Intramolecular Parallel [4+3] Cycloadditions of Cyclopropane 1,1-Diesters with [3]Dendralenes: Efficient Construction of [5.3.0]Decane and Corresponding Polycyclic Skeletons

Article abstract of DOI:10.1002/chem.201605190

Aiming to develop efficient and general strategies for construction of complex and diverse polycyclic skeletons, we have successfully developed [4+3]IMPC (intramolecular parallel cycloaddition) of cyclopropane 1,1-diesters with [3]dendralenes. With a combination of the [4+3]IMPC and subsequent [4+n] cycloadditions, trans-[5.3.0]decane skeleton and its corresponding structurally complex and diverse polycyclic variants could be constructed efficiently. This novel [4+3] cycloaddition reaction mode of donor–acceptor cyclopropanes proceeds as a result of the ring-strain relief of a trans-[3.3.0]octane. We strongly believe that the developed methods will demonstrate potential applications in natural products synthesis and drug discovery.

Full text of DOI:10.1002/chem.201605190

A Journal of
Accepted Article
Title: Intramolecular Parallel [4 + 3] Cycloadditions of Cyclopropane
1,1-Diesters with [3]Dendralenes: Efficient Construction of
[5.3.0]decane and Corresponding Polycyclic Skeletons
Authors: Zhongwen Wang, Chi Zhang, Jun Tian, and Jun Ren
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Intramolecular Parallel [4 + 3] Cycloadditions of Cyclopropane
1,1-Diesters with [3]Dendralenes: Efficient Construction of
[5.3.0]decane and Corresponding Polycyclic Skeletons
Chi Zhang, Jun Tian, Jun Ren and Zhongwen Wang*
core skeletons in terpenoids/alkaloids.
Abstract: Aiming to develop efficient and general strategies for
construction of skeletally complex and diverse polycyclic skeletons,
we have successfully developed [4+3]IMPC of cyclopropane 1,1-
Donor–acceptor (D-A) cyclopropanes can be easily obtained
and have been proved to be useful building blocks in organic
synthesis,[4] and in recent years various formal cycloadditions of
which have been developed for efficient construction of
structurally diverse cyclic skeletons. However, compared to
other mostly studied [3+2] and [3+3] cycloadditions for
construction of 5- and 6-membered skeletons, [4+3]
cycloadditions for construction of 7-membered skeletons via D-A
cyclopropane as a 3C-synthon are quite limited. A common
understanding is that due to entropic and enthalpic factors, 7-
membered carbocyclic skeletons are much more difficult to
assemble in high efficiency with conventional methods.[5] Thus,
in the reactions of D-A cyclopropanes with dienes, [3+2]
cycloaddition is considered to be the more favorable one than
[4+3] cycloaddition.[6] Only three intermolecular [4+3]
cycloadditions of D-A cyclopropanes with dienes were reported
(Scheme 1).[7] Ivanova et al reported the first [4+3] cycloaddition
with isobenzofurans[7a,7c] or anthracenes[7b] as dienes (Scheme 1,
A and B), the success of which is probably ascribed to the
aromatization as a driving force. Tang et al reported a [4+3]
cycloaddition with siloxy-substituted dienes (Scheme 1, C),[7d] in
which the steric repulsion between the bulky adamantyl esters
and siloxy groups is considered as the driving force to push the
reaction from the initially formed [3+2] cycloadducts to the
thermodynamically stable [4+3] cycloadducts. It should be
noticed that Budynina et al explored a TiCl4-promoted reaction of
cyclopropane 1,1-diesters with more general alkyl-substituted
dienes.[6b] However, instead of the [4+3] cycloaddition, a [3+2]
one took place exclusively (Scheme 1, D). And in all of these
diesters with [3]dendralenes. With a combination of the [4+3]IMPC
and subsequent [4+n] cycloadditions, trans-[5.3.0]decane skeleton
and its corresponding structurally complex and diverse polycyclic
ones could be constructed efficiently. The [4+3] cycloaddition
reaction mode of D-A cyclopropanes is a novel one which is through
the ring strain relief of a trans-[3.3.0]octane. We strongly believe that
the developed methods will demonstrate their potential applications
to natural products synthesis and leads discovery.
