Synthetic access to a novel binaphthyl ligand bearing a phosphine and a triazole donor site

Article abstract of DOI:10.1515/znb-2009-11-1226

The combination of a diphenylphospinyl and a triazol-3-yl unit was realized for the first time at a 1,1′-binaphthyl backbone. This novel type of P, N-ligand is accessible as an enantiomerically pure compound in just a few steps. First experiments on the coordination chemistry with palladium(II) chloride have been carried out. A series of intermediates and a binuclear palladium(II) complex could be characterized by X-ray crystal structure analysis.

Full text of DOI:10.1515/znb-2009-11-1226

Synthetic Access to a Novel Binaphthyl Ligand Bearing a Phosphine
and a Triazole Donor Site
Claudia May, Yu Sun, Gotthelf Wolmersha¨user, and Werner R. Thiel
Fachbereich Chemie, Technische Universita¨t Kaiserslautern, Erwin-Schro¨dinger-Straße, Geb. 54,
67663 Kaiserslautern, Germany
Reprint requests to Prof. Dr. Werner R. Thiel. Fax: (+49)-631-2054676.
E-mail: thiel@chemie.uni-kl.de
Z. Naturforsch. 2009, 64b, 1438 – 1448; received September 28, 2009
Dedicated to Professor Hubert Schmidbaur on the occasion of his 75th birthday
The combination of a diphenylphospinyl and a triazol-3-yl unit was realized for the first time at
a 1,1ꢀ-binaphthyl backbone. This novel type of P,N -ligand is accessible as an enantiomerically pure
compound in just a few steps. First experiments on the coordination chemistry with palladium(II)
chloride have been carried out. A series of intermediates and a binuclear palladium(II) complex could
be characterized by X-ray crystal structure analysis.
Key words: Binaphthyl, Chiral Ligands, Palladium, Phosphine, Triazole
Introduction
the 2ꢀ-position of the 1,1ꢀ-binaphthyl system, have suc-
cessfully been applied in various palladium-catalyzed
asymmetric reactions, such as allylic substitution and
olefin hydrosilylation [4a, 5]. Especially for the latter
transformation only poor catalytic activity was found
for catalysts with C2-symmetric BINAP-type ligands.
Simple P,N -binaphthyl ligands as MAP [4b, 6] and its
congeners [7] also demonstrated high catalytic activ-
ity in palladium-catalyzed asymmetric allylic substitu-
tion and in other asymmetric coupling reactions [8].
The combination of the P,N -bidentate phosphinoox-
azoline motif and the binaphthyl backbone leads to
another important sub-class of chiral P,N -binaphthyl
ligands [9]. These ligands show high catalytic ac-
tivities and enantioselectivities in various asymmet-
ric palladium-catalyzed coupling reactions, such as
the Heck reaction [9c, 10], allylic alkylation [9] and
amination [9c].
Chiral phosphine ligands, especially those with a bi-
naphthyl backbone, are important tools for transition
metal-catalyzed asymmetric reactions [1]. Due to the
flexible torsion angle of the binaphthyl unit and the
reliable coordination ability of the phosphorus donor,
they form coordination complexes with a series of tran-
sition metal ions.
