[N,P]-pyrrole PdCl2 complexes catalyzed the formation of dibenzo-α-pyrone and lactam analogues

Article abstract of DOI:10.1039/c6dt01022a

We herein report the synthesis and catalytic application of a new family of [N,P] ligands based on the pyrrole ring with alpha-phosphine or phosphole units. Their palladium complexes (3a-d) were obtained in very good yields and their catalytic properties were evaluated in the direct intramolecular arylation to obtain both benzopyranones and phenanthridinones. The air stable complex 3a exhibited the best catalytic performance of this series of complexes, using 1 mol% of catalyst in combination with microwaves to promote this reaction.

Full text of DOI:10.1039/c6dt01022a

View Article Online
View Journal
Dalton
Transactions
Accepted Manuscript
This article can be cited before page numbers have been issued, to do this please use: J. V. Suarez-
Meneses, A. OUKHRIB, M. GOUYGOU, M. Urrutigoity, J. Daran, A. Cordero-Vargas, M. C. Ortega-Alfaro
and J. G. Lopez Cortes, Dalton Trans., 2016, DOI: 10.1039/C6DT01022A.
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. We will replace this Accepted Manuscript with the edited
and formatted Advance Article as soon as it 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/dalton

Please do not adjust margins
Dalton Transactions
Page 1 of 9
View Article Online
DOI: 10.1039/C6DT01022A
Journal Name
ARTICLE
[N,P]-pyrrole PdCl2 complexes catalyzed the formation of
Dibenzo-α-pyrone and lactam analogues
Received 00th January 20xx,
Accepted 00th January 20xx
J. V. Suarez-Meneses,a A. Oukhrib,b,c M. Gouygou,b,c M. Urrutigoïty,b,c J.-C. Daran,b,c A. Cordero-
Vargas,a M. C. Ortega-Alfaro,d and J. G. López-Cortésa*
DOI: 10.1039/x0xx00000x
We herein report the synthesis and catalytic application of a new family of [N,P] ligands based on the pyrrole ring with
alpha-phosphine or phosphole units. Their palladium complexes (3a-d) were obtained in very good yields and their
catalytic properties were evaluated in the direct intramolecular arylation to reach both benzopyranones and
phenanthridinones. The air stable complex 3a exhibited the best catalytic performance of this series of complexes, using 1
mol% of catalyst in combination of microwaves to promote this reaction.
www.rsc.org/
of palladium catalysts are usually required (2–10 mol%) to
assure high yields of the coupling product, and the most of
methodologies are still tied to the use of palladium (II) salts
Introduction
Dibenzo-α-pyrones and their derivatives are an important
structural motif found in several natural products1 with
important biological properties.2 For this reason, these kinds of
compounds are used as key intermediates in the synthesis of
pharmaceutically interesting compounds.3
(Scheme 1).
In this context, the development of novel palladium-
catalyzed approaches for the C-H direct functionalization of
arenes13 focused to decrease the catalyst loadings, remains
being an important challenge.
A
diversity of methodologies exists for building the
-pyranone motif.4 However, synthetic strategies
On the other hand, the development of new synthetic
strategies aimed at obtaining new mixed donor ligands is a
steadily growing field. In particular bidentate ligands [N,P] are
very interesting due to the electronic differentiation that can
be induced in both binding sites. Recently, we have
demonstrated that palladium complexes with [N,P] ligands
based on the pyrrole ring efficiently promote Heck coupling
reactions.14 We have also showed some examples about the
use of these complexes on direct arylation as a potential
strategy to build the chromone motif present in arnottin I.
dibenzo-
α
mainly based on palladium-catalyzed reactions have a crucial
role in its obtainment (Scheme 1). They include reactions like
Suzuki–Miyaura cross-coupling of o-bromoarylcarboxylates
and o-hydroxyarylboronic acids,5 Pd-catalyzed CO insertion
into
boroxarophenanthrenes.7
2-arylphenols6
and
10-hydroxy-10,9-
In particular, direct intramolecular arylation has also been
chosen as powerful synthetic protocol to obtain these kinds of
structural motifs,8 due to its effectiveness in the coupling of
encumbered substrates and its versatile application in the
synthesis of complex natural products like gilvocarcins,9
arnottin I,10 WS-5995A,11 graphislactones A–C,8d,
others (Figure 1).
OMe OH
OMe
R2
OMe
12
among
H
OH
Me
MeO
OH
O
O
O
This approach avoids the use of one or both of the pre-
functionalized coupling partners, leading to a more atom-
economical and environmentally friendly processes than
traditional cross-coupling reactions. However, large amounts
OH
R
OR1
O
O
OH
Gilvocarcin M: R = Me
Gilvocarcin V: R = Vinyl
Gilvocarcin E: R = Ethyl
Graphislactone A: R1 = R2 = H
Graphislactone B: R1 = Me, R2 = H
Graphislactone C: R1 = H, R2 = OH
MeO
Me
O
O
O
O
MeO
O
O
OMe
Arnottin I
Figure 1. Natural products with a dibenzo-α-pyranone motif.
O
OH
O
WS-5995A
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 1
Please do not adjust margins

Please do not adjust margins
Dalton Transactions
Page 2 of 9
View Article Online
DOI: 10.1039/C6DT01022A
ARTICLE
Journal Name
O
OMe
X
R1
O
N2
HO
HOOC
I)
C)
H)
(HO)2B
O2N
R2
O
OH
O
X
R2
O
A) o B)
E) o F) o G)
O
R1
R1
R1
R2
R2
D)
J
R
O
X
HO
H
+
(HO)2B
CO2Me
R2
R1
Scheme 1. Synthetic approaches based on palladium-catalyzed reactions. Conditions: A) Pd(OAc)2, CO, AgOAc, CH3CN, 80 °C, 48 h. B) Pd(OAc)2, Cu(OAc)2, Na2CO3, PivOH, CO, Air,
120 °C, 6 h, mesitylene. C) Pd(PPh3)4, K3PO4, 1,4-dioxane, 50 °C, 4 h. D) Pd(OAc)2, K2CO3, DMF, PPh3, 90 °C. E) Pd(OAc)2, NaOAc, DMA, 140 °C. F) Pd(OAc)2, Ph3P, Cs2CO3, DMF, 110
°C. G) Pd(PPh3)2Cl2, NaOAc, DMA, 130 °C. H) Pd(acac)2, CuCl, DPEphos, K2CO3, NMP, 165 °C. I) Pd(PPh3)4, Cs2CO3, DME, H2O, 125 °C. J) PdCl2, CuCl2, CH3CN, reflux.
In an attempt to explore and to better understand the electronic and steric effects different from those of the
scope of direct intramolecular arylation for obtaining a variety diphenylphosphino one.15
of dibenzo-
α
-pyrone and lactam analogues, we herein report
A good template for building a bifunctional [N,P] ligand is
the synthesis and the catalytic application of a new family of the N,N-dimethylamino pyrrole, which can be easily
[N,P] ligands based on pyrrole including phosphine and functionalized in the 2-position, taking advantage of its
phosphole motifs. The palladium complexes obtained from regioselective lithiation17 using n-BuLi at -78° C in anhydrous
these ligands were used as catalysts on direct arylation of a THF. Thus, the 2-lithiopyrrole obtained is quenched with
variety of esters and amides, using microwaves as an energy diverse chlorophosphine or 1-cyanophosphole18 at
0
°C.
source.
Following this strategy, the bidentate ligands 2a-d were
obtained in good yields (Scheme 2).
Results and discussion
Synthesis of [N,P] ligands based on pyrrole and their
palladium (II) complexes.
In continuing with our studies about the synthesis and catalytic
applications of [N,P]-pyrrole ligands, we have envisaged to
combine the pyrrole moiety to diverse phosphorus motifs, in
order to modulate the stereoelectronic properties of the P-
donor. As N-P phosphole based ligands provide efficient
ligands,15 in particular in Pd-catalyzed reactions,16 we have
investigated the replacement of the diphenylphosphino groups
of the standard [N,P]-pyrrole ligand by dicyclopentylphosphino
and two phospholyl units: the 2,5-diphenylphospholyl (DPP)
and the tetramethylphospholyl (TMP), that will bring
Scheme 2.
2 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Please do not adjust margins
Dalton Transactions
Page 3 of 9
View Article Online
DOI: 10.1039/C6DT01022A
Journal Name
ARTICLE
The [N,P] ligands based on pyrrole 2a-d were characterized was corroborated by the structural confirmation of 3
by spectroscopic techniques and the data obtained are diffraction analysis (Figure 2).
consistent with the literature for these kinds of compounds.
d by X-ray
31P NMR spectra reveal interesting properties for these
ligands, showing that the signals for the phosphanyl pyrrole
2a-d are shifted to lower frequencies in comparison to phenyl
phosphines and phenylphospholes (Table 1),19 as a result of
the electron-releasing effect of the pyrrole ring. Comparing the
chemical shift of ligands 2a with 2c, we observe a similar
behavior; this fact could suggest that both of them could show
a similar coordination ability as ligands. In all the cases, we
observe a similar electronic effect produced by the pyrrole
motif, if we compare the chemical shift with their phenyl
analogues, these ligands show a nearly identical
NMR.
ꢀ
δ in 31P
Table 1. 31P NMR chemical shift for [N,P] ligands based on pyrrole and their phosphine
analogues.
Figure 2. ORTEP representation of ligand 3d. Ellipsoids are shown at 50% probability
level. Selected bond length (Å) and bond angles (°): Pd(1)-P(1), 2.1952(8); Pd(1)-N(1),
2.1331(19); Pd(1)-Cl(1), 2.3806(9); Pd(1)-Cl(2), 2.2718(9); N(1)-N(2), 1.441(3); N(2)-
C(21), 1.378(3); P(1)-C(21), 1.779(2); N(1)-Pd(1)-P(1), 87.62(6); N(1)-Pd(1)-Cl(1),
92.59(6); P(1)-Pd(1)-Cl(2), 87.18(4); Cl(2)-Pd(1)-Cl(1), 92.92(4); N(1)-Pd(1)-Cl(2),
173.84(5); P(1)-Pd(1)-Cl(1), 174.29(2).
Compound
R
PyrrolePR2 (2)
-29.2
PhPR2
-6
ꢀδ
2a
2b
2c
2d
Ph13
Cpe
DPP
TMP
23.2
24.1
24.1
26.3
-25.7
-1.6
-2.9
14
-27.0
-12.3
We studied the coordination ability of ligands 2a-d to Pd
(II) using the [PdCl2(CH3CN)2] as precursor in CHCl3, obtaining
in all cases yellow powders in high yields after recrystallization
We observe an effective coordination mode of the [N,P]-
ligand to palladium atom forming a five-membered chelated
ring with an envelope conformation on Pd(1). The phospholyl
group adopts a pseudo-orthogonal orientation (64.69°) to
prevent steric hindrance with the pyrrole moiety. The
coordination geometry around the palladium atom is pseudo
square-planar (4.06° deviation), the ligand bite angle (87.62°)
being the origin of this distortion. The distances Pd(1)-Cl(1)
and Pd(1)-Cl(2) are slightly different, which confirms the
expected trans influence of phospholyl moiety as a result of his
good σ-donor character.
in a mixture of hexane-CH2Cl2 (Scheme 3). As expected, the 31
P
NMR spectra showed that the coordinated phosphine signals
are shifted to higher frequencies regarding the free ligands,
due to coordination with the Pd atom (Table 2).
R
R
P
PdCl2(CH3CN)2
CHCl3 , RT, 4h
N
N
N
N
P
R
R
Pd
Cl
2a-d
Cl
In order to make evident the role of the pyrrole moiety in
the catalytic performance of these complexes, we have
3a, PR2 = PPh2 (88%)
3b, PR2 = Cpe (95%)
3c, PR2 = DPP (86%)
3d, PR2 = TMP (94%)
synthesized the analogous complex
5 (Scheme 4), which
includes a benzene ring as template and the same donor
atoms than 3a
.
Scheme 3.
Table 2. 31P NMR chemical shift for complexes 3a-d.
N
N
1) n-BuLi, -78°C
δ31
P
16.7
40.5
16.5
28.9
ꢀδligand/complex
Ph
2) ClPPh2 , 0°C
Entry
Complex
R
Br
P
Ph13
Cpe
DPP
TMP
45.9
66.2
43.5
41.2
4
(75%)
1
2
3
4
3a
3b
3c
3d
Ph
Pd(CH3CN)2Cl2
CHCl3 , RT, 4h
Likewise, in 1H NMR the signal assigned to the
dimethylamine moiety coordinated to Pd (II) is shifted by
approximately 1 ppm to a higher frequency in comparison to
N
P
Cl
Cl
Pd
2a-d. This behavior has also been observed in 13C NMR (ꢀδ ≈
9
Ph
Ph
ppm) (see Experimental Section). These spectroscopic data
5 (75%)
suggest that these ligands behave as bidentate donors, which
Scheme 4.
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 3
Please do not adjust margins

Please do not adjust margins
Dalton Transactions
Page 4 of 9
View Article Online
DOI: 10.1039/C6DT01022A
ARTICLE
Journal Name
This compound was obtained by the selective ortho- best results (Table 3, entry 5). Once the best base was found,
lithiation of N,N-dimethylaniline, followed by quenching with we have tested different stoichiometric ratio of base:
chlorodiphenylphosphine. Treatment of
of [PdCl2(CH3CN)2] in CHCl3 at room temperature gives the enough to promote a high yield of the corresponding arylation
corresponding complex as an air-stable yellow solid. product. After that, different temperatures were evaluated.
Compounds and were characterized by using various The results obtained show that a temperature of 160º C and
4 with one equivalent substrate (Table 3, Entries 5-8), where 1.2 equiv of AcONa was
5
4
5
spectroscopic techniques.
the use of DMF as solvent is adequate to favor the coupling
reaction (Entries 5 and 9-10).
Catalytic application on direct arylation
Then, different temperatures and solvents were evaluated
(Entries 5 and 9-13). The temperature of each reaction was
fixed at the boiling point of each solvent plus 10º C. Although,
the results obtained show that NMP and DMA are adequate to
favor this reaction, it is necessary to increase the reaction
temperature, and side-products appear drawing out the
purification. For this reason, we have selected DMF as solvent.