Developing efficient and general strategies to construct
skeletally complex and diverse polycyclic skeletons is quite
important for natural products synthesis, chemical biology
research
and
leads
discovery.
Bicyclo[5.3.0]decane
(hydroazulene), is a core skeleton existing in many structurally
diverse and biologically important natural products (Figure 1).[1-3]
Additionally, many of these natural products contain skeletally
diverse polycyclic skeletons (e.g. the cyclohexane-fused ones)
derived from bicyclo[5.3.0]decane. Thus, it’s quite important to
develop efficient and general strategies for construction of this
core skeleton and corresponding polycyclic ones.
examples, aryl (or vinyl) group as
a donor in the D-A
cyclopropane is necessary for activation of the C-C bond in the
cyclopropane ring, which may restrict the scope of the potential
applications of this method. It should also be noticed that to the
best of our knowledge there is no intramolecular [4+3]
cycloaddition reported up to date.
Intramolecular cycloaddition is one of the most efficient and
direct strategies for construction of polycyclic skeletons. We
have
developed
several
Lewis
acid
(LA)-catalyzed
Figure 1. Some important hydroazulene-derived bicyclic/tricyclic/polycyclic
intramolecular cross (IMCC) and parallel (IMPC) [3+2], [3+3] and
[4+2] cycloadditions of D-A cyclopropanes for construction of
various bridged and fused polycyclic skeletons and applied them
in natural products synthesis.[4h,8] In these examples, we found
that besides the aryl (or vinyl) groups as donors to activate the
D-A cyclopropanes, alkyl groups were also suitable in the
intramolecular cycloadditions and thus make their potential
applications more expansive. We decided to develop
intramolecular [4+3] cycloaddition to build cycloheptane-based
polycyclic skeletons.
[*]
C. Zhang. J. Tian, J. Ren, Prof. Dr. Z. Wang
State Key Laboratory of Elemento-Organic Chemistry
Institute of Elemento-Organic Chemistry, College of Chemistry,
Collaborative Innovation Center of Chemical Science and
Engineering, Nankai University, 94 weijin road, Tianjin 300071 (P.
R. China)
E-mail: wzwrj@nankai.edu.cn
Homepage: http://wzw.nankai.edu.cn
Supporting information for this article is available on the WWW
under http://www.angewandte.org or from the author.
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Scheme 2. Our hypothesis for construction of bicyclo[5.3.0]decane and
corresponding polycyclic skeletons.
To test our hypothesis, we synthesized substrate 1a following
the Fallis’s modified Miginiac-Barbier approach.[11] We were
delighted to find that when the reaction was conducted in 1,2-
o
dichloroethane (DCE) at 50 C under the catalysis of Sc(OTf)3
(10 mol%), the expected [4+3]IMPC cycloadduct 2a was formed,
together with a [3+2]IMPC cycloadduct 3a, both as a single
diasteroisomer. Aiming at improving both the ratio of 2a/3a and
the yield, 1a was used as the model substrate to optimize the
condition (Supporting information). We found that the reaction
was completed within 2 hours under catalysis of most of LAs
and in various solvents, among which 5 mol% of Yb(OTf)3 in
o
toluene at 110 C gave the best result (Scheme 3). Under this
condition 2a and 3a were obtained with a ratio of 7.5:1 and 73%
yield. It should be noticed that even 1 mol% of Yb(OTf)3 could
also efficiently promote the reaction with a longer reaction time
(6 hours).
Under the optimal reaction condition, we explored the scope
of substrates (Scheme 3). It was found that most of the
examples with various substituents on benzene ring gave good
yields and regioiselectivities. It should be pointed out that the
success of methoxyl-substituted examples may guarantee their
potential applications through subsequent dearomatization, e.g.