In 1980 Noyori and coworkers first reported the
high efficiency of the chiral bidentate diphosphine
BINAP in the ruthenium-catalyzed asymmetric hy-
drogenation and rhodium-catalyzed double bond iso-
merization (Takasago Process) [2]. In the following
decades, intensive research efforts were carried out on
the synthesis of novel BINAP analogs and their appli-
cation in asymmetric catalysis [3]. Despite of the ben-
eficial features of C2-symmetric BINAP-type ligands
– relatively simple synthesis, less diastereomers in the
For quite some time our group has been interested
transition state of the catalytic transformation, etc. – in the design and synthesis of novel ligand systems
an increasing number of unsymmetrically functional- containing N-heterocyclic motifs, such as pyrazole and
ized binaphthyl phosphines possessing C1 symmetry pyrimidine units [11, 12]. This was mainly influenced
have been reported in the literature [4]. The introduc- by the fact that these heterocycles can simply be syn-
tion of a second donor site – usually based on oxygen thesized and modified in terms of their steric and elec-
or nitrogen functions – allows a further fine-tuning of tronic features. In the present work we report on the
the electronic and the steric properties of the ligand, synthesis of a novel chiral P,N -binaphthyl ligand with
which has turned out to be beneficial for a whole se- a triazole unit as the N-donor in the 2ꢀ-position and
ries of catalytic transformations. For example, the so- on first results of the investigation of its coordination
called MOP ligands, bearing an alkoxy substituent in chemistry.
c
0932–0776 / 09 / 1100–1438 $ 06.00 ꢀ 2009 Verlag der Zeitschrift fu¨r Naturforschung, Tu¨bingen · http://znaturforsch.com
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C. May et al. · A Novel Binaphthyl Ligand
1439
Results and Discussion
[16] followed by resolution with (8S,9R)-(–)-N-benz-
yl-cinchonidine hydrochloride [17]. rac-, (R)- and
(S)-4 were transferred into the desired 2-diphen-
ylphosphinoyl-2ꢀ-carbamoyl-1,1ꢀ-binaphthyl (8) by a
reaction sequence published in the literature (in
Scheme 2 shown for the (R)-series) [18 – 20]. The
trifluoromethylsulfonic acid diester 5 allows the se-
lective conversion of one of the triflate groups into
a diphenylphosphinoyl unit by a palladium-catalyzed
P–C coupling reaction. Subsequent conversion of the
remaining triflate unit of 6 into a CN group was
achieved by a nickel-catalyzed cyanation. The nitrile
7 could be saponified to give the amide 8.
As published in ref. [13], 3-aryl-1H(1,2,4)triazoles
are accessible in just two steps by treatment aryl-
amides with N,N-dimethylformamide dimethylacetale
(DMFDMA) and subsequent ring closure with hy-
drazine. To the best of our knowledge, solely sys-
tems derived from benzoic acid have been generated
this way by now. To prove, whether this strategy can
be transferred to naphthoic acid derivatives, we first
studied the reaction sequence with 2-naphthoamide (1,
Scheme 1).
Scheme 1. i) DMFDMA, 120 ◦C, 5 h; ii) N2H4·H2O, AcOH,
80 ◦C, 4 h.
Compound 1 was prepared from commercially
available 2-naphthonitrileby a method published in the
literature [14]. Treatment of 1 with DMFDMA gave
the yet unknown naphthylamidine2 in almost quantita-
tive yield. Two singlets at 3.10 and 3.19 ppm in the 1H
NMR spectrum are assigned to the methyl groups indi-
cating a hindered rotation around the CH–NMe2 bond.
The methine proton of the amidine unit is observed
as a singlet at 8.66 ppm, and the carbonyl group dis-
plays a typical resonance at 177.8 ppm in the 13C NMR
spectrum. Subsequent reaction of 2 with hydrazine led
to the naphthyltriazole 3 in good yield (87 %). Up
to now, there exists only one report on the prepara-
tion of 3 by a Relais synthesis starting from amino-
(1,2,4)triazol published by Becker et al. [15] in 1969.
Compound 3 exhibits typical signals for the triazole
ring at 8.30 (HTz) and 14 ppm (NH) in the 1H NMR as
well as in the 13C NMR spectrum (5-CTz: 147.7, 3-CTz:
159.6 ppm), which finally proved the transferability of
this reaction sequence to aryl substituents other than
(functionalized) phenyl groups.
Scheme 2. i) (CF3SO2)2O, C5H5N, CH2Cl2, r. t., 2◦h;
ii) Pd(OAc)2, dppp, PH(O)Ph2, iPr2NEt, DMSO, 100 C,
24 h; iii) NiBr2, PPh3, Zn, KCN, MeCN, 90 ◦C, 6 h; iv) KOH,
tBuOH, 82 ◦C, 20 h.
