Carbonylative cycloaddition between two different alkenes enabled by reactive directing groups: Expedited construction of bridged polycyclic skeletons

Article abstract of DOI:10.1039/d0cc05362g

A novel palladium-catalyzed highly selective hydrocarbonylative cycloaddition reaction with two different alkenes in the presence of CO enabled by a reactive directing-group is developed, which offers efficient and convenient access to lactone-containing bridged polycyclic compounds in high yield with high chemo- and stereoselectivities.

Full text of DOI:10.1039/d0cc05362g

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DOI: 10.1039/D0CC05362G
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Carbonylative Cycloaddition Between two Different Alkenes
Enabled by Reactive Directing Group: Expedite Construction of
Bridged Polycyclic Skeletons
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
Bingjian Gao,a‡ Suchen Zou,a‡ Guoqing Yang,a Yongzheng Ding,a and Hanmin Huanga,b,c
*
A novel palladium-catalyzed highly selective hydrocarbonylative Moreover, the intermolecular Heck reaction initiated via the
cycloaddition reaction with two different alkenes in the presence hydropalladation may also take place to compete with the
of CO enabled by reactive direction-group is developed, which desired carbonylation reaction. Therefore, the development of
offers an efficient and convenient access to the lactone-containing an efficient strategy to selectively assemble two different
bridged polycyclic compounds in high yield with high chemo- and alkenes with CO is highly desirable but challenging.
Scheme 1. Palladium-catalyzed carbonylative cross-coupling
with two alkenes
stereoselectivities.
a: Problem in palladium-catalyzed cabonylative cross-coupling of alkenes
Olefins and CO are important feedstock chemicals in synthetic
organic chemistry. Their abundance from the petrochemical
refining and coal chemical industry has spurred the
development of new methodologies for the efficient
transformation of these simple materials. Transition-metal-
catalyzed hydrocarbonylation reactions, transformations that
mobilize the CO for elongation of the carbon chain and installing
a versatile carbonyl functionality, have allowed for the
upcycling of simple olefin feedstock into higher-order valuable
carbonyl products.1,2 In this context, there have been a large
number of reports on the hydrocarbonylation of a single alkene
with different nucleophiles, resulting in a fertile research field
spanning a diverse range of chemical approaches to carbonyl
compounds.2,3 In particular, the direct sequential
hydrocarbonylation/Heck reaction process by connecting two
molecular of olefins via a carbonyl group represents an
attractive approach to enones. Over the last three decades,
various studies on Pd-catalyzed dimerization and
copolymerization of olefins with CO have been reported.4
However, the carbonylative cross-coupling reaction taken place
with two different alkenes and CO remains largely unexplored
because of the inherent formidable challenges of controlling
the chemoselectivity and regioselectivity (Scheme 1a).
O
O
R1
CO
R2
R1
R1
R2
R2
R1
R2
R1
R2
Pd
[
]
+
O
O
(16 possible isomers)
b: Chelation-assisted coordination-insertion polymerization
coordination
FG
R FG
-insertion
+
R
polymerization
n
R
Pd
Ln
FG
c: Reactive chelation-group assisted carbonylative cycloaddition
O
Pd
[
]
O
R
Ar
CO
+
+
R
Ar
O
CH
2
3
1
PdX
O
Ar
Recently, transition-metal-catalyzed C-H functionalization
reactions assisted by chelation-groups have become useful and
efficient approaches to delivering highly efficient
transformations with high selectivity.5 Notable progress has
been achieved for site-selective reactions by using directing-
groups, such as carboxylic acids,6a amides,6b ethers6c and
ketones.6d Similarly, the chelation-assisted copolymerization of
functionalized olefins with non-polar olefins has been
successfully established and extensively investigated for the
selective synthesis of functionalized polyethylenes (Scheme
a. Hefei National Laboratory for Physical Sciences at the Microscale and Department
of Chemistry, University of Science and Technology of China, Hefei, 230026, P. R.