Birch reduction. When cyclopropane and [3]dendralene were
assembled on the 1,8-position of a naphthalene ring respectively,
Scheme 1. Reported intermolecular [4+3] and [3+2] cycloadditions of D-A
cyclopropanes with dienes.
In this research, we report a LA-catalyzed [4+3]IMPC of
cyclopropane 1,1-diester with [3]dendralene for construction of
[5.3.0]decane skeleton (Scheme 2). [3]Dendralene was first
reported in 1955[9] and can be thought as a diene with a pendent
vinyl group. The most attractive feature of [3]dendralene is its
double Diels-Alder [4+2] cycloadditions for efficient generation of
skeletal complexity.[10] Reasons to choose [3]dendralene are
mainly based on the following considerations: (1) Based on our
previously developed [3+2]IMCC of cyclopropane 1,1-diester
with carbon-carbon double bond for construction of bridged
[n.2.1] carbocyclic skeletons,[8d] we found that a vinyl group
could serve as both an activating group by stabilizing the
o
the reaction proceeded at even lower temperature (60 C) and
with excellent regioiselectivity (2i:3i > 20:1) and yield (90%).
This probably attributes to the rigidity of the naphthalene linker.
carbenium generated in the first cyclization step and
a
regioselectivity-directing group. Thus in the first cyclization step
of this [4+3]IMPC the geminal two vinyl groups will doubly
activate and direct the reaction; (2) a diene moiety in the
[4+3]IMPC cycloadducts will further proceed second [4+n]
cycloadditions for construction of various carbocyclic or
heterocyclic skeletons. This [4+3]IMPC/[4+n] strategy will
provide
a general and efficient one for construction of
bicyclo[5.3.0]decane-derived polycyclic skeletons.
Scheme 3. [a] Ratio of 2/3, determined by 1H NMR spectroscopy of the crude
product. [b] Combined yield. [c] Reaction temperature was 60 oC.
Generation of a diene motif via the [4+3]IMPC provided an
excellent opportunity for post-modifications leading to natural
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Scheme 4. [a] Solvent was dichloromethane (DCM) and the reaction was
conducted at ambient temperature.
products synthesis or leads discovery. Especially, various [4+n]
cycloadditions of diene will provide efficient construction of
additional carbocyclic or heterocyclic skeletons. In Scheme 4,
Diels–Alder [4+2] cycloaddition of 2d with dimethylacetylene
Efficient construction of an additional medium-sized ring by
cycloadditions of diene is also quite important for both natural
products synthesis and leads discovery. To demonstrate this,
two examples were exhibited (Scheme 5). 1c was firstly
converted to an Fe-complex 6[12] and the [4+3]IMPC of which
successfully afforded an additional cycloheptane skeleton (7)
with an excellent diasteroselectivity.[14] The other example is a
[6+4] cycloaddition[15] of 2a with tropone. Pentacylic cycloadduct
8 was obtained as a single diastereoisomer and in an excellent
yield.
dicarboxylate (DMAD) afforded 4a efficiently as
diastereoisomer. Dienophile ethyl propiolate also worked well
with 1d to afford 4b as single isomer, and both the
a single
a
diasteroselectivity and regioselectivity are excellent. When N-
phenylmaleimide was used as dienophile with 1b, 4c was
obtained as a single diastereoisomer[12] in which five new
stereocenters were generated with excellent diastereoselectivity.
1,4-Benzoquinone was also used as dienophile with 1a and 4d
was obtained as a single diastereoisomer. 4d was not very
stable and was quantitatively oxidized to the corresponding
quinone 4e when being exposed to air. A hetero Diels-Alder [4+2]
cycloaddition of dienophile nitrosobenzene[13] was also
conducted with combination of the [4+3]IMPC of 1d.
Cycloadduct 4f was successfully obtained with excellent
regioselectivity. [4+3]IMPC of substrate 1j bearing a tetra-
substituted cyclopropane also successfully proceed and with a
subsequent Diels-Alder [4+2] with DMAD, 4j was afforded.