Single crystals of the racemic nitrile rac-7 and the
racemic amide rac-8 allowed to elucidate the solid-
state structures of these two compounds. Compound
rac-7 crystallizes in the monoclinic space group P21/n.
The solid-state structure is determined by the dihe-
For the synthesis of the desired binaphthyl lig- dral angle between the two naphthyl units (98.5◦) and
and possessing a phosphine and a triazole donor site intermolecular C≡N···H–C and P=O···H–C hydro-
we started from enantiomerically pure 2,2ꢀ-dihydroxy- gen bonds (Fig. 1). Couples of molecules formed by
1,1ꢀ-binaphthyl (BINOL, 4), which was obtained by P=O···H–C hydrogen bonds and containing the (R)-
an iron(III)-mediated oxidative coupling of 2-naphthol and the (S)-enantiomer are linked by C≡N···H–C hy-
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C. May et al. · A Novel Binaphthyl Ligand
Fig. 2. Top: molecular structure of rac-8 in the solid state,
˚
characteristic bond lengths (A), angles (deg) and torsion
angles (deg): P1–O1 1.4877(11), O2–C33 1.223(2), N1–C33
1.341(2), N1–H1A 0.873(18), N1–H1B 0.89(2), N1–H1A
0.873(18), H1A···O1 2.068(18), N1···O1 2.8929(17),
C7–H7 0.95, H7···O2 2.43, C7···O2 3.287(2), C32–H32
0.95, H32···O1 2.59, C32···O1 3.0165(19); O2–C33–
N1 122.42(14), O2–C33–C12 121.33(14), N1–C33–C12
116.02(14), C33–N1–H1A 115.4(13), C33–N1–H1B
119.2(13), N1–H1A···O1 157.3(19), C7–H7···O2 150,
C32–H32···O1 107, O1–P1–C2–C1 –65.71(13), C2–C1–
C11–C12 76.51(19), C11–C12–C33–O2 30.3(2). Bottom:
chain structure of rac-8 formed by hydrogen bonds.
Fig. 1. Top: molecular structure of rac-7 in the solid-state,
˚
characteristic bond lengths (A), angles (deg) and torsion an-
gles (deg): P1–O1 1.4813(10), N1–C21 1.139(2), C12–C21
1.440(2), C10–H10 0.93, H10···N1 2.56, C10···N1
3.336(2), C14–H14 0.93, H14···O1 2.52, C14···O1
3.4156(19); N1–C21–C12 178.63(18), C10–H10···N1 141,
C14–H14···O1 162, O1–P1–C1–C2 1.21(12), C1–C2–C11–
C12 98.54(14). Bottom: polymeric structure of 7 formed by
hydrogen bonds.
drogen bonds leading to a two-dimensional arrange-
ment.
The racemic amide rac-8 crystallizes in the mon-
oclinic space group P21/c. The dihedral angle be-
tween the two napthyl planes is found to be just
The triazole ring could be implemented in two fur-
ther steps, as described above for the naphthyl system
(in Scheme 3 shown for the (R)-series).
Treatment of the amide 8 at elevated temperature
76.5◦. One of the phenyl rings of the phosphinoyl with dimethylformamide dimethylacetal (DMFDMA)
unit is almost coplanar with the amide-functionalized at elevated temperatures makes the amidine 9 accessi-
naphthyl group with an interplanar distance of about ble in high yields. As for the naphthyl system, a sin-
˚
3.2 A. Since compound rac-8 contains typical donat- glet for the methine proton is found at 8.12 ppm in
ing and accepting units for the formation of hydrogen the 1H NMR spectrum. Two resonances for the chem-
bonds, it forms dimers in the solid state, which con- ically different methyl groups were observed at typ-
1
tain both, the (R)- and the (S)-enantiomer (Fig. 2, bot- ical chemical shifts in the H (2.90, 2.48 ppm) and
tom). These dimers are further linked by C=O···H– the 13C NMR spectrum (41.0, 34.8 ppm). Due to the
C hydrogen bonds resulting in a chain-like arrange- large number of nuclei, a detailed assignment of the
ment.
remaining aromatic protons (22) and 13C resonances
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C. May et al. · A Novel Binaphthyl Ligand
1441
(30) was not possible. The NMR spectroscopic char-
acterization of 9 is completed by a single resonance
at 29.2 ppm in the 31P NMR spectrum. MALDI-TOF
mass spectrometry exhibits a signal at m/z = 553.29
([M+H]+). Ring closure with hydrazine introduces the
triazole ring as the desired N-donor site. The presence
of this fragment in compound 10 is supported by a sin-
glet at 7.77 ppm (4HTz) and one broad resonance for
the NH proton (14.59 ppm) in the 1H NMR spectrum.
The absence of aliphatic carbon atoms and the pres-
ence of two novel resonances in the 13C NMR spec-
trum (5CTz: 142.2, 3CTz: 154.9 ppm) indicate a se-
lective transformation. The 31P NMR resonance of the
phosphanoyl unit (31.7 ppm) of 10 is found at almost
the same position as that of 8 (31.5 ppm) but slightly
shifted to lower field compared to 9, which indicates
the persistence of hydrogen bonds in chloroform so-
lution in the case of 8 and 10. Optical rotation data
for R-10 ([α]2D1 = −49◦) and S-10 ([α]2D1 = +46◦) were
measured in chloroform, too. Single crystals of the bi-
naphthyl S-10, which were suitable for X-ray diffrac-
tion analysis, could be obtained by crystallization from
methanol. The molecular structure and characteristic
structural parameters of S-10 are summarized in Fig. 3.
Fig. 3. Top: molecular structure of S-10 in the solid state,
˚
characteristic bond lengths (A), angles (deg) and torsion
angles (deg): P1–O1 1.4861(12), N1–N2 1.357(2), N1–C21
1.323(2), N2–C22 1.314(2), N3–C21 1.354(2), N3–C22
1.327(3), N2–H2N 0.939(19), H2N···O1 1.714(19),
N2···O1 2.651(2), C13–H13 0.95, H13···N1 2.44,
C13···N1 2.788(3), C24–H24 0.95, H24···O1 2.59,
C24···O1 3.010(2), C24–H24 0.95, H24···N1 2.61,
C24···N1 3.551(3); N2–H2N···O1 175.2(18), C13–
H13···N1 101, C24–H24···O1 107, C24–H24···N1 169,
O1–P1–C1–C2- −29.23(16), C1–C2–C11–C12 97.1(2).
Bottom: chain structure of S-10 formed by hydrogen bonds.
ously, the 31P NMR resonance of the triarylphosphines
11 (−13.7 ppm) is shifted to higher field as compared
to the corresponding phosphineoxide 10. In the in-
frared spectrum, the absorption at 1192 cm−1 (νPO) is
missing.
Scheme 3. i) DMFDMA, 130 ◦C, 6 h; ii) N2H4·H2O, AcOH,
100 ◦C, 6 h; iii) SiHCl3, NEt3, toluene, 120 ◦C, 40 h.
Reaction of racemic 11 with PdCl2(PhCN)2 in de-
gassed and refluxing CHCl3 gave the intensely yellow
colored solid rac-12 (Fig. 4) in 82 % yield. This com-
pound is only poorly soluble in all organic solvents
and exhibits a 31P resonance in CHCl3 at 24.9 ppm
(CH3OD: 25.7 ppm), which is close to the value ob-
served by Hayashi et al. for a dichloropalladium com-
plex bearing a similar binaphthyl ligand [10]. In this
In contrast to the solid-state structures of racemic
8 and 9, the enantiomerically pure compound S-10 is
not capable to form dimers linked by hydrogen bonds
and thus has to arrange in a chain-type structure [21].