Taking into account our previous results in the obtainment of
dibenzopyrones by direct arylation,14 we started this study
using the complex 3a. Initially, we performed aryl-aryl coupling
of ester 6a with an iodine atom as a leaving group using 1%
mol of 3a, DMF solvent, at 160 ºC for 40 minutes, using
microwaves and different bases (1.2 equiv) such as t-BuOK,
K2CO3, Et3N, K3PO4, and AcONa, being the last which gave the
Table 3. Evaluation of catalytic conditions for biaryl cyclization reaction.[a]
Entry
1
[Pd]
Base
Base/[Pd]
1.2
1.2
1.2
1.2
1.2
0.5
0.8
2
Solvent
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMSO
NMP
DMA
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
Temperature (ºC)
160
Time (min)
40
40
40
40
40
40
40
40
40
40
40
40
40
40
40
5
% mol [Pd]
Yield of 7a (%)[b]
3a
t-BuOK
K2CO3
1
1
68
36[c]
20
11
94
47
70
95
48
94
17[c]
77[c]
81[c]
10
82
37
69
75
90
92
94
80
79
44
20
80
49
51
54
2
3a
160
3
3a
Et3N
160
1
4
3a
K3PO4
160
1
5
3a
AcONa
AcONa
AcONa
AcONa
AcONa
AcONa
AcONa
AcONa
AcONa
AcONa
AcONa
AcONa
AcONa
AcONa
AcONa
AcONa
AcONa
AcONa
AcONa
AcONa
AcONa
AcONa
AcONa
AcONa
AcONa
160
1
6
3a
160
1
7
3a
160
1
8
3a
160
1
9
3a
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
140
1
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
3a
180
1
3a
200
1
3a
210
1
3a
175
1
3a
160
0.25
0.5
1
3a
160
3a
160
3a
160
10
15
20
30
50
90
40
40
40
40
20
20
20
1
3a
160
1
3a
160
1
3a
160
1
3a
160
140[d]
1
3a
1
3b
160
1
3c
3d
160
1
160
1
5
160
1
2a + Pd(OAc)2
2a + Pd(ACN)2Cl2
Pd(OAc)2
160
1
160
1
160
1
[a] All reactions were performed with 1.0 mmol of the aryl iodide and 6 mL of solvent. [b] Isolated yield after SiO2 column chromatography. [c] A complex mixture of side-
products is observed by TLC, decreasing the yield of desired product. [d] Reaction conducted in reflux conditions.
4 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Please do not adjust margins
Dalton Transactions
Page 5 of 9
View Article Online
DOI: 10.1039/C6DT01022A
Journal Name
ARTICLE
Following the screening of the reaction conditions, we
evaluated different catalyst load, finding that 1% mol of
palladium complex is necessary to obtain a good yield (Entries
Table 4. Scope of biaryl cyclization reaction using esters as substrates.
5
and 14-15). Finally, we have performed a series of
experiments to evaluate the reaction time; we observe that at
20 minutes, the coupling product is obtained in 90% yield and
if we extend the reaction time until 50 minutes, we did not
observe a yield increase (Table 3, Entries 5 and 16-21). The
effectiveness of the microwave irradiation and conventional
heating for direct arylation reaction has been compared. We
performed the direct arylation under thermal conditions using
a DMF reflux (Table 3, entries 9 and 22). We obtain a good
yield of the desired product, being necessary to increase the
reaction time until 90 minutes. Although both methods are
efficient for the direct arylation, the microwave-assisted
reactions were slightly faster in comparison to conventional
thermal conditions, which can be attributed to a small increase
in the pressure, assisted by the microwave reactor.
Entry
1
Compound
R
p-Me
Yield 7 (%)[a]
Yield 8 (%)
6a
6b
6c
6d
6e
6f
94
86[c]
88
0
2
2
m-Me
o-Me
3
0
4
p-H
85
0
5
p-OMe
p-SMe
1-naphtyl[b]
p-F
96
0
6
90
8
8
6g
6h
6i
79
7
9
77
12
16
23
29
25
10
11
12
13
p-Cl
71
6j
p-CO2Et
p-CF3
38[d]
0[d]
0[d]
As a further step, we also compared these findings with
complexes 3b-3d (Table 3, Entry 23-25). We observe that
complex 3b (Entry 23) promotes this reaction, obtaining the
coupling product in 79% yield. However, when we tested the
complexes 3c and 3d, both containing a phosphole moiety, the
direct arylation is not efficient with 44% and 20% yield,
respectively (Entries 24-25). These findings could be explained
for the fragility of these complexes to reaction conditions.
To evaluate the role of pyrrole moiety in the catalytic
performance of these palladium complexes, we proceeded to
6k
6l
p-NO2
[a]
[b]
Isolated yield after SiO2 column chromatography. The starting material was
[c]
naphthalen-1-yl-2-iodobenzoate. A mixture of regioisomers 7b/7b’ is detected
[d]
in (47/53) ratio by NMR. A complex mixture of side-products is observed by
TLC, decreasing the yield of desired product.
Analyzing the results obtained, we observe that the direct
arylation proceeds with yields ranging from 86 to 96% for
substrates containing electron-donor groups (Table 4, Entries
1-6). However, when we incorporate moderate electron-
withdrawing groups in the para-position to ester group, the
benzopyranone was obtained in moderate yields (38-79%) and
evaluate the complex 5, in the direct arylation of compound 6a
(Table 3, entry 26). The result obtained shows that this
complex is similarly active than 3b (Entry 23); however, the
catalytic performance of complex 3a make evident that pyrrole
framework plays an important role in the donor capability of
these ligands.
the formation of triphenylene 8 appears as side-product (Table
4, Entries 8-11). The predominant formation of this last
compound is detected, if strong electron withdrawing groups
such as –NO2 and CF3 are incorporated as substituents (Table
4, Entries 12-13).
Finally, we have also conducted three additional
experiments (Table 3, entries 27-29). The coupling reaction
was performed by preparing the catalyst in situ, mixing the
ligand 2a and Pd(II) and substrate. We have used as
commercially available Pd(II) sources, Pd(OAC)2 and
Pd(ACN)2Cl2. In both cases, the coupling product was obtained
in low yield (around 50%). Finally, as last control experiment,
we have carried out this coupling reaction using Pd(OAc)2 as
palladium precursor, affording a similar result. Analyzing the
results obtained, we confirmed the convenience of using
complex 3a to promote this direct arylation in good yields.
Taking into account these results obtained and in order to
explore the scope of this reaction and the catalytic
performance of complex 3a, we have conducted direct
intramolecular arylation with a wide range of activated and
deactivated esters in the best conditions described above (1%
mol of 3a, AcONa as base, DMF as solvent, at 160º for 20
minutes and using MW to promote this reaction). The results
are listed in table 4.
In order to study the regioselectivity of this reaction, we
have incorporated
a methyl group in different relative
positions to the ester group, obtaining in all cases the
benzopyranone in good yields. In the case of ester 6b, we have
obtained a mixture of regioisomers 7b/7b’ in a relation
(47/53), indicating that the steric effect is not important in this
reaction (Table 4, Entry 2). When the methyl group is in ortho-
position to ester group, we obtain
a
good yield of
could be
benzopyranone 7c. The formation of triphenylene
8
explained by the imminent hydrolysis of ester group affording
a benzoate intermediate, which can form the corresponding
benzyne generated through C–H activation with Pd(II) and
consecutive decarboxylation as previously described.20
In an attempt of extending the scope of this reaction, we
have explored the catalytic performance of complex 3a, using
different amides
9 as substrates (Table 5). As we can see, the
direct arylation proceeds from a clean and efficient manner,
yielding the corresponding phenanthridinone 10 in 73-97%,
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 5
Please do not adjust margins

Please do not adjust margins
Dalton Transactions
Page 6 of 9
View Article Online
DOI: 10.1039/C6DT01022A
ARTICLE
Journal Name
Table 5. Scope of biaryl cyclization reaction using amides as substrates.
sensing is achieved by a hydraulic sensor integrated in the
swiveling cover of the instrument. The reusable 10 mL Pyrex
vial is sealed with PEEK snap caps and standard PTFE coated
silicone septa. Reaction cooling is performed by compressed
air automatically after the heating period has elapsed.
Structure determination by X-ray crystallography
Suitable X-ray-quality crystals of 3d were grown through slow
evaporation of a chloroform/benzene solvent mixture at –5°C.
Single crystal of 3d was mounted on a glass fiber at room
temperature. The crystal was then placed on an EOS Gemini
Agilent-Technologies CCD diffractometer equipped with Mo-
Kα radiation; decay was negligible in all cases. Details of
crystallographic data collected on compound 3d are provided
in Table 6. Systematic absences and intensity statistics were
used in space group determinations. The structure was solved
using direct methods.21
Entry
Compound
R1
p-Me
p-H
R2
H
Yield 10 (%)[a]
1
2
3
4
5
6
7
9a
9b
9c
9d
9e
9f
36[b]
79
73
80
97
87
90
Me
Bz
p-H
p-Me
p-OMe
p-F
Me
Me
Me
Me
9g
p-Cl
[a] Isolated yield after SiO2 column chromatography. [b] A complex mixture of side-
products is observed by TLC, decreasing the yield of desired product.
Anisotropic structure refinements were achieved using full-
matrix least-squares techniques on all non-hydrogen atoms. All
hydrogen atoms were placed in idealized positions, on the
basis of hybridization, with isotropic thermal parameters fixed
at 1.2 times the value of the attached atom. Structure
solutions and refinements were performed using SHELXTL
v6.10.22 Crystallographic data for 3d are available in CIF format
in the Supporting Information.
when we used a tertiary amide group. However, the reaction is
not efficient for secondary amides, obtaining the lactam 10a in
low yield (36%), and an inseparable mixture of side-products
(Table 5, entry 1). The reaction tolerates different substituents
and, we do not observe a strong dependence of the electron
characteristics of these groups on the yield. In comparison to
the precedent reaction, the formation of triphenylene is not
detected.
Table 6. X-ray Data Collection and Structure Refinement Details for complex 3d
Compound
Formula
3d
C14H21Cl2N2PPd
425.60
MW (g-1 mol-1)
Crystal size (mm3)
Crystal system
Space group
a/Å
Experimental
0.250 x 0.150 x 0.070
Monoclinic
P 21/n
General Considerations
All operations were carried out under inert atmosphere of
nitrogen or argon gas using standard Schlenk techniques.
Anhydrous THF was obtained by distillation under an inert
11.598(5)
b/Å
13.656(5)
c/Å
12.222(5)
atmosphere
over
sodium
benzophenone.
Column
α
β
/(°)
/(°)
90.000(5)
chromatography was performed using 70–230 mesh silica gel.
All reagents and solvents were obtained from commercial
suppliers and used without further purification. All compounds
were characterized by IR spectra, recorded on a Perkin-Elmer
283B or 1420 spectrophotometer, by means of film and KBr
techniques, and all data are expressed in wave numbers (cm-1).
Melting points were obtained on a Melt- Temp II apparatus
and are uncorrected. NMR spectra were measured with a
Bruker Avance III +300 using CDCl3 and C2D6SO as solvents.
117.992(5)
90.000(5)
γ
/(°)
Volume/ Å3
1709.3(12)
4
Z
dc/Mg m-3
1.654
Θ/°
2.983 to 26.370
-14≤h≤14
Index Ranges
-17≤k≤17
-15≤l≤15
Reflections collected
Independent reflections
Data/parameters
Final R indices
10189
Chemical shifts are in ppm (δ), relative to TMS. The MS-FAB
3080 [R(int)=0.0202]
3480/ 0 /187
R1=0.0224
wR2=0.0520
wR2=0.0520
R1=0.0.0287
wR2=0.0.0549
1.042
and MS-EI spectra were obtained on a JEOL SX 102A, the values
of the signals are expressed in mass/charge units (m/z),
followed by the relative intensity with reference to a 100% base
peak.
[I>2σ(I)]
Microwave irradiation experiments were performed using
R indices (all data)
a
Monowave 300 single-mode microwave reactor. The
GoF(F2)
reaction temperature is monitored by an internal fiber-optic
(FO) temperature probe (ruby thermometer) protected by a
borosilicate immersion well inserted directly into the reaction
mixture. Reaction times refer to the hold time at the desired
set temperature and not to the total irradiation time. Pressure
Absorptions corrections
Semi-empirical from
equivalents
1412293
CCDC number
6 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Please do not adjust margins
Dalton Transactions
Page 7 of 9
View Article Online
DOI: 10.1039/C6DT01022A
Journal Name
ARTICLE
General synthesis of ligand bidentate [N,P] based on pyrrole (2a-d) 2-(diphenylphosphino)-N,N-dimethylaniline (4). White solid.
1
(85 %). mp: 110-112 °C. H NMR (300.53 MHz, CDCl3) δ 7.31-
The synthesis of ligand 2a was conducted following the
methodology previously described.[14] The 1-cyano-phospholes
7.21 (m, 12H, H3,6,9,10,11aromatic), 6.98 (t, J= 7.4 Hz, 1H, H4aromatic),
6.80 (m, 1H, H5aromatic), 2.60 (s, 1H, H1-N-(CH3)2). 13C NMR (75.58
used in the synthesis of ligands 2c-d were prepared as
described in literature.[17]
MHz, CDCl3) δ 158.1 (d, J = 19.5 Hz, C2ipsoN-aromatic), 138.3 (d, J =
11.8 Hz, C8ipsoP-aromatic), 134.4 C6N-aromatic, 133.9 (d, J = 20 Hz,
A solution of N,N-dimethyl-1H-pyrrol-1-amine (8.3 mmol,
C9,13P-aromatic, 129.9 C4N-aromatic, 128.4 (d, J = 2.0 Hz, C10,12P-aromatic),
1equiv) in anhydrous THF (15 mL) under nitrogen atmosphere,
128.3 C11P-aromatic, 124.5 C3N-Aromatic, 120.7 (d, J = 2.6 Hz, C5
N-
was cooled at -78 °C and then n-butyl lithium (9.9 mmol, 1.2
aromatic), 45.6 (d, J = 3.4 Hz, C1-N-(CH3)). 31P NMR (50 MHz, CDCl3) δ
equiv. Sol. 2.5 M in n-hexane) was added dropwise by syringe.