Under catalysis of Sc(OTf)3 (10 mol%) in DCE at 45 oC,
[4+3]IMPC of substrate 1k with acyclic aliphatic linker also
successfully proceed and with a subsequent Diels-Alder [4+2]
with DMAD, 4k was afforded which was further aromatized to 5k
with oxidation by DDQ. In order to make the construction of
polycyclic skeletons more efficient, we tried to combine the
[4+3]IMPC and the Diels-Alder [4+2] cycloaddition in one-pot.
When the [4+3]IMPC of 1d was completed, DMAD was added
and we were glad to find that the reaction proceeded smoothly
to give 4a as a single diastereoisomer.
Scheme 5.
To further gain insight into the mechanism of the reaction,
we prepared chiral substrate (-)-1a. With the combination of
[4+3]IMPC of (-)-1a and a subsequent [6+4] with tropone, chiral
cycloadduct (+)-8 was successfully obtained (Scheme 6). (+)-8
was obtained as a single enantiomer in which five new
stereogenic centers were generated. The absolute steric
configuration of (+)-8 was unambiguously confirmed by X-ray
crystal analysis.[12] This result indicates an SN2 mechanism in
the first ring-opening/cyclization step of [4+3]IMPC, which is
similar to our previous reported one.[8d] A one-pot version of this
was also successfully carried out and (+)-8 was obtained in 60%.
Scheme 6. Asymmetric [4+3]IMPC of (-)-1a and subsequent [6+4]
cycloaddition.
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In the course of optimizing reaction conditions, we found that
when the reaction was conducted in DCE at temperature below
reflux, besides [4+3]IMPC cycloadduct 2a and [3+2]IMPC cis-
cycloadduct 3a, a third compound 9a was also observed
(Supporting information). With the increase of the reaction
temperature to reflux, 9a disappeared and the ratio of 2a/3a
increased which indicated a conversion of 9a to 2a. 9a was
A respectively and the former one is preferred. The second
[17]
cyclization goes through either [3+2]IMPC
to trans-
[3.3.0]octane (9) or cis-[3.3.0]octane (3), or [4+3]IMPC to trans-
[5.3.0]decane. From the preferred intermediate trans-A, either
[3+2]IMPC to 9 or [4+3]IMPC to 2 may happen, however the
[16]
unstable trans-[3.3.0]octane
9
is converted to the
thermodynamically more stable 2 through trans-A and thus the
[4+3]IMPC dominates the reaction pathway. Conversion of 9 to 2
may be attributed to a synergistic action of the ring strain relief
and push-pull effect of double donors (vinyl groups)/double
acceptors (ester groups) of a trans-[3.3.0]octane. Quite different
from the reported [4+3] cycloaddition reaction modes of D-A
cyclopropanes, this is a novel one.
isolated and the structure of which was confirmed as
a
[3+2]IMPC trans-cycloadduct. An independent experiment was
carried out on 9a (Scheme 7). It was unambiguously confirmed
that 9a was converted to 2a either in DCE or toluene. This result
implied that trans-[3.3.0]octane 9a was thermodynamically less
stable.[16] A synergistic action of the ring strain relief and push-
pull effect of double donors (vinyl groups)/double acceptors
(ester groups) of trans-[3.3.0]octane overcame the difficult
formation of 7-membered ring, which led to a ring-opening of
In conclusion, we have successfully developed LA-catalyzed
[4+3]IMPC cyclopropane 1,1-diesters with [3]dendralenes. To
the best of our knowledge, this is the first intramolecular [4+3]
cycloaddition of D-A cyclopropanes in which the donors can be
either aromatic or aliphatic functional groups. The [4+3]IMPC
reaction mode is also a novel one. By the [4+3]IMPC, a trans-
cyclopentane followed by
cycloheptane.
a
recyclization to afford
a
[5.3.0]decane skeleton was efficiently constructed. With
a
combination of the [4+3]IMPC and subsequent [4+n]
cycloadditions through either stepwise or one-pot process, trans-
[5.3.0]decane-derived structurally complex and diverse
polycyclic ones could be constructed efficiently. We strongly
believe that the developed methods will demonstrate their
potential applications to natural products synthesis and leads
discovery.