Further weak CH···N1 and CH···O give rise to the
formation of a three dimensional network (not shown
in Fig. 3).
The reduction of the phosphine oxide by a standard work, an oxazolinyl group is attached to the 2ꢀ-posi-
method [19c] completed the ligand synthesis. Obvi- tion of the binaphthyl fragment instead of the triazolyl
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C. May et al. · A Novel Binaphthyl Ligand
Fig. 4. Two isomeric palladium complexes 12 of the racemic
ligand 11 (just one enantiomer shown).
Fig. 5. Molecular structure of R-12 in the solid state (hy-
moiety. The 1H NMR spectrum of rac-12 clearly
drogen atoms omitted for clarity), selected bond lengths
shows a broad signal at 9.1 ppm, which we assign to
˚
(A), angles (deg) and torsion angles (deg): Pd1–Cl1
the NH proton of the triazolyl unit. In CHCl3 as well 2.2940(10), Pd1–P1 2.2597(7), Pd1–N1 2.001(3), Pd1–
N5 2.074(2), Pd2–Cl2 2.2867(8), Pd2–P2 2.2631(8), Pd2–
as in CH3OD the typical resonance of the triazolyl CH
N2 2.090(3), Pd2–N4 2.015(2); Cl1–Pd1–P1 88.96(3),
group is observed at 7.93 ppm. Additionally, a second
Cl1–Pd1–N1 177.35(8), Cl1–Pd1–N5 92.59(7), P1–Pd1–
set of signals deriving from a minor species (< 25 %)
N1 92.62(7), P1–Pd1–N5 177.27(7), N1–Pd1–N5 85.75(10),
is observed in CHCl3, which we first assigned to the
Cl2–Pd2–P2 89.62(3), Cl2–Pd2–N2 91.25(8), Cl2–Pd2–N4
176.97(7), P2–Pd2–N2 174.49(8), P2–Pd2–N4 92.76(8),
N2–Pd2–N4 86.21(10), Pd1–N1–N2 123.4(2), Pd2–N2–N1
117.4(2), Pd1–N5–N4 119.61(17), Pd2–N4–N5 120.93(18),
P1–Pd1–N1–N2 113.5(2), P2–Pd2–N4–N5 110.1(2), C1–
C2–C11–C12 –78.5(4), C35–C36–C45–C46 −89.7(4).
isomer rac-12ꢀ.
Reacting the ligands R-11 and S-11 with
PdCl2(PhCN)2 under similar conditions, the pal-
ladium complexes R-12 and S-12 were obtained in
high yields as bright-yellow solids. In contrast to
rac-12, the 31P NMR spectra of R-12 and S-12 show
two signals: one of a major component (> 90 %) at
22.5 ppm and one of a minor component (> 10 %)
at 25.1 ppm, which we assign to a structure similar
to rac-12 (Fig. 4). Thus for the major compound a
significant shift of the 31P resonance to higher field has
to be considered. Additionally there is no resonance
for the NH proton of the triazolyl unit in the 1H NMR
spectrum. Since the solubility of the enantiomerically
pure palladium complexes is much better than that
of the racemic mixture, recrystallization of R-12
from ethanol/dichloromethane gave bright-yellow
prismatic single crystals suitable for X-ray crystal
structure analysis. Complex R-12 crystallizes in the
orthorhombic space group P212121. Fig. 5 presents its
molecular structure in the solid state and together with
selected structural parameters.
force the donor sites into a special position all X–Pd–Y
angles are close to 90◦ or 180◦. Instead of the situ-
ation as in rac-12, there is a negatively charged tri-
azolato ligand in the trans position to the phospho-
rus atom, which explains the increased shielding ob-
served by 31P NMR spectroscopy. The P–N distances
in the six-membered Pd2N4 ring are differing: accord-
ing to the trans influence of the phosphine and the
chlorido ligand palladium forms short bonds of about
˚
2.01 A with the nitrogen atom in the trans position to
the chlorido ligand and distinctively longer bonds (ca.
