Synthesis of new diphosphine ligands and their application in pd-catalyzed alkoxycarbonylation reactions

Article abstract of DOI:10.1002/asia.201301636

Carbocyclic and N-heterocyclic analogues of the industrially applied ligand bis(di-tert-butylphosphinomethyl)benzene (1) have been synthesized in moderate to very good yields. The new ligands are based on benzene, tetralin, lutidine, pyrazine, quinoxaline, and maleimide backbones. Electronic and steric variations of the phosphorous donor sites were performed. As a benchmark reaction, the palladium-catalyzed methoxycarbonylation of 1-octene has been tested. Ester yields up to 64 and high linear selectivities up to 92 were achieved. So much potential: Carbocyclic and N-heterocyclic analogues of bis(di-tert- butylphosphinomethyl) benzene (1) have been synthesized in moderate to very good yields. The new ligands demonstrated their catalytic potential in palladium-catalyzed methoxycarbonylation of 1-octene.

Full text of DOI:10.1002/asia.201301636

FULL PAPER
DOI: 10.1002/asia.201301636
Synthesis of New Diphosphine Ligands and their Application in Pd-Catalyzed
Alkoxycarbonylation Reactions
[
a]
[a]
[a]
[a]
Anahit Pews-Davtyan, Xianjie Fang, Ralf Jackstell, Anke Spannenberg,
[
a]
[b, c]
[a]
Wolfgang Baumann, Robert Franke,
and Matthias Beller*
Abstract: Carbocyclic and N-heterocyclic analogues of the industrially applied
ligand bis(di-tert-butylphosphinomethyl)benzene (1) have been synthesized in
moderate to very good yields. The new ligands are based on benzene, tetralin, luti-
dine, pyrazine, quinoxaline, and maleimide backbones. Electronic and steric varia-
tions of the phosphorous donor sites were performed. As a benchmark reaction,
the palladium-catalyzed methoxycarbonylation of 1-octene has been tested. Ester
yields up to 64% and high linear selectivities up to 92% were achieved.
Keywords: alkoxycarbonylation
homogenous catalysis · ligands ·
palladium · phosphine
·
Introduction
weakly or non-coordinating anions constitute efficient cata-
lyst systems for highly chemo- and regioselective CO–
[5]
Palladium phosphine complexes represent powerful catalytic
alkene copolymerization, hydroformylation of both ali-
[6]
systems for numerous CÀC bond formations in contempo-
phatic and functionalized alkenes, and alkoxycarbonyla-
[1]
[7]
[8]
[9]
[10]
rary organic chemistry. Among the different coupling reac-
tions, carbonylation reactions allow for a straightforward
synthesis of all kinds of carboxylic acid derivatives. As
a result, significant efforts have been dedicated to the devel-
opment of new phosphine ligands for carbonylation cata-
lysts, which are widely used both in academic laboratories
tion of alkynes, nitriles, unsaturated esters, as well as
[11]
terminal and internal alkenes. Notably, this “state-of-the-
art” ligand provides the basis for the so-called Lucite a-pro-
cess, which is applied on an industrial scale for the synthesis
of methyl methacrylate.
We have been interested for more than a decade in the
[2]
[12]
and for industrially relevant processes.
recent example, bis(di-tert-butylphosphinomethyl)benzene
dtbpmb) (1) as well as its (un)symmetrical analogues,
have become important for diverse carbonylation reactions
Figure 1). More specifically, their palladium complexes with
As
a
more
development of novel phosphorus ligands and their cata-
[
3]
[13]
lytic application in various carbonylations.
Some of our
[4]
(
palladium catalysts also have found industrial application in
[14]
the production of active pharmaceutical ingredients.
(
Based on our long lasting interest in the synthesis and ap-
plication of such kind of ligands, recently we became attract-
ed to synthesize carbo- and heterocyclic analogues of
1
(Figure 1) and to test their activity in methoxycarbonyla-
tion reactions of alkenes. Herein, we report the preparation
of novel carbocyclic and N-heterocyclic diphosphine ligands
and their initial catalytic performance in methoxycarbonyla-
tion reactions.
Figure 1. Bis(diphosphinomethyl)benzene ligands and their analogues.
[
a] Dr. A. Pews-Davtyan, X. Fang, Dr. R. Jackstell, Dr. A. Spannenberg,
Dr. W. Baumann, Prof. Dr. M. Beller
Leibniz-Institut fꢀr Katalyse an der Universitꢁt Rostock e.V.
Albert-Einstein-Str. 29a, 18059 Rostock (Germany)
Fax : (+49)381-1281-131
Results and Discussion
Ligand synthesis
So far, there are few examples of dtbpmb-like ligands
known, where two phosphorus atoms are connected to each
E-mail: matthias.beller@catalysis.de
[
b] Prof. Dr. R. Franke
other by a semi-rigid C bridge. In addition, catalytic reac-
4
Evonik Industries AG
Paul-Baumann-Str. 1, 45772 Marl (Germany)
tions in the presence of such dtbpmb derivatives are scarcely
explored. Some of the first examples of carbocyclic ana-
logues of this kind of diphosphine ligands have been syn-
[
c] Prof. Dr. R. Franke
Lehrstuhl fꢀr Theoretische Chemie
Ruhr-Universitꢁt Bochum
[15]
thesized already more than four decades ago by Hayashi
[16]
et al. and were tested in hydroformylation and in one case
4
4780 Bochum (Germany)
[17]
also in methoxycarbonylation reactions. To the best of our
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/asia.201301636.
knowledge, the corresponding N-heterocyclic ligands, for ex-
Chem. Asian J. 2014, 9, 1168 – 1174
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Matthias Beller et al.
ample, based on lutidine, pyrazine, quinoxaline, and malei-
[18]
mide backbones, are not known except for one example,
where 2,3-bis((diisopropylphosphino)methyl)pyrazine was
synthesized as an intermediate for further transformations
without isolation and any characterization.
In general, the novel ligands were prepared by selective
deprotonation at the methyl groups of the corresponding
carbocyclic or N-heterocyclic substrate by using n-butyllithi-
um (nBuLi) in the presence of tetramethylenethylendiamine
(
TMEDA) followed by trapping the resulting lithium inter-
mediate with dialkyl- or diarylchlorophosphines. Advanta-
geously, all substrates and reagents are commercially avail-
able or can be conveniently prepared on multi-gram scale
using known procedures.
At the beginning of this project, we were interested in the
synthesis of (un)symmetrical analogues of bis(di-tert-butyl-
phosphinomethyl)benzene (1) (Scheme 1). Starting from 1-
Figure 2. Molecular structure of the lithium complex with phosphine 2
and TMEDA. Displacement ellipsoids are drawn at the 30% probability
level.
Scheme 2. Synthesis of tetralin backbone-based diphosphine ligand 4.
the borane-protected diphosphine, which upon treatment
with pyrrolidine yielded the desired ligand 4.
Scheme 1. Stepwise phosphorylation of 1-(bromomethyl)-2-methylben-
zene.
Furthermore, nine different N-heterocyclic mono- and di-
phosphines were synthesized. Preliminary experiments
showed that the reaction of 2,3-dibromomethylenequinoxa-
line with potassium diphenylphosphide or diphenylphos-
phine led to mixtures of products. To our delight, the metal-
lation of 2,3-dimethyllutidine, 2,3-dimethylpyrazine, and 2,3-
dimethylquinoxaline proceeded smoothly at low tempera-
ture (À788C). When both metallation of 2,3-dimethylluti-
dine and subsequent phosphorylation reaction with chlorodi-
phenylphosphine were performed at elevated temperatures,
namely above 08C, the main product was the monophos-
phorylated ligand 5 (Table 1, entry 1).
In addition, the unexpected product 6 was formed
(Table 1, entry 2), which is a result of double metallation at
the methyl group in ortho-position to the nitrogen atom. X-
ray analysis of single crystals and NMR investigations
proved the structure of ligand 6 (Figure 3, structure a).
However, decreasing the reaction temperature to À788C
(see the Experimental Section, procedure D) led to the se-
lective formation of 5 in high yield. Although two equiva-
lents of chlorodiphenylphosphine were used, the monophos-
phorylated product at the C-2 methyl group was exclusively
formed. Similar behavior was observed in the synthesis of
the more basic ligand 7 (Table 1, entry 3). Again, the struc-
ture of this ligand was confirmed by X-ray analysis
(Figure 3, structure b).
(
bromomethyl)-2-methylbenzene we aimed to take advant-
age of the different reactivity of the bromomethyl and the
methyl groups. Hence, di-tert-butyl(2-methylbenzyl)phos-
phine (2) was synthesized in a straightforward manner via
the corresponding phosphonium salt, which was subsequent-
ly deprotonated with an excess of base (Scheme 1, see the
Experimental procedures A and B).
Next, we performed metallation of the monophosphine 2.
Surprisingly, X-ray analysis of single crystals of the lithiated
intermediate showed that deprotonation took place on the
CH ÀP group and that the lithium atom is located between
2
the methylene group and ortho-aromatic hydrogen atoms
(
1
Figure 2). The length of C1ÀC2 and C2ÀC3 bonds with
.442 ꢃ and 1.446 ꢃ, respectively, indicates the existence of
an allylic structure. Due to steric hindrance, further reaction
with chlorodiphenylphosphine led to the formation of prod-
uct 3.
Next, we attempted the synthesis of ligands with a tetralin
backbone. Thus, 1,4-dibromo-1,2,3,4-tetrahydronaphthalene
was synthesized by refluxing 1,2,3,4-tetrahydronaphthalene
with N-bromosuccinimide in carbon tetrachloride in the
[19]
presence of benzoyl peroxide (Scheme 2). This bromina-
tion reaction was completed before any appreciable dehy-
drobromination to naphthalene took place. The dibromote-
tralin derivative was immediately reacted with freshly pre-
pared borane-protected lithium diphenylphosphide to give
Having a reliable protocol in hand (procedure D), we con-
tinued our experiments with 2,3-dimethylpyrazine (Table 1,
entries 4–6) and 2,3-dimethylquinoxaline (Table 1, entries 7–
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Matthias Beller et al.
[
a]
Table 1. Synthesis of heterocyclic mono- and diphosphine ligands.
[
b]
Entry Substrate
1
Product
Procedure Yield [%]
[c,d]
5
6
D
E
57
35
[c,e]
2
3
4
5
6
7
8
9
7
D
D
D
D
D
D
D
88
75
86
53
49
43
51
8
9
10
11
12
13
[
a] Reaction conditions were not optimized: Heterocyclic substrate
(
20 mmol), nBuLi (2.2 equiv), TMEDA (2.2 equiv), À788C to RT, then
disubstituted chlorophosphine (2.2 equiv), À788C to RT. [b] Isolated
yield. [c] Partly calculated from NMR data. [d] Along with 7% of prod-
uct 6. [e] Along with 20% of product 5.
9). The targeted diphosphine ligands were obtained in good
to very good yields without any modifications. Notably, all
products were isolated by crystallization with a purity
>
95%.
Pyrazine-based aryl- or alkyldiphosphines (Table 1, en-
tries 4–5) were obtained in better yields compared to the
corresponding bulky, electron-rich ligand 10 with tert-butyl
groups at the phosphorus atoms (Table 1, entry 6). In case
of the quinoxaline backbone-based ligands the yields were
not affected by electronic or steric factors of substituents
Figure 3. Molecular structures of ligands 6 (a), 7 (b), and 13 (c, only one
of two molecules in the asymmetric unit is depicted). Displacement ellip-
soids are drawn at the 30% probability level. Hydrogen atoms are omit-
ted for clarity.