Scheme 7. Conversion of [3+2]IMPC trans-cycloadduct 9a to [4+3]IMPC
cycloadduct 2a.
Acknowledgements
We thank NSFC (Nos 21372126, 21572103 and 21421062) for
financial support.
Keywords: cyclopropane • cycloaddition • medium-sized ring •
polycyclic skeleton • natural products
[1]
[2]
E. Breitmaier, Terpenes: Flavors, Fragrances, Pharmaca, Pheromones,
WILEY-VCH, Weinheim, 2006.
One general review: a) D. A. Foley, A. R. Maguire, Tetrahedron 2010,
66, 1131. Some other related reviews: b) R. Dorel, A. M. Echavarren, J.
Org. Chem. 2015, 80, 7321; c) N. Nishiwaki, Methods and Applications
of Cycloaddition Reactions in Organic Syntheses, John Wiley & Sons,
Inc., Hoboken, New Jersey, 2014 ； d) A. Brandi, S. Cicchi, F. M.
Cordero, A. Goti, Chem. Rev. 2014 , 114, 7317; e) L. Jiao, Z. Yu, J. Org.
Chem. 2013, 78, 6842; f) P. A. Wender, Tetrahedron 2013, 69, 7529; g)
I. Fernandez, J. L. Mascarenas, Org. Biomol. Chem. 2012, 10, 699; h)
A. Padwa, Tetrahedron 2011, 67, 8057; i) F. Lopez, J. L. Mascarenas,
Chem. Eur. J. 2011, 17, 418; j) H. Pellissier, Adv. Syn. Catal. 2011, 353,
189; k) A. G. Lohse, R. P. Hsung, Chem. Eur. J. 2011, 17, 3812; l) W.
Zhao, Chem. Rev. 2010, 110, 1706; m) M. Harmata, Chem. Commun.
2010, 46, 8904; n) M. Harmata, Chem. Commun. 2010, 46, 8886; o) H.
Butenschon, Angew. Chem. 2008, 120, 5367; Angew. Chem. Int. Ed.
2008, 47, 5287; p) V. Nair, T. D. Suja, Tetrahedron 2007, 63, 12247; q)
M. Rubin, M. Rubina, V. Gevorgyan, Chem. Rev. 2007, 107, 3117; r) M.
A. Battiste, P. M. Pelphrey, D. L. Wright, Chem. Eur. J. 2006, 12, 3438;
s) M. Harmata, Adv. Synth. Catal. 2006, 348, 2297; t) I. Coldham, R.
Hufton, Chem. Rev. 2005, 105, 2765; u) G. Mehta, S. Muthusamy,
Tetrahedron 2002, 58, 9477; v) M. Harmata, Acc. Chem. Res. 2001, 34,
595; w) L. Yet, Chem. Rev. 2000, 100, 2963; x) E. J. Kantorowski, M. J.
Scheme 8. Proposed mechanism.
Based on the above results, a stepwise mechanism was
proposed (Scheme 8). The initial step is an SN2 attack of internal
C=C of [3]dendralene to open the cyclopropane ring. Two
transition states were involved in this SN2 attack: TSRe and TSSi.
These two transition states led to intermediates trans-A and cis-
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Kurth, Tetrahedron 2000, 56, 4317; y) M. Filippini, J. Rodriguez, Chem.
Rev. 1999, 99, 27; z) L. Yet, Tetrahedron 1999, 55, 9349; aa) G. A.
Molander, Acc. Chem. Res. 1998, 31, 603; ab) M. Harmata,
Tetrahedron 1997, 53, 6235; ac) M. Ramaiah, Synthesis 1984, 529.
Trushkov, P. V. Verteletskii, Eur. J. Org. Chem. 2008, 5329; c) A. O.