˚
2.08 A) to the nitrogen atom in the trans position to the
phosphine donor. Although there are a series of solid-
state structures of coordination compounds wherein at
least two metal sites are bridged by at least two µ2,η2-
coordinating triazolato ligands rings reported in the lit-
erature [22] only two systems containing palladium
have been characterized by X-ray crystal structure
analysis [23]. Due to their molecular structures these
compounds are not comparable to R-12. Therefore
dinuclear neutral palladium compounds bearing two
µ2,η2-coordinating pyrazolato ligands are used for the
discussion of the structural features of R-12 [24]. Es-
pecially the compound bis(chlorido(µ2-3,5-dimethyl-
pyrazolato)dimethylphenylphosphinepalladium) [24a]
is closely related to R-12. Here the Pd–P distances are
Instead of monomeric (R-9)PdCl2 an almost C2-
symmetric dimer is formed by elimination of HCl. The
metal centers are bridged by two µ2,η2-coordinating
triazolato ligands resulting in the formation of a folded
six-membered Pd2N4 ring with a Pd–Pd distance of
˚
3.464 A. One phosphorus donor and one chloride lig-
and are completing the distorted square-planar coor-
dination geometry of the palladium atoms. Since the
flexible eight-membered ring formed by the chelat-
ing P,N -donor R-11 and the palladium center does not
˚
˚
at about 2.24 A (R-12: 2.2597(7), 2.2631(8) A), the
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C. May et al. · A Novel Binaphthyl Ligand
1443
bond must distinctively be weakened. Solvent evapora-
tion under vacuum will thus remove HCl (Scheme 4).
Conclusion
We have demonstrated that a new enantiomerically
pure P,N -ligand with a triazole motif as N-donor site
can be prepared in just a few steps starting from the
correspondingbinaphthyl carboxylicacidamideprecur-
sor. Its coordination to a palladium center leads to
a dimeric chelate complex due to the intermolecular
elimination of HCl. This effect will be avoided by alky-
lation of the free NH group in the ligand. The examina-
tion of catalytic applications of the novel ligand system
in standard processes like asymmetric allylic alkyla-
tion and amination and further investigation of its co-
ordination chemistry are on the way.
Experimental Section
General information
All commercially available starting materials were used
without further purification. The compounds 1, R-4, S-4,
R-5, S-5, R-6, S-6, R-7, S-7, R-8, and S-8 were prepared
by published procedures [14, 18 – 20]. NMR spectra (Bruker
DPX 400 and Bruker AVANCE 600), IR spectra (Jasco FT-
IR-6100typeA), mass spectra (Bruker ultraflex TOF/TOF),
X-ray crystal structure analyses, elemental analyses (Perkin-
Elmer Analyzer EA 2400 CHN), measurements of melting
points (Bibby Sterlin Stuart SMP3), and optical rotations
(Kru¨ss P 3001 RS) were carried out at the Department of
Chemistry at the University of Kaiserslautern.
Scheme 4. Formation of hetero- and homochiral dimers (bold
lines represent naphthyl wings pointing upward).
˚
Pd–Cl distances are at about 2.30 A (R-12: 2.2940(10),
˚
2.2867(8) A), and the Pd–N distances are at about
˚
˚
2.03 A (R-12: 2.001(3), 2.015(2) A) trans to the chloro
Nꢀ-Naphthoyl-N,N-dimethylformamidine (2)
˚
ligand and at about 2.08 A (R-12: 2.074(2), 2.2867(8),
˚
2.090(3) A) trans to the phosphine ligand.
A suspension of 2.00 g of 1 (11.7 mmol) in DMFDMA
(25 mL) was heated to 120 ◦C for 5 h. The excess of
DMFDMA was removed in vacuo, and product 2 was iso-
lated as◦ a light-yellow solid. Yield: 2.61 g (99 %). M. p.