China. E-mail: hanmin@ustc.edu.cn.
b. Center for Excellence in Molecular Synthesis of CAS, Hefei, 230026, P. R. China
c. State Key Laboratory of Oxo Synthesis and Selective Oxidation, Lanzhou Institute of
Chemical Physics, Chinese Academy of Sciences, Lanzhou, 730000, P. R. China
†Electronic
DOI: 10.1039/x0xx00000x
‡These authors contributed equally to this work
Supplementary
Information
(ESI)
available.
See
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1b).7 The above results prompted us to envision that the poor styrenes are competent coupling partners for giving the
View Article Online
DOI: 10.1039/D0CC05362G
chelation-assisted strategy would be competent for enhancing desired products (3ab-3ak) in moderate to good yields (up to
the
selectivity
of
the
transition-metal-catalyzed 81% yield) with excellent selectivities (dr >20:1). With regard to
hydrocarbonylative coupling reactions taking place between the steric effect, more sterically hindered ortho-substituents
two alkenes. However, the directing group itself in most of such generally reduce the yields. In addition, broad functional group
C-H functionalization reactions and copolymerization reactions compatibility was observed with the tolerance towards halide
remains intact during the reactions and has to be removed or and alkyl ether. Besides the substituted styrenes, the 1-
transformed in some cases, which leads to a lower atom- and vinylnaphthalene also gave the tandem product 3al in 56%
step-economy.8 One way to circumvent this drawback is yield. Prop-1-en-2-ylbenzene and (E)-prop-1-en-1-ylbenzene
identifying a reactive directing group, which could not only be were also tested, giving the corresponding products (3am-3an)
utilized as a directing group to enhance the selectivity, but also in good yields with good selectivities. Further broadening the
be incorporated into the desired product via a simple substrate scope indicated the tandem reaction of 2-
transformation. Aldehyde is a class of ubiquitously available and vinylbenzaldehyde 1a with a series of 1,3-dienes and CO could
readily interconvertible functional group, which has proved to also be achieved to give the desired adducts (3ao-3aq) in
be a useful directing-group for transition-metal-catalyzed C-H moderate to good yields. Unfortunately, only product 3a was
functionalization reactions.9 Inspired by these results and in detected when the simple aliphatic alkenes and electron-
connection with our interests in hydrocarbonylation deficient alkenes, such as ethyl acrylate, diethyl maleate, were
reactions,10 we herein report an unprecedented chelation- tested. It is impressive that cis-cyclooctene could participate in
assisted palladium-catalyzed carbonylative cycloaddition this reaction, in which the cross-coupling cycloaddition reaction
reaction with two alkenes and CO, in which the aldehyde- occurred and the desired product 3ar was obtained in 76% yield
functionality contained in the alkene participated in the with excellent diastereoselectivities (dr >20:1). We speculated
carbonylation reaction to form a lactone-containing dienophile, that the observed high reactivity might be attributed to the ring
which enabled the following [4+2]-cycloaddition with another tension of cyclooctene. Noteworthily, the structures of
alkenes (Scheme 1c). This method offers an efficient solution for products of endo-3aa, endo-3am and endo-3an were confirmed
the highly selective cross-carbonylative coupling of olefins and by X-ray single-crystal diffraction analysis.17
the expedient synthesis of bicyclic [2.2.2] lactones, which are Table 2. Substrate Scope of Alkenes for Cross-annulationa
O
common structural motifs in numerous natural products.11-14
[Pd(allyl)Cl]2 (2.5 mol%)
R2
O
R1
RuPhos (5.5 mol%)
anisole, 120 oC, 12 h
R1
R3
R3
+
CO
+
Results and discussion
R2
CHO
1a
2
3
Our investigation initiated by evaluating the reactivity and
product profile of 2-vinylbenzaldehyde (1a) and styrene (2a)
under CO atmosphere in the presence of [Pd(allyl)Cl]2 and
NH4Cl. Extensive experimentation using this standard substrate
(see ESI†) revealed a number of critical reaction parameters. In
particular, no reaction occurred when bidentate phosphines
were utilized as ligands. The observed no reaction may stem
from that the palladium-complex ligated with a bidentate ligand
cannot provide with coordination site to coordinate with
aldehyde-functionality. Among the monophosphines that have
been evaluated, the RuPhos exhibited the highest efficiency to
provide the desired product 3aa with 84% isolated yield as well
as excellent chemoselectivity and stereoselectivity.15 The
exceptionally high reactivity of RuPhos ligated catalyst might be
attributed to the unique structure of the ligand which is capable
of forming weak dative O-Pd interaction to stabilize the 3-
coordinate Pd.16 The inverse electron demand Diels-Alder
reaction and steric effect might be responsible for the result
that only trace amount of homo-coupling product 3a was
detected. In addition, product 3a was obtained in 89% isolated
yield with an excellent stereoselectivity under the same
reaction conditions when only 1a was utilized as a substrate
(see ESI†).
