-VDCPs 4, which has a longer tether; the results
are shown in Scheme 6. In path a, gold complex 14 undergoes
7-exo-dig cyclization to give intermediate 15 via transition
state TS4 with an energy barrier of 14.6 kcalmolÀ1. Subse-
quently, intermediate 15 passes through transition state TS5
with an energy barrier of 11.9 kcalmolÀ1, producing another
We have reported a novel cycloisomerization/rearrangement of
newly synthesized yne-VDCPs 2 or 4 catalyzed by a sterically
hindered gold catalyst such as I under mild conditions, thereby
efficiently producing the corresponding bicyclic products as
well as the rearranged VDCP products in moderate to good
yields. The substrate scope of these novel transformations has
been investigated, and plausible reaction mechanisms have
Scheme 6. Theoretical investigations on the reaction pathways for the formation of products 5 and 6.
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been proposed on the basis of isotope labeling experiments
and DFT calculations. Further investigations on the mechanistic
details of the reaction as well as further explorations of other
useful chemical transformations of vinylidenecyclopropanes
are in progress.
Experimental Section
General procedure for the gold-catalyzed cycloisomerization
of VDCPs 2
VDCPs 2 (0.1 mmol), gold catalyst I (5 mol%) and anhydrous DCE
(1.0 mL) were added to a flame-dried tube under argon and the re-
sulting solution was stirred at RT for 0.5 h. The reaction mixture
was evaporated to dryness and the residue was purified by flash
column chromatography on silica gel (PE/EtOAc 20:1) to give the
desired products.
General procedure for the gold-catalyzed cycloisomerisa-
tion/rearrangement of VDCPs 4
To a flame dried tube was added VDCPs 4 (0.1 mmol), gold catalyst
I (5 mol%) and anhydrous DCE (1.0 mL) were added to a flame-
dried tube under argon and the resulting solution was stirred at RT
for 1 h. The reaction mixture was evaporated to dryness and the
residue was purified by flash column chromatography on silica gel
(PE/EtOAc 20:1) to give the desired products.
Acknowledgements
We thank the Shanghai Municipal Committee of Science and
Technology (11JC1402600), the National Basic Research Pro-
gram of China (973)-2009CB825300, and the National Natural
Science Foundation of China for financial support (21102166,
21072206, 20472096, 21372241, 21302203, 20672127,
21121062, 21361140350, and 20732008).
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Keywords: alkynes · cycloaddition · gold · isomerization ·
rearrangement · vinylidenecyclopropanes
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also tested, however, there no significant differences were observed.
For details, see the Supporting Information.
Received: November 22, 2013
Published online on February 12, 2014
[13] CCDC-870106 (3h’) contains the supplementary crystallographic data
for this paper. These data can be obtained free of charge from The
Chem. Eur. J. 2014, 20, 3198 – 3204
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3204
ꢀ 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim