Phenylphosphinacalix[3]trifuran: Synthesis, coordination and application in the Suzuki-Miyaura cross-coupling reaction in water

Article abstract of DOI:10.1039/c5ra11778j

Phenylphosphinacalix[3]trifuran and supramolecular assemblies with palladium have been synthesized. Phenylphosphinacalix[3]trifuran affords turnover numbers as high as 3.05 × 10⁷ in Suzuki-Miyaura cross-coupling reactions in pure water.

Full text of DOI:10.1039/c5ra11778j

View Article Online
View Journal
RSC Advances
This article can be cited before page numbers have been issued, to do this please use: Y. Sun, M. Yan, Y.
Liu, Z. Lian, T. Meng, J. chen, S. Liu and G. Yu, RSC Adv., 2015, DOI: 10.1039/C5RA11778J.
This is an Accepted Manuscript, which has been through the
Royal Society of Chemistry peer review process and has been
accepted for publication.
Accepted Manuscripts are published online shortly after
acceptance, before technical editing, formatting and proof reading.
Using this free service, authors can make their results available
to the community, in citable form, before we publish the edited
article. This Accepted Manuscript will be replaced by the edited,
formatted and paginated article as soon as this is available.
You can find more information about Accepted Manuscripts in the
Information for Authors.
Please note that technical editing may introduce minor changes
to the text and/or graphics, which may alter content. The journal’s
standard Terms & Conditions and the Ethical guidelines still
apply. In no event shall the Royal Society of Chemistry be held
responsible for any errors or omissions in this Accepted Manuscript
or any consequences arising from the use of any information it
contains.
www.rsc.org/advances

Page 1 of 5
RSC Advances
View Article Online
DOI: 10.1039/C5RA11778J
Journal Name
RSCPublishing
COMMUNICATION
Phenylphosphinacalix[3]trifuran: synthesis,
coordination and application in the Suzuki-Miyaura
cross-coupling reaction in water†
Cite this: DOI: 10.1039/x0xx00000x
Received 00th January 2015,
Accepted 00th January 2015
Yue Sun,a MengꢀQi Yan,c Yan Liu,c ZeꢀYu Lian,b Tong Meng,a ShengꢀHua Liu,a Jian
Chen,a GuangꢀAo Yu*a
DOI: 10.1039/x0xx00000x
www.rsc.org/
Phenylphosphinacalix[3]trifuran
and supramolecular the trimeric macrocycle may be the thermodynamically favored
have been synthesized. product.
assemblies
with
palladium
Phenylphosphinacalix[3]trifuran affords turnover numbers as
high as 3.05 × 107 in SuzukiꢀMiyaura crossꢀcoupling reactions in
pure water.
The development of methods for construction of
supramolecular architectures offers chemists the ability to
synthesize many potentially useful species. Ultimately, control
over the synthesis of compounds containing wellꢀdefined cavities
enables the design of species that can arrange molecules in a
specific and predictable fashion for catalysis.1 Indeed, chemists
are now beginning to utilize supramolecular chemistry as a tool
toward the realization of catalytic systems with enzymeꢀlike
properties.2 Acyclic phosphine compounds play an important role
in catalysis3 and supramolecular chemistry. However, studies on
phospha macrocycles are relatively limited.4 Recently, Edwards
established a metalꢀtemplate hydrophosphination method to
construct a cyclic structure on a metal center by a selfꢀcoupling
reaction of primary or secondary alkenylphosphines. Using this
ingenious template method, a dozen phospha macrocycles were
Scheme 1 Oneꢀpot fourꢀstep synthesis of 1.
The proposed mechanism for the formation of
phenylphosphinacalix[3]trifuran (
reaction between 2ꢀfuryllithium and phenylphosphorus
dichloride should yield the di(2ꢀfuryl)phenyl phosphine ( ).
1) is shown in Scheme 2. The
A
B.
n
Reaction of
Diphosphine intermediate
reaction of , 2ꢀfuryllithium and phenylphosphorus dichloride.
would react with BuLi to give the dianion
would be generated by the reaction between dianion
A
with BuLi would then provide intermediate
C
would then be produced by the
B
n
C
D
. Finally,
1
D
and
prepared.5 Herein,
phenylphosphinacalix[3]trifuran,
we
report
the
preparation
construction
of
of
phenylphosphorus dichloride. To confirm the reaction
mechanism, 31P NMR spectra of the reaction mixture at every
the
supramolecular assemblies via metal coordination chemistry, and
application in palladiumꢀpromoted Suzuki crossꢀcoupling
reactions using pure water as solvent.
step
were
studied.
In
addition,
2,4ꢀbis(2ꢀ
furylphenylphosphino)furan (
mixture (see ESI†).
C) was isolated from the reaction
The facile deprotonation of thiophene or furan by a strong
base such as nBuLi is a wellꢀknown process. A wide variety of
bisꢀelectrophiles react with these anions to give bisꢀsubstituted
compounds in high yields, and extension of this reaction to
dianions allows the synthesis of cyclic compounds.6 Using this
Compound
required to handle it under ordinary laboratory conditions. It is
also sufficiently soluble in common organic solvents (e.g.
1 is stable in air, so no special precautions are
,
dichloromethane, chloroform, benzene, and THF) to permit
1
routine spectroscopic analysis. In H NMR and 31P{1H} NMR
procedure, compound 1, a white solid, was obtained as the main
spectra, only one furan proton signal and a sharp phosphorus
product from a oneꢀpot synthesis (Scheme 1). TLC on silica
showed that there were three minor byꢀproducts in the reaction
mixture, but the yields were too low for them to be isolated.
The essential absence of larger cyclic oligomers suggests that
signal were observed, indicating that
structure.
1 has a symmetric cyclic
The corresponding trioxide (
2
) of compound
1
could be
produced by reaction of with H2O2 in CH2Cl2.
1
1 could also be
This journal is © The Royal Society of Chemistry 2012
J. Name., 2012, 00, 1-3 | 1

RSC Advances
Page 2 of 5
COMMUNICATION
VJieowuArrtnicalelONnlainme e
DOI: 10.1039/C5RA11778J
1
converted cleanly to the corresponding trisulfide (3) by reaction of the cyclophane fragment (indicated by H NMR); (ii) observed
with elemental sulfur or to triselenide by reaction with elemental shift in the 31P NMR from −61.95 ppm to −5.19 and −63.46 ppm;
selenium in 91% and 92% yield, respectively. The molecular (iii) a single crystal Xꢀray diffraction study (Figure 2).
structures of
31P{1H} NMR spectra. The 31P{1H} NMR spectra of
contained singlets at 2.62 and 9.01 ppm, respectively. The 31P{1H}
NMR spectra of displayed one major signal with selenium
2
,
3
and
4
were initially elucidated based upon
2
and
3
4
satellites at −5.17 ppm, due to the P atoms bonded to
magnetically inactive Se nuclei, and a doublet (JPꢀSe = 821 Hz)
stemming from the P nucleus bonded to 77Se (7.5% natural
abundance, I
=1/2).7
Figure 2 Molecular structure of 5 with 30% probability level ellipsoids.
Compound
5 is C2v symmetric, and looks like a Si Muwu square
vessel (an ancient cauldron with four legs) (see ESI†). Four
benzene rings bonded to the coordinated phosphine atoms form
four legs. The palladium atom is coordinated in a distorted square
planar geometry with a cis arrangement of two Pꢀdonors and two
Cl atoms. The average Pd–Cl and Pd–P bond lengths are
comparable with those observed in other phosphinopalladium(II)
chloride complexes.8 A pseudoꢀrectangular geometry, where the
four corners are occupied by coordinated
dimensions of approximately 5.50 × 3.53 Å. The internal
geometry of the cyclophane ligands in is different from that in
. The two furanyl moieties in the metallamacrocycle are almost
parallel and separated by 3.385 Å, similar to other compounds
that contain π–π stacking interactions.8 Both furanyl oxygen
atoms point towards the cavity of the metallamacrocycle.
Structural effects due to the formation of the metallamacrocycle
also result in different P–P distances (P(1)–P(2) = 5.512 Å, P(2)–
P(2A) = 5.453 Å).
P atoms, has
Figure 1 Molecular structure of 2 with 30% probability level ellipsoids.
5
1
The structure of
analysis (Figure 1). Compound
2
was confirmed by Xꢀray crystallographic
is C3v symmetric, and looks
2
like a type of threeꢀlegged Chinese Bronze Tripod (an ancient
cauldron) (see ESI†), wherein three furan units and three Ph–P
groups are alternately linked to form a conical framework.
Atoms C(2), C(3), C(6), C(7), C(10) and C(11) form the upper
rim, and all six atoms are nearly coplanar with a mean deviation
of 0.0225 Å. The three oxygen atoms bonded to phosphorus
atoms are all directed to the upper rim of the cone. The P(1)–
C(13), P(2)–C(19) and P(3)–C(25) bonds are almost
perpendicular to the plane mentioned above, so the three
benzene rings bonded to the phosphorus atoms form three legs.
The molecular structures of 3 and 4 were also confirmed by Xꢀray
crystallography (see ESI†). The structures of 3 and 4 are very similar
to that of 2. For example, (i) they also look like Chinese Bronze
Tripods, (ii) the average distance between the two O atoms of the
furan rings is about 2.87 Å for 2, 2.80 Å for 3 and 2.81 Å for 4, and
the three O atoms of the furan ring form an equilateral triangle, (iii)
the P atoms in 3 and 4 possess a tetrahedral configuration with
comparable C–P–C bond angles, and (iv) P=O, P=S and P=Se bonds
are directed to the upper rim of the cone, and O, S or Se, together
with the 3ꢀ and 4ꢀposition carbons of the furan ring form the upper
rim of the cone.
The propensity of 1 toward chelation was tested through its
reaction with PdCl2(NCCH3)2. The single product was assigned as
dinuclear [cisꢀPdCl2(1)]2 (5) on the basis of (i) broken C3 symmetry
Scheme 2 Possible mechanism for the formation of 1.
2 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 2012

Page 3 of 5
Journal Name
RSC Advances
View Article Online
DOI:C10O.1M03M9/CU5NRIAC11A7T78IOJ N
Table 1 The SuzukiꢀMiyaura coupling of various aryl halides with
arylboronic acid in the presence of 1/Pd(OAc)2 in watera
Since the original discovery and development of Pdꢀcatalyzed
coupling reactions that led to the recent chemistry Nobel Prize
being awarded to Heck, Suzuki and Negishi, a great deal of
attention has focused on the development of catalytic systems
that would improve their efficiency.9 The use of phosphine
ligands allows very high turnover numbers (TONs) to be reached
in SuzukiꢀMiyaura couplings, and the search for catalytic systems
allowing ultraꢀlow loadings is an ongoing field.10 In addition,
there has been increasing interest in the use of water as a solvent
for many homogeneously catalyzed reactions. Cost,
environmental benefits, and safety are among the reasons most
often used to justify the replacement of organic solvents by water
in organic transformations.11
Entry
Halide
Boronic acid
Product
Yieldb
90
1
2
92
94
98
61
21
0
3
4
Recently, cavityꢀshaped ligands have been shown to add value
to the efficiency of the SuzukiꢀMiyaura coupling reaction.12 With
5
compound
/Pd as a catalyst in SuzukiꢀMiyaura coupling in water at low
loadings. We applied similar conditions to those reported for the
αꢀCytep tetraphosphine. Using Pd(OAc)2 as palladium
precursor together with compound in a 3:2 ratio, but at a
1 in hand, we then studied the scope and limitations of
1
6
a
1
7
slightly higher (2×10ꢀ8%) loading than the lowest used with αꢀ
Cytep, and K3PO4⋅3H2O in refluxing water for 3 days led to TONs
of up to 3.05 × 107. While the TONs is up to 2.55× 107, using
bromobenzene and 2ꢀmethoxyphenylboronic acid as reactant.
The TONs is just 1.50× 107, using Pd(OAc)2 and
phenyldifuranphosphine as catalyst to the reaction of bromobenzene
with phenylboronic acid (see ESI†). However, this catalytic
system is not as efficient as Buchwald’s ligand for aryl chlorides.
This observation suggests that these high TONs are not due to a
facilitated oxidative addition step but, as previously noted,
longevity of the catalyst can be a key to reach high TONs.13
Under the optimized reaction conditions, a wide array of aryl
bromides reacted smoothly with phenylboronic acid to provide
the corresponding products (see ESI†). For example,
bromobenzene reacted efficiently with phenylboronic acid within
8 h, providing a 90% yield of the desired product (Table 1, entry
1). The reaction of aryl bromides bearing electronꢀwithdrawing
groups, such as –NO2, –CHO, and –COCH3, with phenylboronic
acid also gave the required products in good to excellent yields
(Table 1, entries 2–4). It is also noteworthy that the present
protocol is applicable to the crossꢀcoupling reaction of 2ꢀ
bromothiophene with phenylboronic acid, providing the desired
heterocyclic product in 61% yield (Table 1, entry 5). Furthermore,
crossꢀcoupling reactions of aryl chlorides with phenylboronic
acid resulted in low yields (Table 1, entries 6, 7). The reaction of
phenylboronic acid with aryl bromides bearing electronꢀdonating
substituents such as –NH2, –CH3, –OCH3 gave the desired
products in moderate to high yields (Table 1, entries 8ꢀ16). This
catalyst system can also be used in the coupling reactions of
moderately hindered aryl boronic acids with aryl bromides. For
example, the reaction of 2ꢀmethoxyphenylboronic acid with 4’ꢀ
bromoacetophenone proceeded smoothly to give the biaryl
product in 72% yield (Table 1, entry 18). 2ꢀmethylphenylboronic
acid and 2ꢀnaphthylboronic acid also reacted efficiently with 4’ꢀ
bromoacetophenone to give the desired products in good yields
(Table 1, entries 19, 20).
8
85
82
65
81
87
87
89
91
93
63
72
87
97
9
10
11
12
13
14
15
16
17
18
19
20
aReaction conditions: 1.0 mmol of aryl halide, 1.2 mmol of boronic acid, 0.5
mol% Pd(OAc)2, 1.5 mol% 1, 3.0 mmol of K3PO4·3H2O, 2.0 mL H2O,
100ºC, reaction time 8 h. bIsolated yield (%).
In summary, we have developed a oneꢀpot synthesis of
phenylphosphinacalix[3]furan (
1), representing the first example
of a Pꢀbridged heteracalix[3]arene and expanding the range of
heteracalixarenes. The reaction of
1
with PdCl2(NCCH3)2 gives
This journal is © The Royal Society of Chemistry 2012
J. Name., 2012, 00, 1-3 | 3

RSC Advances
Page 4 of 5
VJieowuArrtnicalelONnlainme e
COMMUNICATION
DOI: 10.1039/C5RA11778J
1859; (c) (h) P. D. Zeits, G. P. Rachiero, F. Hampel, J. H. Reibenspies
and J. A. Gladysz, Organometallics, 2012, 31, 2854; (d) M. Stollenz, N.
Bhuvanesh, J. H. Reibenspies and J. A. Gladysz, Organometallics, 2011,
30, 6510; (e) M. Stollenz, M. Barbasiewicz, A. J. NawaraꢀHultzsch, T.
Fiedler, R. M. Laddusaw, N. Bhuvanesh, and J. A. Gladysz, Angew.
Chem. Int. Ed., 2011, 50, 6647.
(a) JꢀC. Hierso, M. Beaupérin and P. Meunier, Eur. J. Inorg. Chem., 2007,
24, 3767; (b) R. Martin and S. L. Buchwald, Acc. Chem. Res., 2008, 41,
1461.
the binuclear trimacrocyclic system 5. Compound 5 represents
the first example of a metallamacrocycle containing a Pꢀbridged
cavityꢀshaped ligand. Compound does not display exceptionally
high yield. The complex generated with Pd(OAc)2 and ligand
1
1
that exhibit high activities in SuzukiꢀMiyaura crossꢀcoupling.
This property could be associated with its ability of the ligand in
stabilizing the catalytic species by coordination through multiple
binding sites. We have therefore shown that Pꢀbridged
heteracalixarenes can serve as interesting platforms for catalysis
under aqueous conditions.
9
10 (a) A. Fihri, D. Luart, C. Len, A. Solhy, C. Chevrin and V. Polshettiwar,
Dalton Trans., 2011, 40, 3116; (b) D. Schaarschmidt and H. Lang, ACS
Catal., 2011, 1, 411.
11 (a)S.ꢀL. Mao, Y. Sun, GꢀA. Yu, C. Zhao, ZꢀJ. Han, J. Yuan, XꢀL. Zhu, Qꢀ
H. Yang and SꢀH. Liu, Org. Biomol. Chem., 2012, 10, 9410; (b) MꢀO,
Simon and CꢀJ. Li, Chem. Soc. Rev., 2012, 41, 1415; (c) B. Karimi and
P. F. Akhavan, Chem. Commun., 2011, 47, 7686.
12 (a) E. Zaborova, J. Deschamp, S. Guieu, Y. Blériot, G. Poli, M. Ménand,
D. Madec, G. Prestat and M. Sollogoub, Chem. Commun., 2011, 47,
9206; (b) L. Monnereau, D. Sémeril, D. Matt and L. Toupet, Chem. Eur.
J., 2010, 16, 9237.
Acknowledgements
The authors would like to thank the National Natural Science
Foundation of China (Nos. 21472060, 21072071 and 21272088),
selfꢀdetermined research funds of CCNU from the colleges’ basic
research and operation of MOE (Nos. CCNU15A02012).
13 R. B. Bedford, S.L. Hazelwood and M. E. Limmert, Chem. Commun.,
2002, 2610.
Notes and references
aKey Laboratory of Pesticide & Chemical Biology, Ministry of Education,
Central China Normal University, Wuhan 430079, China. E-Mail:
yuguang@mail.ccnu.edu.cn
bState Key Laboratory of Elemento-Organic Chemistry, Nankai University,
Tianjin 300071, China
cState Key Laboratory of Catalysis, Dalian Institute of Chemical Physics,
Chinese Academy of Sciences, Dalian 116023, China
Electronic supplementary information (ESI) available: CCDC reference
numbers 862559-862561 and 913612. For ESI and crystallographic data in
CIF or other electronic format see DOI: 10.1039/b000000x
1
2
3
(a) C. G. Oliveri, P. A. Ulmann, M. J. Wiester and C.A. Mirkin, Acc.
Chem. Res., 2008, 41, 1618; (b) N. C. Gianneschi, M. S. Masar III and C.
A. Mirkin, Acc. Chem. Res., 2005, 38, 825.
(a) H.J. Yoon, J. P. Kuwabara, JꢀH. Kim and C. A. Mirkin, Science, 2010,
330, 66; (b) R. Chakrabarty, P. S. Mukherjee and P. J. Stang, Chem. Rev.,
2011, 111, 6810.
(a) D. S. Surry and S. L. Buchwald, Chem. Sci., 2011, 2, 27; (b) D. Maiti,
B. P. Fors, J. L. Henderson, Y. Nakamura and S. L. Buchwald, Chem.
Sci., 2011, 2, 57; (c) JꢀH. Xie, SꢀF. Zhu and QꢀL. Zhou, Chem. Rev., 2011,
111, 1713.
4
(a) A. J. Saunders, I. R. Crossley, M. P. Coles and S. M. Roe, Chem.
Commun., 2012, 48, 5766; (b) Y. Matano and H. Imahori, Acc. Chem.
Res., 2009, 42, 1193; (c) C. D. Swor and D. R. Tyler, Coord. Chem.
Rev., 2011, 255, 2860; (d) P. G. Edwards and F. E. Hahn, Dalton Trans.,
2011, 40, 10278; (e) T. Albers and P. G. Edwards, Chem. Commun.,
2007, 858; (f) T. Mizuta, T. Aotani, Y. Imamura, K. Kubo and K.
Miyoshi, Organometallics, 2008, 27, 2457; (f) B. P. Friedrichsen, D. R.
Powell and H. W. Whitlock, J. Am. Chem. Soc., 1990, 12, 8931; (g) B. J.
Whitlock, H. W. Whitlock and H. Alles, J. Am. Chem. Soc., 1974, 96,
3959.
5
(a) P. G. Edwards, R. Haigh, D. Li and P. D. Newman, J. Am. Chem.
Soc., 2006, 128, 3818; (b) P. G. Edwards and M. L. Whatton, Dalton
Trans., 2006, 442; (c) P. G. Edwards, K. M. A. Malik, L. Ooi and A. J.
Price, Dalton Trans., 2006, 433; (d) A. R. Battle, P. G. Edwards, R.
Haigh, D. E. Hibbs, D. Li, S. M. Liddiard and P. D. Newman,
Organometallics, 2007, 26, 377; (e) O. Kaufhold, A. Stasch, T. Pape, A.
Hepp, P. G. Edwards, P. D. Newman and F. E. Hahn, J. Am. Chem. Soc.,
2009, 131, 306; (f) T. Albers, J. Baker, S. J. Coles, P. G. Edwards, B.
Kariuki and P. D. Newman, Dalton Trans., 2011, 40, 9525.
B. Koenig, M. Roedel, P. Bubenitschek, P. G. Jones and I. Thondorf, J.
Org. Chem., 1995, 60, 7406.
H. Tsuji, T. Inoue, Y. Kaneta, S. Sase, A. Kawachi and K. Tamao,
Organometallics, 2006, 25, 6142.
(a) T. L. Stott, M. O. Wolf and A. Lam, Dalton Trans., 2005, 652; (b) M.
Fessler, G. Czermak, S. Eller, B. Trettenbrein, P. Brüggeller, L. Bettucci,
C. Bianchini, A. Meli, A. Lenco and W. Oberhauser, Dalton Trans., 2009,
6
7
8
4 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 2012

Page 5 of 5
RSC Advances
View Article Online
DOI: 10.1039/C5RA11778J
Graphic Abstract
Phenylphosphinacalix[3]trifuran: synthesis, coordination
and application in the Suzuki-Miyaura cross-coupling
reaction in water
Yue Sun, Meng-Qi Yan, Yan Liu, Ze-Yu Lian, Tong Meng, Sheng-Hua Liu, Jian Chen, Guang-Ao
Yu
Phenylphosphinacalix[3]trifuran and supramolecular assemblies with palladium
have been synthesized. Phenylphosphinacalix[3]trifuran affords turnover numbers
as high as 3.05 × 107 in Suzuki-Miyaura cross-coupling reactions in pure water.