Chagarovskiy, O. A .Ivanova, E. M. Budynina, E. L. Kolychev, M. S.
Nechaev, I. V. Trushkov, M. Ya. Mel’nikov, Russ. Chem. Bull. 2013, 62,
2407; d) H. Xu, J. Hu, L. Wang, S. Liao, Y. Tang, J. Am. Chem. Soc.
2015, 137, 8006. A hetero-[4+3] cycloaddition: e) L. K. B. Garve, M.
Pawliczek, J. Wallbaum, P. G. Jones, D. B. Werz, Chem. Eur. J. 2016,
22, 521. A Palladium-catalyzed example: f) R. Shintani, M. Murakami,
T. Tsuji, H. Tanno, T. Hayashi, Org. Lett. 2009, 11, 5642.
[3]
Representative natural products: Presphaerol: a) J. Lee, J. Hong, J.
Org. Chem. 2004, 69, 6433; b) F. Cafieri, E. Fattorusso, B. di Blasio, C.
Redone, Tetrahedron Lett. 1981, 22, 4123; c) F. Cafieri, L. de Napoli, E.
Fattorusso, M. Piattelli, S. Sciuto, Tetrahedron Lett. 1979, 20, 963；
Englerins: d) G. Yue, Q. Huang, P. Zou, Chin. Prog. Chem. 2012, 24,
1742; e) Y. Lu, H. Yao, B. Sun, Chin. J. Org. Chem. 2012, 32, 1; f) R. H.
Pouwer, J.-A. Richard, C.-C. Tseng, D. Y.-K. Chen, Chem. Asian J.
2012, 7, 22; g) W. J. Chain, Synlett 2011, 2605; Daphniphyllum
alkaloids: h) J. Kobayashi, T. Kubota, Nat. Prod. Rep. 2009, 26, 936; i)
Z. Li, Y. Guo, Chin. J. Org. Chem. 2007, 27, 565; j) C. H. Heathcock,
Angew. Chem. 1992, 104, 675; Angew. Chem. Int. Ed. 1992, 31, 665;
Sordarin: k) H. Liang, M. Ciufolini, Org. Prep. Proced. Int. 2010, 42,
111; l) H, Liang, Beilstein J. Org. Chem. 2008, 4, 1.
[8]
a) Z. Wang, S. Chen, J. Ren, Z. Wang, Org. Lett. 2015, 17, 4184; b) W.
Ma, J. Fang, J. Ren, Z. Wang, Org. Lett. 2015, 17, 4180; c) J. Zhang, S.
Xing, J. Ren, S. Jiang, Z. Wang, Org. Lett. 2015, 17, 218; d) W. Zhu, J.
Ren, Z. Wang, Eur. J. Org. Chem. 2014, 2014, 3561; e) J. Ren, J. Bao,
W. Ma, Z. Wang, Synlett 2014, 25, 2260; f) W. Zhu, J. Fang, Y. Liu, J.
Ren, Z. Wang, Angew. Chem. 2013, 125, 2086; Angew. Chem. Int. Ed.
2013, 52, 2032; g) Z. Wang, J. Ren, Z. Wang, Org. Lett. 2013, 15, 5682;
h) Y. Bai, W. Tao, J. Ren, Z. Wang, Angew. Chem. 2012, 124, 4188;
Angew. Chem. Int. Ed. 2012, 51, 4112 ; i) S. Xing, Y. Li, Z. Li, C. Liu, J.
Ren, Z. Wang, Angew. Chem. 2011, 123, 12813; Angew. Chem. Int. Ed.
2011, 50, 12605 ; j) S. Xing, W. Pan, C. Liu, J. Ren, Z. Wang, Angew.
Chem. 2010, 122, 3283; Angew. Chem. Int. Ed. 2010, 49, 3215 ; k) B.
Hu, S. Xing, J. Ren, Z. Wang, Tetrahedron 2010, 66, 5671.
[4]
Selected reviews: a) V. A. Rassadin, Y. Six, Tetrahedron 2016, 72, 4701;
b) H. K. Grover, M. R. Emmett, M. A. Kerr, Org. Biomol. Chem. 2015,
13, 655; c) R. A. Novikov, Y. V. Tomilov, Mendeleev Commun. 2015, 25,
1; d) F. de Nanteuil, F. De Simone, R. Frei, F. Benfatti, E. Serrano, J.
Waser, Chem. Commun. 2014, 50, 10912; e) M. A. Cavitt, L. H. Phun,
S. France, Chem. Soc. Rev. 2014, 43, 804; f) T. F. Schneider, J.
Kaschel, D. B. Werz, Angew. Chem. 2014, 126, 5608; Angew. Chem.
Int. Ed. 2014, 53, 5504; g) Y. Wang, J. J. Yin, Chem. Reagents 2013,
35, 318; h) Z. Wang, Synlett 2012, 23, 2311; i) P. Tang, Y. Qin,
Synthesis 2012, 44, 2969; j) M. Y. Mel'nikov, E. M. Budynina, O. A.
Ivanova, I. V. Trushkov, Mendeleev Commun. 2011, 21, 293; k) T. P.
Lebold, M. A. Kerr, Pure Appl. Chem. 2010, 82, 1797; l) M. J. Campbell,
J. S. Johnson, A. T. Parsons, P. D. Pohlhaus, S. D. Sanders, J. Org.
Chem. 2010, 75, 6317; m) C. A. Carson, M. A. Kerr, Chem. Soc. Rev.
2009, 38, 3051; n) F. De Simone, J. Waser, Synthesis 2009, 3353; o) D.
Agrawal, V. K. Yadav, Chem. Commun. 2008, 6471; p) M. Yu, B. L.
Pagenkopf, Tetrahedron 2005, 61, 321; q) H.-U. Reissig, R. Zimmer,
Chem. Rev. 2003, 103, 1151; r) H. N. C. Wong, M.-Y. Hon, C.-W. Tse,
Y.-C. Yip, J. Tanko, T. Hudlicky, Chem. Rev. 1989, 89, 165; s) E.
Wenkert, Acc. Chem. Res. 1980, 13, 27; t) S. Danishefsky, Acc. Chem.
Res. 1979, 12, 66. A special issue on D-A cyclopropanes (edited by H.-
U. Reissig and D. B. Werz): u) I. V. Trushkov, Israel J. Chem. 2016, 56,
369; v) A. A. Tabolin, S. L. Ioffe, Israel J. Chem. 2016, 56, 385; w) Y.
Deng, M. P. Doyle, Israel J. Chem. 2016, 56, 399; x) C. Lin, B. Plietker,
Israel J. Chem. 2016, 56, 409; y) V. Ganesh, P. Sridhar, S.
Chandrasekaran, Israel J. Chem. 2016, 56, 417; z) N. R. O’Connor, J. L.
Wood, B. M. Stoltz, Israel J. Chem. 2016, 56, 431; aa) R. Talukdar, A.
Saha, M. K. Ghorai, Israel J. Chem. 2016, 56, 445; ab) T. Selvi, K.
Srinivasan, Israel J. Chem. 2016, 56, 454; ac) L. Wang, Y. Tang, Israel
J. Chem. 2016, 56, 463; ad) M. A. Kerr, Israel J. Chem. 2016, 56, 476;
ae) M. C. Martin, R. Shenje, S. France, Israel J. Chem. 2016, 56, 499;
af) A. K. Pandey, A. Ghosh, P. Banerjee, Israel J. Chem. 2016, 56, 512;
ag) O. Reiser, Israel J. Chem. 2016, 56, 531; ah) T. Hudlicky, Israel J.
Chem. 2016, 56, 540.
[9]
a) W. J. Bailey, J. Economy, J. Am. Chem. Soc. 1955, 77, 1133; b) W.