(
Table 1, entries 7–9). Interestingly, we observed that 2,3-
bis((di-tert-butylphosphino)methyl)quinoxaline 13 (Table 1,
entry 9) forms in methanol fast growing large yellow single
crystals. Their X-ray analysis showed the existence of two
crystal forms in an asymmetric unit, which differ in the ar-
rangement of the methylene-bridged di-tert-butylphosphine
groups to the aromatic ring (Figure 3, structure c).
product 14, which combines both phosphine and phosphine
31
oxide moieties in one molecule (Scheme 3). The P NMR
4
signals are observed as doublets with a coupling constant J-
A
H
U
G
R
N
N
(P,P) of 5.8 Hz, for the phosphine moiety at À15.1 ppm and
for the phosphine oxide at 30 ppm, respectively. The differ-
ent oxidation states of the P atoms are also evident from the
heteronuclear coupling constants J(P,Ph-Cipso) [>90 Hz for
1
Finally, we attempted the synthesis of related maleimide-
derived diphosphines (Scheme 3). Starting from the corre-
sponding maleinanhydrid, more stable N-alkylated and N-
arylated 3,4-dimethylmaleimide substrates were synthesized
on a multi-gram scale according to known literature proce-
V
III
P , about 16 Hz for P ].
Based on the structure of 14, we assume that the follow-
ing reaction sequence takes place: First, addition of nBuLi
to the carbonyl group, then deprotonation of the vicinal
methyl group. Subsequent phosphorylation leads to the for-
mation of the phosphinite–phosphine intermediate, which
[20]
dures. To our surprise, metallation and phosphorylation of
N-cyclohexyl 3,4-dimethylmaleimide gave the unknown
Chem. Asian J. 2014, 9, 1168 – 1174
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Matthias Beller et al.
moderate to very good yields.
All substrates and reagents for
the ligand syntheses are com-
mercially available or easily ac-
cessible on multi-gram scale.
The ligands are constructed on
benzene, tetralin, lutidine, pyra-
zine, quinoxaline, and malei-
mide backbones. In addition,
we performed electronic and
steric variations of the phos-
phorous substituents, which en-
Scheme 3. Transformations of N-cyclohexyl 3,4-dimethylmaleimide according to experimental procedure F.
undergoes allylic 2,3-sigmatropic rearrangement to form
compound 14 with both phosphine–phosphine oxide func-
tions. In agreement with this proposal, recently Knochel and
co-workers described 2,3-sigmatropic rearrangements of
cyclic and open-chain allylic phosphinites to chiral phos-
ables a “fine tuning” of the resulting homogeneous palladi-
um catalysts. To demonstrate a catalytic application, alkoxy-
carbonylation of 1-octane was performed at low catalyst
loadings. Obviously, these ligands have additional potential
for a variety of other catalytic applications.
[21]
phine oxides. To confirm our proposal, we performed the
reaction with 1 equivalent of nBuLi. In fact, only phosphin-
oxide was formed and no traces of monophosphine or com-
pound 14 were observed. An attempt to introduce tert-butyl
groups at phosphorus atoms was unsuccessful probably due
to the increased sterical demand.
[
a]
Table 2. Pd-catalyzed methoxcarbonylation of 1-octene.
Entry Ligand
Conv. Olefin iso- Total
Linear
selec.
[%]
[
b]
Catalytic Investigations: Methoxycarbonylation
[%]
mers yield ester
[
b]
[b]
[
%]
yield
As a benchmark reaction, the methoxycarbonylation of 1-
[b]
[
%]
octene was carried out using 0.04 mol% Pd
ACHTUNGTNERUNNG( acac) and
2
1
2
1
3
>98
–
93
0
96
-
0.16 mol% of the new ligands in the presence of 0.6 mol%
methane sulfonic acid in methanol under 40 bar of CO pres-
sure. As expected, the ligand structure has a significant in-
fluence on the conversion and regioselectivity. Alkyl- and
aryl-substituted monophosphine ligands, such as 2, 5, 7, and
trace
amounts
1–2
1
4 did not show any catalytic activity. Similarly, diphenyl-
trace
amounts
phosphine ligands show almost no activity (Table 2, entries 3
and 4) or gave only very low conversions at moderate linear
selectivity (Table 2, entries 5 and 8). However, conversions
and selectivity to methyl nonanoate were considerably im-
proved parallel to increased ligand basicity and bulkiness of
substituents. Interestingly, ligands 9 and 12 with cyclohexyl
substituents were quite active and gave full conversion. Un-
fortunately, they were not able to convert internal olefins
3
4
4
6
1–2
1–2
0
0
-
-
trace
amounts
5
6
7
8
9
8
9
8–10
4–6
4
69
83
92
70
83
92
(
formed by isomerization from 1-octene) into the desired
ester with a significant reaction rate (Table 2, entries 6 and
). Gratifyingly, the better s-donor di-tert-butylphosphino li-
>98
65–70
35–40
26
56
13
31
9
gands 10 and 13 led to improved results (Table 2, entries 7
and 10), and total ester yields up to 64% and linear regiose-
lectivites up to 92% were reached. Variations of electronic
effects from pyrazine to quinoxaline backbones led to some-
what improved alkoxycarbonylation yields relative to com-
peting olefin isomerization at retained linear selectivity.
10 >98
11 22–25 8–10
12 >98
13 >98
55–60
25–30
1
0
64
Conclusions
[
a] Reaction conditions: 1-Octene (2 mmol), Pd
A
H
U
G
R
N
U
G
2
(0.04 mol%), di-
3
phosphine ligand (0.16 mol%), MeSO H (0.6 mol%), MeOH (1.25 mL),
We synthesized 9 new carbocyclic and N-heterocyclic ana-
logues of bis(di-tert-butylphosphinomethyl)benzene (1) in
1
008C, 20 h. [b] Conversion, yield, and regioselectivity were determined
by GC analysis using isooctane as internal standard.
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Matthias Beller et al.
Procedure C
Step 1: To a solution of diphenylphosphine (3.6 mmol) in THF (7 mL) at
Experimental Section
General Information
0
8C was slowly added via a syringe a solution of BH ·THF (3.6 mmol, 1m
3
in THF). The resulting solution of PPh H·BH
2
3
was cooled to À788C, and
All reactions were carried out under argon atmosphere. Chemicals were
purchased from Aldrich, Fluka, Acros, AlfaAsar, or Strem and, unless
otherwise noted, were used without further purification. Solvents were
additionally purified, degased, or distilled under argon atmosphere. All
then a solution of nBuLi (3.6 mmol, 1.6m in n-hexane) was added drop-
wise via a syringe over 10 min. The light-yellow reaction mixture was al-
lowed to warm slowly to room temperature. Step 2: This solution was
added dropwise to a cooled (À258C) solution of 1,4-dibromo-1,2,3,4-tet-
1
13
compounds were characterized by H NMR and C NMR spectroscopy,
[
18]
1
rahydronaphthalene (1.8 mmol, freshly prepared) in THF (5 mL). The
reaction mixture was again allowed to warm slowly to room temperature.
A white precipitate was formed overnight, which was isolated. Step 3:
The borane complex was dissolved in THF (25 mL) to which pyrrolidine
and by GC-MS and HRMS. H NMR spectra were recorded on Bruker
1
3
31
AV 300 and AV 400 spectrometers. C NMR and P NMR spectra were
recorded at 75.5 or 101 MHz and 121 or 162 MHz, respectively. Chemical
shifts are reported in ppm relative to the center of solvent resonance.
Electron ionization (EI) (70 eV) mass spectra were recorded on a MAT
(
18 mL) was added. Deprotection was complete after 15 h at room tem-
perature. Pyrrolidine was removed under vacuum, and the crude product
was recrystallized from THF/methanol/heptane and washed with cold
methanol to give the desired product as white, shiny crystals.
9
5XP instrument (Thermo Electron Corporation). GC was performed on
Agilent 6890 chromatograph with a 30 m HP5 column. HRMS was per-
formed on MAT 95XP (EI) and Agilent 6210 Time-of-Flight LC/MS
(
ESI) system. GC-MS was performed on an Agilent 5973 chromatogra-
1,4-Bis(diphenylphosphino)-1,2,3,4-tetrahydronaphthalene (4): Yield:
1
phy mass selective detector system. All yields reported refer to isolated
yields under non-optimized reaction conditions.
74%, 665 mg; H NMR (300 MHz, CDCl
3
): d=7.45–7.38 (m, 4H), 7.33–
7.09 (m, 16H), 6.69 (dd, J=5.7, 3.4 Hz, 2H), 6.50–6.38 (m, 2H), 3.72 (dq,
J=4.6, 2.6, 2.0 Hz, 2H), 2.09 (dtd, J=12.6, 7.3, 5.9, 3.0 Hz, 2H),
1
3
Procedure A
1.65 ppm (tt, J=6.6, 2.5 Hz, 2H); C NMR (75 MHz, CDCl
1
4
3
): d=
37.80–137.20 (m, 4C), 137.13–136.55 (m, 2C), 133.89 (ddd, J=23.5, 14.0,
.0 Hz, 8C), 129.80–129.38 (m, 4C), 128.74 (d, J=19.4 Hz, 4C), 128.21
A toluene solution (30 mL) of 2-methylbenzylbromide (20 mmol) and di-
tert-butylphosphine (1 equiv) was refluxed for 4 h. After a few minutes of
heating, a white precipitate was formed. After cooling to room tempera-
ture, heptane (20 mL) was added, and the hydrobromide salt of the prod-
uct was filtered off as a white powder ( P NMR signal at 27 ppm). Then,
a KOH solution (1.1 equiv, in 10 mL water) was added slowly to the
water solution of the hydrobromide salt (20 mL). The formed suspension
(
(
dt, J=30.7, 3.4 Hz, 8C), 125.19 (m, 2C), 37.76–37.22 (m, 2C), 24.14 ppm
31
t, J=9.9 Hz, 2C); P NMR (121 MHz, CDCl
3
): d=0.76 ppm; MS (EI):
: 500.1817; found:
+
m/z (%) 500 (9) [M ]; HRMS (EI): calcd for C34
00.1814.
30 2
H P
3
1
5
General Procedure for the Synthesis of Symmetric Bis-disubstituted
Phosphines and Mono-disubstituted Phosphines: Procedure D
2 4
was extracted with diethyl ether (4ꢄ20 mL) and dried over Na SO . The
solvent was evaporated and the product was isolated by vacuum distilla-
tion (b.p. 1058C at 0.67 mbar pressure) to give the desired product as
a colorless syrup.
Step 1: To 40 mL of an ethereal solution or suspension of the correspond-
ing 2,3-dimethyl pyrazine or quinoxaline (20 mmol) was slowly added an
ethereal solution of nBuLi (15 mL, 2.2 equiv, 1.6m in n-hexane, which
was replaced with diethyl ether) and TMEDA (2.2 equiv) at À788C. The
intensively colored reaction mixture was allowed slowly to warm to room
temperature. After stirring overnight, heptane (20 mL) was added, and
the heterogeneous reaction mixture was refluxed at 60–808C for 2 h.
Step 2: The reaction mixture was again cooled to À788C, and an ethereal
solution (15 mL) of di-tert-butylchlorophosphine, chlorodiphenylphos-
phine, or chlorodicyclohexylphosphine (2.2 equiv) was slowly added via
a syringe. After 1 h at that temperature, the reaction mixture was allowed
to warm slowly to room temperature overnight. Then, water was slowly
1
Di-tert-butyl(2-methylbenzyl)phosphine (2): Yield: 87%, 4.36 g; H NMR
(
3
(
(
2
300 MHz, CDCl
.1 Hz, 2H), 2.46 (s, 3H), 1.17 ppm (d, J=10.8 Hz, 18H); C NMR
75 MHz, CDCl ): d=139.10 (d, J=9.9 Hz), 135.96 (d, J=3.1 Hz), 130.48
d, J=12.9 Hz), 130.22, 125.55, 125.38 (d, J=1.9 Hz), 31.85 (d, J=
2.2 Hz, 2C), 29.77 (d, J=13.0 Hz, 6C), 25.61 (d, J=24.3 Hz), 20.57 ppm
3
): d=7.54–7.47 (m, 1H), 7.19–7.01 (m, 3H), 2.87 (d, J=
1
3
3
3
1
(
d, J=5.0 Hz); P NMR (121 MHz, CDCl ): d=28.41 ppm; GC-MS (EI,
3
+
+
7
28
0 eV): m/z (%) 250 (40) [M ]; HRMS (ESI ): calcd for C16H P
+
[
M+H] : 251.1923; found: 251.1925.
added and the product was extracted with CH
drying over Na SO and solvent evaporation, the crude product was re-
crystallized from ether or methanol.
-((Diphenylphosphino)methyl)-3-methylpyridine (5): Yield: 57%, 3.32 g;
2 2
Cl (4ꢄ20 mL). After
Procedure B
2
4
Step 1: An ethereal solution (3 mL) of di-tert-butyl(2-methylbenzyl)phos-
phine (2, 1.27 mmol) was slowly added via a syringe to a previously pre-
pared ethereal solution of nBuLi (5 mL, 1.2 equiv, 1.6m in n-hexane,
which was replaced with diethyl ether) and TMEDA (1.2 equiv) at room
temperature. The yellow solution was cooled to À788C for 4 h and the
formed lithium salt was isolated. Step 2: Heptane (5 mL) was added to
the lithiated compound , and then chlorodiphenylphosphine (2.2 equiv)
was slowly added via a syringe at room temperature. Conversion was
complete after heating of the reaction mixture for 30 min at 508C. Then,
water was slowly added and the product was extracted with toluene (4ꢄ
2
1
H NMR (300 MHz, CD
2
Cl
2
): d=8.37–8.17 (m, 1H), 7.47 (ddtd, J=7.1,
5
.3, 2.9, 1.3 Hz, 5H), 7.41–7.37 (m, 1H), 7.34 (dq, J=4.5, 1.8, 1.3 Hz,
5
H), 7.02 (dd, J=7.6, 4.9 Hz, 1H), 3.64 (s, 2H), 2.25 ppm (s, 3H);
C NMR (75 MHz, CD Cl ): ): d=157.09 (d, J=6.8 Hz), 146.79, 139.32
2 2
13
(
d, J=15.5 Hz, 2C), 137.73, 133.21 (d, J=19.2 Hz, 4C), 132.16 (d, J=
3
3
CD
.0 Hz), 128.87 (2C), 128.61 (d, J=6.4 Hz, 4C), 121.56 (d, J=2.7 Hz),
31
6.54 (d, J=15.6 Hz), 19.29 ppm (d, J=4.4 Hz); P NMR (121 MHz,
+
2
Cl
2
): ): d=À15.58 ppm; GC-MS (EI, 70 eV): m/z (%) 291 (78) [M ];
2
2 4
0 mL). After drying over Na SO and solvent evaporation, the crude
HRMS (EI): calcd for C19
18 1 1
H N P : 291.1171; found: 291.1170.
product was recrystallized from methanol.
Di-tert-butyl(2-(diphenylphosphino)-6-methylbenzyl)phosphine (3): Yield:
Procedure E
1
4
1
1
1
1
2
6%, 254 mg; H NMR (300 MHz, CD
2
Cl
2
): d=7.46 (dt, J=7.9, 1.8 Hz,
The product was synthesized using general procedure D with steps 1 and
carried out at room temperature instead of À788C.
2-(Bis(diphenylphosphino)methyl)-3-methylpyridine (6): Yield: 35%,
H), 7.38–7.20 (m, 10H), 7.10 (dd, J=8.6, 1.6 Hz, 1H), 7.00 (td, J=7.6,
.7 Hz, 1H), 2.86 (d, J=2.8 Hz, 2H), 2.39 (s, 3H), 1.14 ppm (d, J=
2
1
3
2 2
0.7 Hz, 18H); C NMR (75 MHz, CD Cl ): d=141.22 (d, J=10.2 Hz),
1
38.21 (d, J=11.5 Hz, 2C), 136.98 (dd, J=8.0, 2.8 Hz), 136.04 (d, J=
2.5 Hz), 133.93 (d, J=19.5 Hz, 4C), 133.80–133.41 (m), 131.42–131.02
2 2
3.33 g; H NMR (300 MHz, CD Cl ): d=8.29 (dd, J=4.8, 1.8 Hz, 1H),
7.42 (dtd, J=7.8, 3.7, 1.6 Hz, 5H), 7.21–7.06 (m, 15H), 7.04–7.00 (m,
(
1
m, 2C), 128.97–128.63 (m, 6C), 32.22 (d, J=23.4 Hz, 2C), 29.95 (d, J=
1H), 6.77 (dd, J=7.6, 4.7 Hz, 1H), 4.82 (t, J=3.0 Hz, 1H), 1.91 ppm (s,
3
1
13
3.3 Hz, 6C), 26.25 (d, J=26.0 Hz), 20.78 ppm (d, J=5.8 Hz); P NMR
Cl
3H); C NMR (75 MHz, CD
2
Cl
2
): d=158.60, 146.95, 137.59, 137.43 (t,
(
121 MHz, CD
2
2
): d=28.61, À6.16 ppm; GC-MS (EI, 70 eV): m/z (%)
J=4.2 Hz, 2C), 136.89 (t, J=7.5 Hz, 2C), 134.77 (t, J=11.6 Hz, 4C),
133.92 (t, J=10.6 Hz, 4C), 132.19, 129.16 (2C), 128.54 (2C), 128.07 (dt,
+
4
4
28 37 2
34 (32) [M ]; HRMS (EI): calcd for C H P : 435.2365; found:
3
1
35.2369.
J=23.7, 3.8 Hz, 8C), 120.64, 43.32 (t, J=24.7 Hz), 19.51 ppm; P NMR
Chem. Asian J. 2014, 9, 1168 – 1174
1172
ꢂ 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

www.chemasianj.org
Matthias Beller et al.
+
(
121 MHz, CD
2
Cl
2
): d=0.95 ppm; MS (EI): m/z (%) 475 (1) [M ];
Procedure F
This product was synthesized from prepared 1-cyclohexyl-3,4-dimethyl-
+
+
HRMS (ESI ): calcd for C31
H
28
N
1
P
2
[M+H] : 476.1692; found: 476.1702.
2
4
7
2
-((Di-tert-butylphosphino)methyl)-3-methylpyridine (7): Yield: 88%,
3
): d=8.29 (dd, J=4.9, 1.7 Hz, 1H),
.34 (d, J=7.6 Hz, 1H), 6.97 (dd, J=7.6, 4.9 Hz, 1H), 3.12 (d, J=2.5 Hz,
H), 2.45 (s, 3H), 1.13 ppm (d, J=10.9 Hz, 18H); C NMR (75 MHz,
): d=159.38 (d, J=8.9 Hz), 146.04, 137.76, 131.77, 120.92, 32.00 (d,
J=22.7 Hz, 2C), 30.35 (d, J=27.0 Hz), 29.71 (d, J=13.2 Hz, 6C),
1
H-pyrrole-2,5-dione (5 mmol) and chlorodiphenylphosphine (2.2 equiv)
1
.43 g; H NMR (300 MHz, CDCl
using the general procedure D without heating at the end of step 1.
1
3
5-Butyl-1-cyclohexyl-4-((diphenylphosphino)methyl)-3-(diphenylphos-
phoryl)-3-methyl-1H-pyrrol-2ACHTNUGTRENNUNG
CDCl
3
1
H NMR (300 MHz, CDCl
3
3
1
7.48–7.20 (m, 16H), 4.00 (dd, J=14.2, 2.2 Hz, 1H), 3.01 (dt, J=14.2,
2.1 Hz, 1H), 2.83 (t, J=12.2 Hz, 1H), 2.20–1.89 (m, 2H), 1.68 (td, J=7.2,
6.7, 3.3 Hz, 2H), 1.59–1.46 (m, 2H), 1.41 (dd, J=16.0, 1.6 Hz, 3H), 1.34–
1
9.95 ppm (d, J=10.1 Hz); P NMR (121 MHz, CDCl
3
): d=26.20 ppm;
+
GC-MS (EI, 70 eV): m/z (%) 194 (100) [M-tBu]; HRMS (ESI ): Calcd
+
for C15
27 1 1
H N P [M+H] : 252.1876; found: 252.1872.
1
3
.18 (m, 2H), 1.13–0.94 (m, 4H), 0.91–0.81 (m, 2H), 0.63 (t, J=7.2 Hz,
H), 0.55 ppm (ddd, J=10.3, 4.9, 2.6 Hz, 2H); C NMR (75 MHz,
2
,3-Bis((diphenylphosphino)methyl)pyrazine (8): Yield: 75%, 7.15 g;
): d=8.12 (s, 2H), 7.28–7.18 (m, 20H),
.41 ppm (s, 4H); C NMR (101 MHz, CDCl ): d=152.93–152.74 (m,
C), 141.31 (2C), 137.74 (d, J=15.0 Hz, 4C), 132.77 (d, J=19.4 Hz, 8C),
28.78 (4C), 128.38 (d, J=6.4 Hz, 8C), 35.57 ppm (dd, J=17.4, 5.0 Hz,
13
1
H NMR (400 MHz, CDCl
3
CDCl
J=17.5 Hz), 138.36 (d, J=15.6 Hz), 133.64 (d, J=18.9 Hz, 2C), 132.96
d, J=9.0 Hz, 2C), 132.71 (d, J=17.7 Hz, 2C), 131.80 (d, J=8.7 Hz, 2C),
3
): d=177.76 (d, J=3.0 Hz), 142.26 (dd, J=10.4, 7.6 Hz), 139.24 (d,
1
3
3
2
1
2
3
(
1
1
31.73 (d, J=3 Hz, 2C), 131.54 (d, J=2.8 Hz), 130.70 (d, J=94.5 Hz),
30.50 (d, J=97.1 Hz), 128.66, 128.31 (d, J=5.4 Hz, 2C), 128.20, 128.16
3
1
C); P NMR (162 MHz, CDCl
3
): d=À14.00 ppm; GC-MS (EI, 70 eV):
[M+H] :
NaP
+
+
+
m/z (%) 476 (30) [M ]; HRMS (ESI ): calcd for C30
4
27 2 2
H N P
(
d, J=6.6 Hz), 128.06 (d, J=11.9 Hz, 2C), 127.66 (d, J=11.9 Hz, 2C),
+
77.1644; found: 477.1652; HRMS (ESI ): calcd for
C
30
H
26
N
2
2
1
10.92 (t, J=6.4 Hz), 56.16 (d, J=57.9 Hz), 54.08, 29.62 (t, J=3.3 Hz),
+
[
M+Na] : 499.1463; found: 499.1454.
2
8.93, 28.47, 26.33 (d, J=16.0 Hz), 26.22, 25.94, 24.94, 23.55, 22.32, 17.57
2
8
1
1
(
9
,3-Bis((dicyclohexylphosphino)methyl)pyrazine
(9):
Yield:
86%,
31
(
dd, J=7.8, 3.5 Hz), 13.57 ppm; P NMR (121 MHz, CDCl
3
): d=30.02
1
.61 g; H NMR (300 MHz, CDCl
.56 (m, 24H), 1.31–1.07 ppm (m, 20H); C NMR (75 MHz, CDCl
54.84 (d, J=7.2 Hz, 2C), 140.68 (2C), 33.68 (d, J=15.3 Hz, 4C), 30.12
3
): d=8.22 (s, 2H), 3.26 (s, 4H), 1.81–
(
d, J=5.9 Hz), À15.12 ppm (d, J=5.3 Hz); MS (EI): m/z (%) 633 (4)
1
3
+
+
3
): d=
[
[
M ], 448 (100) [MÀPPh
]; HRMS (ESI ): Calcd for C40
H
46NO
P
2
2
2
+
+
M+H] : 634.2998; found: 634.2991; HRMS (ESI ): calcd for
dd, J=23.1, 9.6 Hz, 2C), 29.59 (dd, J=22.7, 11.2 Hz, 8C), 27.29 (dd, J=
.5, 6.4 Hz, 8C), 26.41 ppm (4C); P NMR (121 MHz, CDCl ): d=
+
40 2 2
C H45NNaO P [M+Na] : 656.2818; found: 656.2807. More information
3
1
3
on NMR signal assignment can be found in the Supporting Information.
+
À2.57 ppm; GC-MS (EI, 70 eV): m/z (%) 499 (1) [M ], 417 (100) [M-
+
+
Cy]; HRMS (ESI ): calcd for C30 [M+H] : 501.3522; found:
H
51
N
2
P
2
Catalytic Experiments: Methoxycarbonylation of 1-Octene
5
01.3521.
A vial (4 mL) was charged with monophosphine (0.32 mol%) or diphos-
phine ligand (0.16 mol%) and a stirring bar was added. Then, 1.25 mL of
2
4
1
,3-Bis((di-tert-butylphosphino)methyl)pyrazine (10): Yield: 53%,
1
3
.2 g; H NMR (400 MHz, CDCl ): d=8.23 (s, 2H), 3.32–3.29 (m, 4H),
.10 ppm (d, J=10.9 Hz, 36H); C NMR (101 MHz, CDCl ): d=155.36
3
a clear, light-yellow stock solution (prepared from Pd
2
ACHTUNGTNERNU(GN acac) (2.92 mg,
1
3
0
.04 mol%), MeSO H (9.4 mL, 0.6 mol%), and MeOH (15 mL)) and 1-
3
(
d, J=8.6 Hz, 2C), 140.36 (2C), 31.84 (d, J=23.6 Hz, 4C), 29.77 (d, J=
octene (315 mL, 2 mmol) were injected by using a syringe. The vial was
placed in an alloy plate, which was transferred into an autoclave
3
1
1
3.4 Hz, 12C), 29.54 ppm (d, J=6.8 Hz, 2C); P NMR (162 MHz,
): d=27.00 ppm; GC-MS (EI, 70 eV): m/z (%) 339 (100) [M-tBu];
CDCl
HRMS (ESI ): calcd for C22
,3-Bis((diphenylphosphino)methyl)quinoxaline (11): Yield: 49%, 5.17 g;
3
(
600 mL) from Parr Instruments under an argon atmosphere. After flush-
ing three times with nitrogen, the autoclave was pressurized by CO at
0 bar. The reaction was performed for 20 h at 1008C. Then, the auto-
+
+
43 2 2
H N P [M+H] : 397.2896; found: 397.2902.
2
4
1
H NMR (400 MHz, CDCl
.42–7.37 (m, 8H), 7.30–7.25 (m, 12H), 3.75 ppm (s, 4H); C NMR
75 MHz, CDCl ): d=153.23 (d, J=8.4 Hz, 2C), 140.76 (2C), 137.77 (d,
J=14.8 Hz, 4C), 133.04 (4C), 132.79 (4C), 128.98–128.31 (m, 16C),
3
): d=7.90–7.85 (m, 2H), 7.60–7.55 (m, 2H),
clave was cooled to room temperature and the pressure was carefully re-
leased. Isooctane (200 mL) was added as an internal standard to the solu-
tion before the conversion, yield, and regioselectivity were determined
by GC analysis.
1
3
7
(
3
3
1
3
6.59 ppm (dd, J=17.6, 5.9 Hz, 2C); P NMR (121 MHz, CDCl ): d=
3
+
À14.09 ppm; GC-MS (EI, 70 eV): m/z (%) 526 (15) [M ], 341 (100) [M-
X-ray Crystal Structure Analysis of the Lithium Salt of Compound 2 and
Products 6, 7, and 13
+
+
PPh
2
]; HRMS (ESI ): calcd for C34
H
29
N
2
P
2
[M+H] : 527.1801; found:
+
+
5
27.1811; HRMS (ESI ): calcd for C34
H
28
N
2
NaP
2
[M+Na] : 549.1620;
Data were collected on a STOE-IPDS II (for the lithium salt of com-
pound 2 and product 6) or on a Bruker Kappa APEX II Duo (for prod-
ucts 7 and 13) diffractometer. The structures were solved by direct meth-
found: 549.1611.
2
4
7
1
6
4
2
,3-Bis((dicyclohexylphosphino)methyl)quinoxaline (12): Yield: 43%,
.74 g; H NMR (400 MHz, CDCl
.61 (dt, J=6.4, 3.4 Hz, 2H), 3.51 (s, 4H), 1.86–1.61 (m, 24H), 1.37–
3
.08 ppm (m, 20H); C NMR (101 MHz, CDCl ): d=155.40 (d, J=
.4 Hz, 2C), 140.65 (2C), 128.45 (2C), 128.20 (2C), 33.77 (d, J=15.5 Hz,
C), 31.13 (dd, J=23.6, 10.7 Hz, 2C), 29.64 (dd, J=21.1, 11.3 Hz, 8C),
1
3
): d=7.93 (dd, J=6.3, 3.5 Hz, 2H),
2
ods and refined by full-matrix least-squares procedures on F with the
[
22]
1
3
SHELXTL software package. XP (Bruker AXS) was used for graphi-
cal representations.
2
Crystal data for the lithium salt of compound 2: C22H42LiN P, M=372.49,
3
1
monoclinic, space group P2 /c, a=11.0250(4), b=16.5445(4), c=
7.28 (dd, J=9.7, 6.3 Hz, 8C), 26.39 ppm (4C); P NMR (162 MHz,
): d=À2.80 ppm; GC-MS (EI, 70 eV): m/z (%) 467 (100) [MÀCy];
HRMS (ESI ): calcd for C34 [M+H] : 551.3679; found: 551.3678.
,3-Bis((di-tert-butylphosphino)methyl)quinoxaline (13): Yield: 51%,
1
3
1
3.6678(5) ꢃ, b=109.189(3)8, V=2354.53(13) ꢃ , T=150(2) K, Z=4,
44566 reflections collected, 6358 independent reflections (Rint =0.0348),
final R values (I>2s(I)): R =0.0350, wR =0.0886, final R values (all
data): R =0.0495, wR =0.0918, 254 parameters.
Crystal data for 6: C31 , M=475.48, monoclinic, space group P2
a=7.8660(2), b=22.4909(5), c=14.3707(4) ꢃ, b=98.184(2)8, V=
CDCl
3
+
+
53 2 2
H N P
1
2
2
4
7
1
2
3
1
1
2
.55 g; H NMR (400 MHz, CDCl
.61 (dt, J=6.4, 3.3 Hz, 2H), 3.65 (t, J=1.6 Hz, 4H), 1.13 ppm (d, J=
1.0 Hz, 36H); C NMR (101 MHz, CDCl ): d=156.07 (d, J=7.8 Hz,
3
3
): d=7.97 (dd, J=6.3, 3.5 Hz, 2H),
H
27NP
2
1
/c,
1
3
3
2
516.48(11) ꢃ , T=293(2) K, Z=4, 44527 reflections collected, 6781 in-
C), 140.34 (2C), 128.53 (2C), 128.30 (2C), 32.04 (d, J=23.6 Hz, 4C),
1.07 (dd, J=28.0, 9.9 Hz, 2C), 29.91 ppm (d, J=13.3 Hz, 12C);
dependent reflections (Rint =0.037), final R values (I>2s(I)): R =0.0322,
1
3
1
wR =0.0811, final R values (all data): R =0.0445, wR =0.0834, 308 pa-
P NMR (162 MHz, CDCl
%) 389 (100) [M-tBu]; HRMS (ESI ): calcd for C26
47.3053; found: 447.3054.
3
): d=25.86 ppm; GC-MS (EI, 70 eV): m/z
2
1
2
+
+
rameters.
(
4
45 2 2
H N P [M+H] :
Crystal data for 7: C15H26NP, M=251.34, orthorhombic, space group
3
Aba2, a=21.6794(5), b=15.0690(3), c=9.5202(2) ꢃ, V=3110.13(12) ꢃ ,
T=150(2) K, Z=8, 51602 reflections collected, 2045 independent reflec-
tions (Rint =0.0404), final R values (I>2s(I)): R
1 2
=0.0239, wR =0.0608,
final R values (all data): R =0.0269, wR =0.0628, 161 parameters.
1
2
Chem. Asian J. 2014, 9, 1168 – 1174
1173
ꢂ 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

www.chemasianj.org
Matthias Beller et al.
ꢀ
Crystal data for 13: C26
1
H
44
N
2
P
2
, M=446.57, triclinic, space group P1, a=
Metals for Organic Synthesis, Wiley-VCH, Weinheim, 2008, pp. 49–
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2.3690(2), b=15.1086(3), c=15.8064(3) ꢃ, a=92.094(1), b=99.194(1),
g=112.064(1)8, V=2687.28(9) ꢃ , T=150(2) K, Z=4, 70125 reflections
collected, 12333 independent reflections (Rint =0.0338), final R values
3
(
I>2s(I)): R
1 2 1
=0.0327, wR =0.0806, final R values (all data): R =
0
.0437, wR =0.0887, 565 parameters.
2
[10] a) A. J. Rucklidge, G. E. Morris, A. M. Z. Slawin, D. J. Cole-Hamil-
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Acknowledgements
This work has been supported by the State of Mecklenburg-Western
Pomerania, the BMBF, the Fonds der Chemischen Industrie (FCI), the
DFG (Leibniz-price; GRK 1113). We thank Dr. C. Fischer, S. Schareina,
S. Buchholz, A. Lehmann, A. Koch, and K. Fiedler for their excellent
technical and analytical support.
[
13] For recent examples of carbonylations, see: a) X.-F. Wu, M. Sharif,
K. Shoaib, H. Neumann, A. Pews-Davtyan, P. Langer, M. Beller,
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