-14.49.
. : 3056 (=C-H),2960 (-CH),
IR (KBr, cm-1) νmax
The mixture was gradually warmed to room temperature.
After reaching this temperature, the reaction mixture was
cooled at 0ºC, followed by the addition of the corresponding
phosphor-electrophile (8.3 mmol, 1equiv) and stirring at room
temperature for 2 h. The solvent was evaporated at reduced
1591(C=Carom), 756 (Ph monosust arom). MS (DART): m/z (% x103):
306 [M+1] (1200). HR-MS (DART): calcd for C20H21NP [M+]
306.14116; found 306.14179.
General procedure for complexation reaction
pressure and the crude was purified by column To a solution of the corresponding ligand
2 (0.5 mmol) in
chromatography. Elution with hexane/ethyl acetate.
chloroform (15 mL) was added [Pd (CH3CN)2Cl2] (0.5 mmol),
then the mixture was stirred for 4 h at room temperature. The
2-(dicyclopentylphosphino)-N,N-dimethyl-1H-pyrrol-1-amine
1
(2b). Colorless oil (80 %). H NMR (300.53 MHz, CDCl3) δ 7.06 solvent was removed under vacuum leaving a yellow residue
(s, 1H, H2pyrrole), 6.17 (d, J = 8.1 Hz, 2H, H3,4pyrrole), 2.82 (s, 6H, which was dissolved in dichloromethane. The resulting
H1), 2.28 – 2.21 (m, 2H, H10,12), 1.94 – 1.90 (m, 2H, H6,11), 1.67 – solution was filtered through celite and finally it is
1.24 (m, 14H, H7,8,9,10,12,13,14,15). 13C NMR (75.58 MHz, CDCl3) δ concentrated to a minimum and hexane was added to
5
128.9 (d, J = 6.2 Hz, Cipso pyrrole), 115.5 C2pyrrole , 112.3 (d, J = 2.6 precipitate the complex, which was filtered, washed with
Hz, C3pyrrole), 107.6 (d, J = 3.0 Hz, C4pyrrole), 48.1 C1-N-(CH3)2, 36.9 hexane, and dried under vacuum.
(d, J = 6.4 Hz, C6, 11cyclopenthyl), 31.2 (d, J = 6.1 Hz, C10,12cyclopenthyl), Palladium dichloro[2-(diphenylphosphino-kP)-N,N-dimethyl-
31 (d, J = 2.8 Hz, C7,15cyclopenthyl), 26.7 (d, J = 7.9 Hz, 1H-pyrrol-1-amine-kN] (3a). Yellow solid. (95 %). mpdec: 280
C9,13cyclopenthyl), 25.8 (d, J = 6.5 Hz, C8, 14cyclopenthyl). 31P NMR (50 °C.[14]
MHz, CDCl3) δ -25.71. IR (KBr, cm-1) νmax: 3096 (=C-H), 2946 (- Palladium
dichloro[2-(dicyclopentylphosphino-kP)-N,N-
CH). MS (DART): m/z (% x106): 279.12512 [M+1] (18). HR-MS dimethyl-1H-pyrrol-1-amine-kN] (3b). Yellow solid. (95 %).
(DART): calcd for C16H28N2P [M+] 279.1990; found 279.19851.
mpdec: 280 °C. 1H NMR (300.53 MHz, CDCl3) δ 7.26-7.23 (m, 1H,
H2pyrrole), 6.63-6.61 (m, 1H, H4pyrrole), 6.34-6.32 (m, 1H, H3pyrrole),
2-(2,5-diphenyl-1H-phosphol-1-yl)-N,N-dimethyl-1H-pyrrol-1-
amine (2c). Yellow solid. (45 %). mp: 64-66 °C. 1H NMR (300.53 3.66 (s, 6H, H1), 2.67 (h, J = 8.1 Hz, 2H, H10,12), 2.38 – 2.30 (m,
MHz, CDCl3) δ 7.55 (d, J = 7.8 Hz, 4H, Hortho-phenyl), 7.29 – 7.13 2H, H6,11), 2.05–1.66 (m, 14H, H7,8,9,10,12,13,14,15). 13C NMR (75.58
(m, 8H, Haromatic, Hβ-phosphole), 6.96 (s, 1H, H2pyrrole), 6.30-6.27 (m, MHz, CDCl3) δ 120.2 (d, J = 6.2 Hz, C5ipso-pyrrole), 119.4 C2
,
,
pyrrole
1H, H4pyrrole), 6.07 (q, J = 2.9 Hz, 1H, H3pyrrole), 2.48 (s, 1H, H1
116.4 (t, J = 7.7, 6.4 Hz, C4pyrrole), 111.4 C3pyrrole), 57.2 C1
-N-
-N-(CH3)2
(CH3)2). 13C NMR (75.58 MHz, CDCl3) δ 150.3 (d, J = 5.1 Hz, Cipsoα- 37.8 (d, J = 37.4 Hz, C6, cyclopenthyl), 29.7 (d, J = 2.7 Hz,
11
phosphole), 137.1 (d, J = 16.6 Hz, Cipso phenyl
Cβ-phosphole), 128.6 Cpara phenyl, 126.8 Cmeta phenyl
Hz, Cortho phenyl
116.9 C4pyrrole, 108.5 (d, J = 9.4 Hz, C3pyrrole), 47.9 C1
-
), 131.1 (d, J = 12.5 Hz, C10,12cyclopenthyl), 29.3 (d, J = 2.9 Hz, C7,15cyclopenthyl), 26.4 (d, J =
-
-
, 126.4 (d, J = 9.4 10.1 Hz, C9,13cyclopenthyl), 25.6 (d, J = 12.2 Hz, C8, 14cyclopenthyl). 31P
5
-
), 118.5 C2pyrrole, 118.3 (d, J = 3.6 Hz, Cipso
,
NMR (50 MHz, CDCl3) δ 40.54. IR (KBr, cm-1) νmax: 3103 (=C-
pyrrole
.
31P H), 2952 (-CH). MS (FAB+): m/z (100 %): 421 [M+1-Cl] (55), 421
-N-(CH3)
NMR (50 MHz, CDCl3) δ -27.02. IR (KBr, cm-1) νmax: 3056 (=C- [M+1-] (55). HR-MS (FAB+): calcd for C16H27ClN2PPd [M+]
H),2960 (-CH), 1591(C=Carom), 756 (Ph monosust arom). MS (DART): 421.0633; found 421.0639.
m/z (% x106): 345 [M+] (35).
Palladium
dichloro[2-(2,5-diphenyl-1H-phosphol-1-yl-kP)-
N,N-dimethyl-2-(2,3,4,5-tetramethyl-1H-phosphol-1-yl)-1H
N,N-dimethyl-1H-pyrrol-1-amine-kN] (3c). Orange solid. (86
pyrrol-1-amine (2d). Yellow solid. (50 %). mp: 58-60 °C. 1H %). mpdec: 280 °C. H NMR (300.53 MHz, CDCl3) δ 7.88 (d, J =
NMR (300.53 MHz, CDCl3) δ 6.98 (q, J= 2.6 Hz, 1H, H2pyrrole), 7.6 Hz, 4H, Hortho-phenyl), 7.62 – 7.08 (m, 10H, Haromatic, Hβ-
6.05 (t, J= 3.0 Hz, 1H, H4pyrrole), 5.70 (dd, J= 2.2, 1.1 Hz, 1H, phosphole, H2pyrrole), 6.52 (m, 1H, H4pyrrole), 6.17 (m, 1H, H3pyrrole),
H3pyrrole), 2.74 (s, 1H, H1-N-(CH3)2) 1.93 (d, J = 10.7 Hz, 6H, 3.70 (s, 1H, H1-N-(CH3)2). 31P NMR (50 MHz, CDCl3) δ 16.5. MS
H7,13CH3CP), 1.82 (d, J = 1.9 Hz, 6H, H9,11CH3). 13C NMR (75.58 (FAB+): m/z (100 %): 487 [M+1-Cl] (5). HRMS (FAB+): calcd for
1
MHz, CDCl3) δ 142.2 (d, J = 13.3 Hz, Cipsoα-phosphole), 133.6 (d, J = C22H21ClN2PPd [M+] 487.0162; found 487.0170.
5
5.2 Hz, Cipso
-
β phosphole), 122.9 (d, Cipso pyrrole), 116.5 C2
,
Palladium dichloro[N,N-dimethyl-2-(2,3,4,5-tetramethyl-1H-
pyrrole
111.5 (d, J = 3.4 Hz,C4pyrrole, 108.5 (d, J = 3.9 Hz, C3pyrrole), 48.2 phosphol-1-yl-kP)-1H-pyrrol-1-amine-kN] (3d). Yellow solid.
C1-N-(CH3), 14.0 (d, J = 3.2 Hz, C7,13CH3CP), 13.2 (d, J = 21.5 Hz, (94 %). mpdec: 280 °C. H NMR (300.53 MHz, CDCl3) δ 7.30 (m,
1
C9,11CH3), 31P NMR (50 MHz, CDCl3) δ -12.25. IR (KBr, cm-1) νmax
:
1H, H2pyrrole), 6.59 (m, 1H, H4pyrrole), 6.05 (m, 1H, H3pyrrole), 3.72
2909 (-CH), 1512(C=Carom). MS (DART): m/z (% x106): (s, 1H, H1-N-(CH3)2) 2.06 - 1.97 (m, 12H, H7,9,11,13CH3CP). 13C NMR
249.08447 [M+1] (16). HR-MS (DART): calcd for C14H22N2P [M+] (75.58 MHz, CDCl3) δ 150.2 (d, J = 21.5 Hz, Cα-phosphole), 124.9,
249.15206; found 249.15144.
124.1 Cβ-phosphole, 1117.8 (d, J = 6.8 Hz, C2pyrrole), 116.9 C5
ipso-
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 7
Please do not adjust margins

Please do not adjust margins
Dalton Transactions
Page 8 of 9
View Article Online
DOI: 10.1039/C6DT01022A
ARTICLE
Journal Name
pyrrole, 116.6 (d, J = 7.2 Hz,C4pyrrole), 110.8 (d, J = 2.9 Hz, C3pyrrole), IN205014, LIA Mexico-France: Laboratoire de Chimie
57.2 C1-N-(CH3), 14.5 (d, J = 14.2 Hz, C7,13CH3CP), 11.4 (d, J = 17.0 Moléculaire avec applications dans les Matériaux et la Catalyse
Hz, C9,11CH3), 31P NMR (50 MHz, CDCl3) δ 28.91. IR (KBr, cm-1) (LCMMC), ECOS M13P02 (Conacyt 229470) projects and
νmax: 3128 (=C-H), 2912 (-CH). MS (FAB+): m/z (100 %): 391 CONACYT for the Ph.D. grant extended to J. V. Suarez-
[M+1-Cl] (5). HR-MS (FAB+): calcd for C14H21ClN2PPd [M+] Meneses.
391.0170; found 391.0170.
Palladium
dichloro[2-(diphenylphosphino-kP)-N,N-
dimethylaniline-kN] (5). Yellow solid. (95 %). m.pdec: 280 °C. 1H
NMR (300.53 MHz, CDCl3) δ 7.59 (dd, 4H, H9,19,13,15arom), 7.73 (s,
2H, H10,17arom), 7.61-7.56 (m, 2H, H5,3arom), 7.51-7.38 (m, 6H,
H4,6,11,12,16,18arom), 3.56 (s, 1H, H1-N-(CH3)2). 13C NMR (75.58 MHz,
CDCl3) δ 160.9 (d, J = 17.2 Hz, C2ipsoN-arom), 134.7 (d, J = 2.2 Hz,
C8,14ipsoP-arom), 133.8 (d, J = 11.3 Hz, C11,12,16,18P-arom), 136.6
Notes and references
1
Z. Mao, W. Sun, L. Fu, H. Luo, D. Lai and L. Zhou, Molecules,
2014, 19, 5088-5108.
2
a) A. H. Aly, R. Edrada-Ebel, I. D. Indriani, V. Wray, W. E. G.
Muller, F. Totzke, U. Zirrgiebel, C. Schächtele, M. H. G.
Kubbutat, W. H. Lin, P. Proksch and E. Rainer, J. Nat. Prod.
2008, 71, 972–980; b) I. Watanabe, M. Kakishima, Y. Adachi
and H. Nakajima, Mycotoxins 2007, 57, 3–9; c) D. Bialonska,
S. G. Kasimsetty, S. I. Khan and D. Ferreira, J. Agric. Food
Chem. 2009, 57, 10181–10186; d) S.-J. Jeong, N.-Y. Kim, D.-H.
Kim, T.-H Kang, N.-H. Ahn, T. Miyamoto, R. Higuchi and Y.-C.
Kim, Planta Med. 2000, 66, 76–77; e) X. Meng, Z. Mao, J. Lou,
L. Xu, L. Zhong, Y. Peng, L. Zhou and M. Wang, Molecules
2012, 17, 11303–11314; f) E. Hormazabal, G. Schmeda-
Hirschmann, L. Astudillo, J. Rodriguez and C. Theoduloz, Z.
Naturforsch. C 2005, 60, 11–21; g) M. A. P. Moreno, I. G.
Alonso, R. Martin de Santos and T. G. Lacarra, Nutr. Hosp.
2012, 27, 1772–1781; h) G. F. Griffin and F. S. Chu, Appl.
Environ. Microbiol. 1983, 46, 1420–1422; i) V. Ostry, World
Mycotoxin J. 2008, 1, 175–188; j) F. S. Chu, J. Am. Oil Chem.
Soc. 1981, 58, 1006–1008; k) R. W. Pero, D. Harvan and M. C.
Blois, Tetrahedron Lett. 1973, 12, 945–948; l) N. Maeda, Y.
Kokai, S. Ohtani, H. Sahara, I. Kuriyama, S. Kamisuki, S.
Takahashi, K. Sakaguchi, F. Sugawara and H. Yoshida,
Biochem. Biophys. Res. Commun. 2007, 352, 390–396.
C10,17P-arom, 133.7 C9P-arom, 128.9 C3arom, 128.4 (d, J = 2.0 Hz, C12
P-
arom), 132.4 (d, J = 3.2 Hz, C6N-arom), 130.3 (d, J = 6.7 Hz, C7N-arom),
129.2 (d, J = 12.2 Hz, C9,13,15,19P-arom), 128.2 C4N-arom, 127.3 C5
N-
arom, 122.6 (d, J = 12.4 Hz, C3N-arom), 55.5 C1
.
31P NMR (50
-N-(CH3)
MHz, CDCl3) δ 42.11. IR (KBr, cm-1) νmax: 3052 (=C-H),2983(-CH),
1578(C=Carom), 687 (Ph monosust arom). MS (FAB+): m/z (100 %):
448 [M+1-Cl] (10). HR-MS (FAB+): calcd for C20H20ClNPPd [M+]
448.0063; found 448.0061.
General procedure for catalytic reactions under microwave
A 30 mL microwave-transparent process vial was filled with
the substrate (0.62 mmol, 1 equiv), base (0.74 mmol 1.2 equiv)
and the corresponding palladium complex 3a-d or 5 (l mol %)
in 10 ml of solvent (DMF). The vial is sealed with PEEK snap
caps and standard PTFE coated silicone septa. The reaction
mixture was then exposed to microwave heating to the
desired temperature. The reaction vial is thereafter cooled to
room temperature and the mixture is diluted with 30 mL of
water and extracted with 3 × 20 mL of hexane. The combined
organic layers are dried over anhydrous sodium sulfate. The
crude product is finally purified by flash column
chromatography on silica-gel using ethyl acetate/hexanes
mixtures.
3
a) J. Teske and A. Deiters, Org. Lett. 2008, 10, 2195–2198; b)
J. P. Edwards, S. J. West, K. B. Marschke, D. E. Mais, M.
Gottardis and T. K. Jones, J. Med. Chem. 1998, 41, 303-310;
c) M. J. Coghlan, P. R. Kym, S. W. Elmore, A. X. Wang, J. R.
Luly, D. Wilcox, M. Stashko, C. W. Lin, J. Miner, C. Tyree, M.
Nakane, P. Jacobson and B. C. Lane, J. Med. Chem. 2001, 44,
2879-2885; d) K. V. Sashidhara, A. Kumar, M. Kumar, R.
Sonkar, G. Bhatia and A. K. Khanna, Bioorg. Med. Chem. Lett.
2010, 20, 4248–4251; e) J. M. Schmidt, G. B. Tremblay, M.
Page, J. Mercure, M. Feher, R. Dunn-Dufault, M. G. Peter and
P. R. Redden, J. Med. Chem. 2003, 46, 1289-1292.
Conclusions
4
a) M. E. Jung and D. A. Allen, Org. Lett. 2009, 11, 757-760; b)
P. R. Nandaluru and G. J. Bodwell, Org. Lett. 2012, 14, 310-
313; c) K. K. Sanap and S. D. Samant, ARKIVOC, 2013, iii, 109-
118; d) I. Hussain, V. T. H. Nguyen, M. A. Yawer, T. T. Dang, C.
Fischer, H. Reinke and P. Langer, J. Org. Chem., 2007, 72,
6255-6258; e) E. E. Prust, E. J. Carlson and B. J. Dahl,
Tetrahedron Lett. 2012, 53, 6433–6435; f) S. Zarrabi, N. O.
Mahmoodi, K. Tabatabaeian and M. A. Zanjanchi, Chinese
Chem. Lett. 2009, 20, 1400–1404; g) H. Togo, T. Muraki and
M. Yokoyama, Tetrahedron Lett. 1995, 36, 7089-7092; h) S.
A. Glover, S. L. Golding, A. Goosen and C. W. McCleland, J.
Chem. Soc., Perkin Trans. 1 1981, 842-848; i) Y. Wang, A. V.
Gulevich and V. Gevorgyan, Chem. Eur. J. 2013, 19, 15836–
15840; j) W. Zhang and G. Pugh, Tetrahedron Lett. 2001, 42,
5613–5615; k) C.-L. Sun, Y.-F. Gu, W.-P. Huang and Z.-J. Shi,
Chem. Commun. 2011, 47, 9813–9815; l) A. Hager, D.
Mazunin, P. Mayer and D. Trauner, Org. Lett. 2011, 13, 1386-
1389; m) N. Thasana, R. Worayuthakarn, P. Kradanrat, E.
Hohn, L. Young and S. Ruchirawat, J. Org. Chem. 2007, 72,
9379-9382; n) S. Ceylan, T. Klande, C. Vogt, C. Friese and A.
Kirschning, Synlett 2010, 2009-2013.
We have developed the synthesis of a novel family of ligand
[N,P] including pyrrole as framework and different phosphine
or phosphole units as phosphorus donor. Their palladium
complexes (3a-d) were obtained in very good yields and their
catalytic properties were evaluated in the direct arylation to
obtain both benzopyranones and phenanthridinones.
We also demonstrated that complex 3a exhibited the best
catalytic performance of this series of complexes, using 1
mol% of catalyst in combination with microwaves to promote
this reaction. While the catalytic activity of complex 3b-d in
direct arylation was not expected, these complexes are
interesting prospects for other catalytic applications.
Acknowledgements
The authors would like to acknowledge the technical
assistance provided by Martin Cruz Villafañe, M. Rocio Patiño
Maya, Luis Velasco and Javier Pérez. We also thank the DGAPA
5
a) G. J. Kemperman, B. T. Horst, D. Van de Goor, T. Roeters, J.
Bergwerff, R. Van der Eem and J. Basten, Eur. J. Org. Chem.
8 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Please do not adjust margins
Dalton Transactions
Page 9 of 9
View Article Online
DOI: 10.1039/C6DT01022A
Journal Name
ARTICLE
2006, 3169–3174; b) K. Vishnumurthy and A. Makriyannis, J.
Comb. Chem. 2010, 12, 664–669; c) J. Luo, Y. Lu, S. Liu, J. Liu
and G.-J. Deng, Adv. Synth. Catal. 2011, 353, 2604–2608; d) 17 a) H. W. Pinnick, S. P. Brown, E. A. McLean and L. W. Zoller
1599-1602; l) C. Thoumazet, M. Melaimi, L. Ricard and P. Le
Floch, C. R. Chimie 2004, 7, 823-832.
R. Singha, S. Roy, S. Nandi, P. Ray and J. K. Ray, Tetrahedron
Lett. 2013, 54, 657–660.
a) S. Luo, F.-X. Luo, X.-S. Zhang and Z.-J. Shi, Angew. Chem.
III, J. Org. Chem. 1981, 46, 3760; b) J. Clayden, in
Organolithiums: Selectivity for Synthesis, Elsevier Science
Ltd., 2002, pp 70-71.
6
Int. Ed. 2013, 52, 10598-10601; b) T.-H. Lee, J. Jayakumar, C.- 18 See: a) G. Mora, B. Deschamps, S. van Zutphen, X. F. Le Gloff,
H. Cheng and S.-C. Chuang, Chem. Commun., 2013, 49,
11797-11799.
L. Ricard and P. Le Floch, Organometallics 2007, 26,
1846−1855 for the 1-cyano-2,5-diphenylphosphole; b) J.
Hydrio, M. Gouygou, F. Dallemer, J.-C. Daran and G. G. A.
Balavoine, Tetrahedron: Asymmetry 2002, 13, 1097–1102 for
the 1-cyano-2,3,4,5-tetramethylphosphole
7
8
Q. J. Zhou, K. Worm and R. E. Dolle, J. Org. Chem., 2004, 69,
5147-5149.
a) G. Bringmann, J. R. Jansen and H.-P. Rink, Angew. Chem.,
Int. Ed. 1986, 25, 913-915; b) G. Bringmann, T. Pabst, P. 19 For NMR data of PPh3, see: a) E. Pretsch, P. Bühlmann and M.
Henschel, J. Kraus, K. Peters, E.-M. Peters, D. S. Rycroft and J.
D. Connolly, J. Am. Chem. Soc. 2000, 122, 9127-9133; c) G.
Bringmann and D. Menche, Angew. Chem., Int. Ed. 2001, 40,
1687-1690; d) D. Alberico, M. E. Scott and M. Lautens, Chem.
Rev. 2007, 107, 174-238; e) Y. Li, Y.-J. Ding, J.-Y. Wang, Y.-M-
Su and X.-S. Wang, Org. Lett. 2013, 15, 2574-2577.
Badertscher, in Structure Determination of Organic
Compounds, Springer-Verlag, Berlin Heidelberg, 2009, pp
261; for NMR data of PPh(cpe)2, see: b) S. Grim, W.
McFarlane and E. F. Davidoff, J. Org. Chem. 1967, 32, 781-
784; for NMR data of PhDPP, see: c) B. Lukas, R. B. G.
Roberts, J. Silver and A. S. Wells, J. Organomet. Chem. 1983
,
9
a) P. P. Deshpande and O. R. Martin, Tetrahedron Lett. 1990
,
256, 103-110; for NMR data of PhDMP, see: d) A. Breque, F.
Mathey and P. Savignac, Synthesis, 1981, 983-985, for NMR
data of PhTMP, see e): P. J. Fagan and W. A. Nugent, J. Am.
Chem. Soc. 1988, 110, 2310-2312; f) T. Douglas and K. H.
Theophold, Angew. Chem. Int. Ed. 1989, 28, 1367-1368.
31, 6313-6316; b) T. Matsumoto, T. Hosoya and K. Suzuki, J.
Am. Chem. Soc. 1992, 114, 3568-3570; c) T. Hosoya, E.
Takashiro, T. Matsumoto and K. Suzuki, J. Am. Chem. Soc.
1994, 116, 1004-1015.
10 a) T. Harayama and H. Yasuda, Heterocycles 1997, 46, 61-64; 20 A. A. Cant, L. Roberts and M. F. Greaney Chem. Commun.
2010, 46, 8671–8673.
b) T. Harayama, H. Yasuda, T. Akiyama, Y. Takeuchi and H.
Abe, Chem. Pharm. Bull. 2000, 48, 861-864.
11 G. Qabaja and G. B. Jones, J. Org. Chem. 2000, 65, 7187-
7194.
21 G. Altomare, C. Cascarano, A. Giacovazzo, M. C. Burla, G.
Polidori and M. Canalli, J. Appl. Crystallogr. 1994, 27, 435.
22 G. M. Sheldrick, Acta Crystallogr., 2008, A64, 112-122.
12 H. Abe, K. Nishioka, S. Takeda, M. Arai, Y. Takeuchi and T.
Harayama, Tetrahedron Lett. 2005, 46, 3197-3200.
13 For selected references on Palladium catalyzed C-H direct
functionalization of arenes see: a) R. Giri, S. Thapa and A.
Kafle, Adv. Synth. Catal. 2014, 356, 1395-1411; b) T. Jin, J.
Zhao, N. Asao and Y. Yamamoto, Chem. Eur. J. 2014, 20,
3554-3576; c) F. Zhang and D. R. Spring, Chem. Soc. Rev.
2014, 43, 6906-6919; d) J. Wencel-Delord, T. Dröge, F. Liu
and F. Glorius, Chem. Soc. Rev. 2011, 40, 4740-4761; e) T. W.
Lyons and M. S. Sanford, Chem. Rev. 2010, 110, 1147-1169;
f) X. Chen, K. M. Engle, D.-H. Wang and J.-Q. Yu, Angew.
Chem. Int. Ed. 2009, 48, 5094-5115.
14 J. V. Suárez-Meneses, E. Bonilla-Reyes, E. A. Blé-González, M.
C. Ortega-Alfaro, R. A. Toscano, A. Cordero-Vargas and J. G.
López-Cortés, Tetrahedron 2014, 70, 1422-1430.
15 For a revue on phosphole-based ligands in catalysis see: K.
Fourmy, D. H. Nguyen, O. Dechy-Cabaret and M. Gouygou,
Catalysis Science & technology 2015, 5, 4289-4323.
16 a) M. Hissler, L. Toupet and R. Réau, Angew. Chem. Int. Ed.
2000, 39, 1812-1815; b) C. Thoumazet, M. Melaimi, L. Ricard,
F. Mathey and P. Le Floch, Organometallics 2003, 22, 1580-
1581; c) M. Peer, J. C. de Jong, M. Kiefer, T. Langer, H. Rieck,
H. Schell, P. Sennhenn, J. Sprinz, H. Steinhagen, B. Wise and
G. Helmchen, Tetrahedron 1996, 52, 7547-7583; d) X. Sava,
A. Marinetti, L. Ricard and F. Mathey, Eur. J. Inorg. Chem.
2002, 1657-1665; e) H. Doucet, E. Fernandez, T. P. Layzell
and J. M. Brown Chem. Eur. J. 1999, 5, 1320-1330; f) S.
Morgues, D. Serra, F. Lamy, S. Vincendeau, J-C. Daran, E.
Manoury and M. Gouygou, Eur. J. Inorg. Chem. 2003, 2820-
2826; g) A. Aeby, F. Bangerter and G. Consiglio J. Chem. Soc.,
Dalton Trans. 1999, 655-656; h) M. Sauthier, F. Leca, L.
Toupet and R. Réau, Organometallics 2002, 21, 1591-1602; i)
R. F. de Souza, K. Bernardo-Gusmao, G. A. Cunha, C. Lescop,
F. Leca and R. Réau, J. Catal. 2004, 226, 235-239; j) M. Peer,
J. C. de Jong, M. Kiefer, T. Langer, H. Riech, H. Schell, P.
Sennhenn, J. Sprinz, H. Steinhagen, B. Wiese and G.
Helmchen Tetrahedron 1996, 52, 7547-7583; k) T. Langer, J.
Janssen and G. Helmchen, Tetrahedron: Asymmetry 1996, 7,
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 9
Please do not adjust margins