J. Bailey, C. H. Cunov, L. Nicholas, J. Am. Chem. Soc. 1955, 77, 2787.
[10] Reviews on dendralenes: a) M. S. Sherburn, Acc. Chem. Res. 2015, 48,
1961; b) H. Hopf, M. S. Sherburn, Angew. Chem. 2012, 124, 2346;
Angew. Chem. Int. Ed. 2012, 51, 2298; c) H. Hopf, Angew. Chem. 2001,
113, 727; Angew. Chem. Int. Ed. 2001, 40, 705; d) J. D. Winkler, Chem.
Rev. 1996, 96, 167; e) H. Hopf, Angew. Chem. 1984, 96, 947; Angew.
Chem. Int. Ed. 1984, 23, 948.
[11] S. Woo, N. Squires, A. G. Fallis, Org. Lett. 1999, 1, 573.
[12]
CCDC 1499504 ((+)-8), 1499506 (4c) and 1499505 (6) contain the
supplementary crystallographic data for this paper. These data can be
obtained free of charge from The Cambridge Crystallographic Data
Centre via www.ccdc.cam.ac.uk/data_request/cif.
A. Anand, G. Bhargava, P. Singh, M. P. Mahajan, Heterocycles 2009,
77, 547.
[13]
[14]
H. Takaya, S. Makino, Y. Hayakawa, R. Noyori, J. Am. Chem. Soc.
1978, 100, 1765.
[15] J. H. Rigby, Org. React. 1997, 49, 331.
[16] H. L. Gordon, S. Freeman, T. Hudlicky, Synlett 2005, 19, 2911.
[17] A EtAlCl2-promoted [3+2]IMPC with 1,1-dimethyl alkene was reported: R.
B. Beal, M. A. Dombroski, B. B. Snider, J. Org. Chem. 1986, 51, 4391.
[5]
[6]
a) C. Galli, L. Mandolini, Eur. J. Org. Chem. 2000, 2000, 3117; b) G.
Illuminati, L. Mandolini, Acc. Chem. Res. 1981, 14, 95; c) M. A. Winnik,
Chem. Rev. 1981, 81, 491.
[3+2] cycloadditions of D-A cyclopropanes with dienes under various
conditions: a) A. G. Amador, E. M. Sherbrook, T. P. Yoon, J. Am. Chem.
Soc. 2016, 138, 4722; b) E. M. Budynina, O. A. Ivanova, A. O.
Chagarovskiy, Y. K. Grishin, I. V. Trushkov, M. Ya. Melnikov, J. Org.
Chem. 2015, 80, 12212; c) C. Wang, X. Ren, H. Xie, Z. Lu, Chem. Eur.
J. 2015, 21, 9676; d) S. Racine, F. de Nanteuil, E. Serrano, J. Waser,
Angew. Chem. 2014, 126, 8624; Angew. Chem. Int. Ed. 2014, 53,
8484; e) J. Fang, J. Ren, Z. Wang, Tetrahedron Lett. 2008, 49, 6659; f)
P. G. Gassman, R. J. Riehle, J. Am. Chem. Soc. 1989, 111, 2319.
a) O. A. Ivanova, E. M. Budynina, Y. K. Grishin, I. V. Trushkov, P. V.
Verteletskii, Angew. Chem. 2008, 120, 1123; Angew. Chem. Int. Ed.
2008, 47, 1107; b) O. A. Ivanova, E. M. Budynina, Y. K. Grishin, I. V.
[7]
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Intramolecular Parallel [4 + 3]
Cycloadditions of Cyclopropane 1,1-
Diesters with [3]Dendralenes:
Efficient Construction of
[5.3.0]decane and Corresponding
Polycyclic Skeletons
[4+3]IMPC of cyclopropane 1,1-diesters with [3]dendralenes have been
successfully developed. With a combination of the [4+3]IMPC and subsequent [4+n]
cycloadditions, trans-[5.3.0]decane skeleton and its corresponding structurally
complex and diverse polycyclic ones could be constructed efficiently.
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