3
product
2
3
2
alkene
product
O
alkene
O
O
O
Ar
O
O
Ar
2a:
2b:
Ar = C6H5
3aa:
3ab:
84%
66%
76%
73%
79%
64%
81%
60%
2m
2n
3am:
66%
Ar = 2-MeC6H4
Ar = 3-MeC6H4
Ar = 4-MeC6H4
2c:
2d:
2e:
2f:
3ac:
3ad:
3ae:
3af:
3ag:
3ah:
3ai :
3aj:
Ar = 4-MeOC6H4
Ar = 4-t-BuC6H4
Ar = 4-CF3C6H4
Ar = 2-ClC6H4
Ar = 3-ClC6H4
Ar = 4-ClC6H4
Ar = 4-FC6H4
3an:
2g:
2h:
2i:
60%
O
Ar
%
O
71
Ar
2j:
71%
71%
56%
2k:
2l:
3ak:
3al:
2o:
2p
2q:
Ar = C6H5
: Ar = 4-MeC6H4
Ar = 4-FC6H4
3ao:
3ap:
54%
56%
Ar = 1-Napth
3aq: 30
O
%
O
O
O
-3aa
endo
2r
3ar:
76%
a Reaction conditions: 1 (0.5 mmol), 2 (0.6 mmol), CO (20 atm), [Pd(allyl)Cl]2
(2.5 mol%), RuPhos (5.5 mol%), NH4Cl (5 mol%), anisole (1.0 mL), 120 oC, 12
h, isolated yield and in all case dr > 20:1.
To extend the applications of this reaction, a variety of
substituted 2-vinylbenzaldehydes were then subjected to the
standard reaction conditions by using styrene 2a in the
presence of CO (20 atm). Under the optimized reaction
conditions, a series of 2-vinyl aryl aldehydes with electron-
donating or -withdrawing substituents on the phenyl ring could
react with styrene to give the corresponding products 3ba-3ia
in good yields with excellent diastereoselectivities (Table 3).
Typical functional groups such as chloride, fluoride, methoxyl
and alkyl were well-tolerated under the optimized reaction
With the optimized reaction conditions in hand, the scope of
alkenes was studied first (Table 2). It appeared that the
electronic nature of the para and meta substituents on the
phenyl ring of the styrenes did not have a strong influence on
the reactivity and selectivity. Both electron-rich and electron-
2 | J. Name., 2012, 00, 1-3
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conditions. Notably, no apparent steric effect or electronic benzo[b]fluorene
COMMUNICATION
the tandem
7
via
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effect was observed in these reactions. After successfully decarboxylation/nucleophilic additionDOI/:d10e.h10y3d9r/aDt0ioCnC053a6n2Gd
examining the tandem cross-coupling annulation reaction, the aromatization process under the same reaction conditions.
substrate scope of homo-annulation reactions was then These new transformations provide an alternative synthetic
explored. The corresponding endo-type bicyclo[2,2,2] lactones approach to biaryl compounds and polycyclic aromatic
3a-j were obtained in good to excellent yields with excellent hydrocarbons (PAHs), which are important building blocks in
diastereoselectivities in all cases. The reaction was found to be material chemistry.18a Reducing the 3aa with Et3SiH in the
marginally affected by the electronics and sterics of the presence of the catalytic amount of InBr3 afforded the bridged
substituents on the aromatic aldehydes as shown by the cyclic ether 5 in 70% yield.18b The aldehyde functionality could
reaction of 1d and 1j, both of which gave relatively lower yields. be facilely reduced to alcohol by NaBH4, providing product 8 in
Typical substituents such as the halide, alkyl, alkoxyl were 92% yield. In addition, the lactone could be hydrolysed in the
tolerated. Additionally, 2-vinyl-1-naphthaldehyde afforded the acidic condition to afford product 6 in 84% yield.18c Moreover,
product 3j in 48% yield with excellent diastereoselectivities (dr the product 3aa could be transferred to the product 9 in 90%
>20:1). The solid structures of endo-3a and exo-3a were yield by conventional Wittig reaction.18d
confirmed by X-ray single-crystal diffraction analysis.17
Table 3. Substrate Scope of 2-vinylbenzaldehydes for Cross- mechanism experiments were conducted. No product 3aa was
annulation and Homo-annulation
To get some insight into the reaction mechanism, a series of
obtained when 3a served as the substrate to react with 2a
under the standard conditions. This result excluded the
possibility that the adduct 3aa was generated from product 3a
and suggested that the cycloaddition reaction was irreversible
(see ESI†). The observed kinetic isotope effects (kH/kD = 1.04)
indicated that the carbon-hybridization change from sp2 to sp3
event of CH=O was most unlikely involved in the rate-
determining step (see ESI†). Further competition reaction with
1a, 2a, and MeOH under the standard reaction condition
disclosed that the product 3aa was obtained as the major
product, suggesting that aldehyde-functionality facilitated the
hydrocarbonylation and enabled the high chemoselectivity (see
ESI†). Kinetic analysis of the standard homo-annulation reaction
of 1a under standard conditions was conducted. The reaction
profile showed that producing the adduct 3a paralleled the
consumption of 1a (see ESI†), which indicated that the
intermediate produced from the hydrocarbonylation was
quickly consumed in the catalytic system. The initial reaction
rate investigation shows an induction period of ~35 min. We
assumed that the induction period may originate from the
generation of HPdCl species from the palladium precursor.
O
[Pd(allyl)Cl]2 (2.5 mol%)
O
Ar
RuPhos (5.5 mol%)
anisole, 120 oC, 12 h
R
CO
+
+
Ar
R
CHO
2a
3
1
Cross-annulationa
O
, R1 = F, R2 = H, 74% yield;
, R1 = Cl, R2 = H, 78% yield;
, R1 = Me, R2 = H, 53% yield;
, R1 = OMe, R2 = H, 63% yield;
, R1 = H, R2 = OMe, 65% yield;
3fa
, R1 = CF3, R2 = H, 74% yield;
, R1 = OMe, R2 = OMe, 73% yield;
3ba
3ca
3da
3ea
3ga
3ha
O
Ph
R1
3ia
, -OCH2O-, 74% yield;
R2
Homo-annulationb
O
O
O
CHO
CHO
CHO
O
O
O
Cl
F
F
3a
X-Ray structure of 3a
, 89%
3b
, 82%
3c
, 85%
Cl
O
O
O
O
CHO
CHO
CHO
CHO
O
O
O
O
CF3
MeO
OMe
MeO
3g
, 92%
3d
3e
3f
, 89%
, 48%
, 95%
CF3
OMe
O
O
O
CHO
CHO
CHO
O
O
O
MeO
MeO
O
OMe
OMe
O
O
O
3h
3j
, 48%
, 84%
3i
, 73%
a Reaction conditions: 1 (0.5 mmol), 2a (0.6 mmol), CO (20 atm), [Pd(allyl)Cl]2
(2.5 mol%), RuPhos (5.5 mol%), NH4Cl (5 mol%), anisole (1.0 mL), 120 oC, 12
h, isolated yield and in all case dr > 20:1. b 1 (0.8 mmol), 2 (0 mmol), isolated
yield and in all case dr > 20:1.
Further kinetic experiments demonstrated
dependence on the pressure of CO and
a
a
zero-order
first-order
Fe(OTf)3 (10 mol%)
PhCl, 130 oC, 6 h
Fe(OTf)3 (10 mol%)
PhCl, 130 oC, 6 h
dependence on the concentration of both 1a and palladium
catalyst (see ESI†). The kinetic results for each factor suggested
that the hydropalladation of the alkene with palladium-hydride
species is the rate-determining step of the tandem reaction,
7
HO
, 88%
4,
84%
O
O
O
InBr3 (10 mol%)
NaBH4
3aa
3a
Et3SiH, CHCl3
60 oC, 1 h
,
CH3OH, 25 oC, 4 h
8
5,
, 92%
70%
CO2Me
which is consistent with the KIE experiment.
O
Pd2+
O
HCl (2.0 eq.)
MeOH/H2
100 oC, 4h
Ph3PCH3Br
t-BuOK, 0-25 o
C
O
CO RuPhos
/
C4
C
NH3
O
O
O+
4 h
9
, 90%
6,
(RuPhos)Pd(0)
84%
NH4Cl
Cl-
O
V
NH4Cl
I
C1
Scheme 2. Synthetic utility
VI
NH3
To demonstrate the synthetic potential of this reaction, a
gram-scale reaction has been conducted to afford 3aa and 3a in
70% and 82% yields, respectively (see ESI†). The synthetic utility
of the bridged polycyclic compounds was demonstrated by
simple transformations (Scheme 2). Under the catalysis of
Ph
O
2
O
C
C
O
Cl
Pd
RuPhos
H
O
(RuPhos)Pd
II
Ph
IV
Cl
3
Fe(OTf)3, the 1-methyl-2-phenylnaphthalene
obtained in 84% yield by heating of 3aa in chlorobenzene at 130
oC via extrusion of CO2 and aromatization. It is interesting to find
4 could be
Cl
CO
Pd
O
RuPhos
O
CH
1
III
that the product 3a was converted to the 5-methyl-11H- Fig. 1. Plausible Reaction Mechanism
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 3
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On the basis of the above results and previous studies,10
a
4
(a) C. Pisano, G. Consiglio, A. Sironi and M. Moret, J. Chem.
View Article Online
Soc., Chem. Commun., 1991, 421; (b) DMO.I:B1r0o.1o0k3h9a/Drt0,CFC.0C5.36R2ixG,
J. M. DeSimone and J. C. Barborak, J. Am. Chem. Soc., 1992,
114, 5894; (c) A. Nakamura, K. Munakata, S. Ito, T. Kochi, L. W.
Chung, K. Morokuma and K. Nozaki, J. Am. Chem. Soc., 2011,
133, 6761; (d) X. F. Wu, H. Neumann and M. Beller, Chem. -
Asian J., 2012, 7, 1199; (e) H. Heeres, A. J. Minnaard, B. Hessen
and H. J. Heeres, Org. Process Res. Dev., 2012, 16, 400; (f) W.
Chang, J. Dai, J. Li, Y. Shi, W. Ren and Y. Shi, Org. Chem. Front.,
2017, 4, 1074; (g) H. Wang and X-F. Wu, J. Organomet. Chem.,
2020, 910, 121134.
tentative reaction pathway for this carbonylative cycloaddition
reaction was proposed (Fig. 1). Initially, palladium hydride
species II is formed via oxidative addition of NH4Cl to
(RuPhos)Pd(0) I, which is formed in situ via reduction of Pd(II)
with CO or phosphine ligand. The selective hydropalladation of
2-vinylbenzaldehyde with II under the assistance of aldehyde
affords the benzylpalladium species III, which further reacts
with CO to produce the intermediate IV. The subsequent
reductive elimination of IV gives the intermediate V and
regenerates the Pd(0) species. The transient benzopyran-2-one
VI is then generated by deprotonation under the assistance of
base, which undergoes [4+2]-cycloaddition with an alkene to
give the desired product 3. Huckel calculations showed that the
LUMO of VI has much larger coefficients at C-1 than at C-4,
which lead to highly regioselectivity.15b, 18c
In summary, we have designed and implemented a new and
efficient strategy to realize an efficient palladium-catalyzed
carbonylative cross-coupling reaction with two different
alkenes and CO. With commercially available catalyst
components, a variety of 2-vinyl aryl aldehydes and simple
alkenes could be directly carbonylated to complex bridged
polycyclic compounds in good to excellent yields. Remarkable
chemo- and stereoselectivity were observed by using the
aldehyde-functionality as the reactive directing group. The
resulting bridged polycyclic products could be derivatized to
useful synthons. Notably, this transformation proceeds in a
100% atom economy and builds a connection between a
palladium-catalyzed hydrocarbonylation and cycloaddition.
Mechanism studies suggest that the reactive aldehyde-
functionality facilitates the hydrocarbonylation and enables the
high chemoselectivity. We expect that these controllable
hydrocarbonylation/cycloaddition processes will provide new
routes to upcycle the simple olefin and CO feedstock into
valuable carbonyl products with versatile uses. Further studies
on substrate scope and mechanism are currently underway and
will be reported in due course.
5
(a) J. R. Hummel, J. A. Boerth and J. A. Ellman, Chem. Rev.,
2017, 117, 9163; (b) C. Sambiagio, D. Schonbauer, R. Blieck, T.
Dao-Huy, G. Pototschnig, P. Schaaf, T. Wiesinger, M. F. Zia, J.
Wencel-Delord, T. Besset, B. U. W. Maes and M. Schnurch,
Chem. Soc. Rev., 2018, 47, 6603; (c) P.Gandeepan and L.
Ackermann, Chem, 2018, 4, 199
(a) R. Giri and J.-Q. Yu, J. Am. Chem. Soc., 2008, 130, 14082;
(b) M. Wasa, K. M. Engle and J.-Q. Yu, J. Am. Chem. Soc., 2010,
132, 3680; (c) A. Iglesias, R. Alvarez, A. R. de Lera and K. Muniz,
Angew. Chem., Int. Ed., 2012, 51, 2225; (d) C. P. Lenges and
M. Brookhart, J. Am. Chem. Soc., 1993, 121, 6616.
6
7
(a) H. Yasuda, R. Nakano, S. Ito and K. Nozaki, J. Am. Chem.
Soc., 2018, 140, 1876; (b) C. Tan and C. Chen, Angew. Chem.,
Int. Ed., 2019, 131, 7268.
8
9
F. Zhang and D. R. Spring, Chem. Soc. Rev., 2014, 43, 6906.
(a) K. Padala and M. Jeganmohan, Org. Lett., 2012, 14, 1134;
(b) C. Liu, M. Liu, J. Sun, C. Li and L. Dong, Org. Chem. Front.,
2018, 5, 2115; (c) J. Yin, M. Tan, D. Wu, R. Jiang, C. Li and J.
You, Angew. Chem., Int. Ed., 2017, 56, 13094; (d) X. Liu, G. Li,
F. Song and J. You, Nat Commun., 2014, 5, 5030; (e) R.
Santhoshkuma, S. Mannathan and C. H. Cheng, J. Am. Chem.
Soc., 2015, 137, 16116.
10 (a) B. Gao, G. Zhang, X. Zhou and H. Huang, Chem. Sci., 2018,
9, 380; (b) G. Zhang, B. Gao and H. Huang, Angew. Chem., Int.
Ed., 2015, 54, 7657; (c) X. Zhou, A. Chen, W. Du, Y. Wang, Y.
Peng and H. Huang, Org. Lett., 2019, 21, 9114; (d) S. Zou, B.
Gao, Y. Huang, T. Zhang and H. Huang, Org. Lett., 2019, 21,
6333; (e) J. Li, S. Wang, S. Zou and H. Huang, Commun. Chem,
2019, 2, 14; (f) Y. Hu and H. Huang, Org. Lett., 2017, 19, 5070;
(g) Y. Hu, Z. Shen and H. Huang, ACS Catal., 2016, 6, 6785.
11 N. Uchiyama, F. Kiuchi, M. Ito, G. Honda, Y. Takeda, O. K.
Khodzhimatov and O. A. Ashurmetov, Tetrahedron, 2006, 6,
4355.
12 Y. Y. Fan, J. B. Xu, H. C. Liu, L. S. Gan, J. Ding, and J. M. Yue, J.
Nat. Prod., 2017, 80, 3159.
13 K.-C. Hsu, J.-M. Fang and Y.-S. Cheng, J. Nat. Prod., 1995, 58,
1592.
This research was supported by the National Natural Science
Foundation of China (21790333, 21925111, 21672199 and
21702197).
14 C. H. Brieskorn, A. Fuchs, J. B. Bredenberg, J. D. McChesney
and E. Wenkert, J. Org. Chem., 1964, 29, 2293.
15 (a) K. Afarinkia, M. J. Bearpark and A. Ndibwami, J. Org. Chem.,
2005, 70, 1122; (b) D. A. Bleasdale and D. W. Jones, J. Chem.
Soc., Perkin Trans., 1991, 1, 1683.
Conflicts of interest
There are no conflicts to declare
16 (a) F. Pan, G. B. Boursalian and T. Ritter, Angew. Chem., Int.
Ed., 2018, 57, 16871; (b) R. Martin and S. L. Buchwald, Acc.
Chem. Res., 2008, 41, 1461.
17 CCDC 1990497 (3a), 1991852 (exo-3a) 1990498 (3aa),
1990499 (3am) and 1990501 (3an) contain the
supplementary crystallographic data for this paper. This data
can be obtained free of charge from The Cambridge
Notes and references
1
2
S. Zhang, H. Neumann and M. Beller, Chem. Soc. Rev. 2020,
49, 3187.
(a) P. Kalck and M. Urrutigoity, Chem. Rev., 2018, 118, 3833;
(b) X.-F. Wu, X. Fang, L. Wu, R. Jackstell, H. Neumann and M.
Beller, Acc. Chem. Res. 2014, 47, 1041; (c) T. Kégl,
Carbonylation of Alkenes and Dienes. In Modern
Carbonylation Methods; pp. 161-198 (Wiley, 2008).
(a) J. Yang, J. Liu, H. Neumann, R. Franke, R. Jackstell and M.
Beller, Science, 2019, 366, 1514; (b) D. Ding, G. Zhu, and X.
Jiang, Angew. Chem., Int. Ed., 2018, 57, 9028; (c) A. Acerbi, C.
Carfagna, M. Costa, R. Mancuso, B. Gabriele, and N. Della Ca’,
Chem. Eur. J. 2018, 24, 4835.
Crystallographic
Data
Centre
via
www.ccdc.cam.ac.uk/data_request/cif.
18 (a) D. Wu, H. J. Ge, S. H. Liu and J. Yin, RSC Adv., 2013, 3,
22727; (b) N. Sakai, T. Moriya and T. Konakahara, J. Org.
Chem., 2007, 72, 5920; (c) D. A. Bleasdale and D. W. Jones, J.
Chem. Soc., Chem. Commun., 1985, 1027; (d) A. Abengózar, P.
García-García, D. Sucunza, A. Pérez-Redondo and J. J.
Vaquero, Chem. Commun., 2018, 54, 2467.
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4 | J. Name., 2012, 00, 1-3
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DOI: 10.1039/D0CC05362G
O
R2
R1
R2
R3
O
R1
Pd
cat. [
]
R3
CO
+
+
Ar
120 oC, anisole
O
Ar
36 examples
up to 95% yield
bicyclo[2,2,2] structure