81 – 82 C. – IR (KBr): ν = 3060 (w), 2926 (w), 1632 (s,
C=O), 1580 (s), 1564 (s), 1427 (s), 1348 (s), 1285 (s),
1116 (s), 783 (m), 768 (m) cm−1. – 1H NMR (600 MHz,
At the moment there is just speculation on the rea-
son why deprotonation of the triazole ring occurs in
the case of the enantiomerically pure ligand. One ex-
planation may arise from the poor solubility of the
racemic species rac-12. It can form dimers via hy-
drogen bonds, as we have observed for another pal-
ladium complex bearing a P,N -ligand with a protic CDCl3, 25 ◦C): δ = 8.85 (s, 1 H, Hnaph), 8.66 (s, 1 H, =CH),
3
4
NH group [11b]. Such a stable dimer, which would
be structurally similar to the dimeric subunit of rac-8
(Fig. 2, bottom) should consist of one R- and one S-
enantiomer. This is impossible for the enantiomically
pure system, which in contrast might form a homochi-
ral dimer with bridging triazole ligands in equilibrium
via the N4-protonated triazole tautomer. Since in this
case two of the three triazole nitrogen atoms will coor-
8.32 (dd, JHH = 8.5 Hz, JHH = 1.6 Hz, 1 H, Hnaph), 7.96
3
3
(d, JHH = 8.0 Hz, 1 H, Hnaph), 7.85 (d, JHH = 8.2 Hz
3
1 H, Hnaph), 7.84 (d, JHH = 7.1 Hz, 1 H, Hnaph), 7.52 (dt,
3JHH = 8.0 Hz, 3JHH = 6.8 Hz, 4JHH = 1.1 Hz, 1 H, Hnaph),
3
3
4
7.48 (dt, JHH = 7.8 Hz, JHH = 6.9 Hz, JHH = 1.1 Hz,
1 H, Hnaph), 3.19 (s, 3 H, CH3), 3.10 (s, 3 H, CH3) ppm. –
1
13C{ H} NMR (150.9 MHz, CDCl3, 25 ◦C): δ = 177.8
(C=O), 160.8 (N=CH), 135.3, 134.2, 132.8, 130.9, 129.5,
dinate to Lewis-acidic palladium(II) centers, the N–H 127.7, 127.6, 127.5, 126.2, 126.1 (10 Cnaph), 41.4 (CH3),
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C. May et al. · A Novel Binaphthyl Ligand
35.3 (CH3) ppm. – C14H14N2O (226.26): calcd. C 74.31, (S)-2-Carbamoyl-2ꢀ-diphenylphosphanoyl-1,1ꢀ-binaphthyl
H 6.24, N 12.38; found C 74.22, H 6.26, N 12.34.
(S-8)
This compound was synthesized similar to R-8 and ob-
3-Naphth-2-yl-1H(1,2,4)triazole (3)
tained as a light-yellow solid in 96 % yield. M. p. decomp.
◦
> 160 C. – IR (KBr): see R-8. – NMR data: see R-8. –
1.00 g of 2 (4.42 mmol) and 0.23 mL of hydrazine mono-
hydrat◦e were dissolved in 30 mL of acetic acid and heated
to 80 C for 4 h. The reaction mixture was evaporated un-
der reduced pressure, and the resulting oil was dissolved in
30 mL of dichloromethane. This solution was washed with
water (2 × 10 mL) and a saturated solution of NaHCO3
(10 mL), dried with Na2CO3 and filtered. The solvent was
removed to obta◦in 0.75 g (87 %) of 3 as a colorless solid.
M. p. 135 – 138 C. – IR (KBr): ν = 3149 (m), 3094 (m),
3055 (m), 2953 (m), 2906 (m), 1605 (w), 1562 (m), 1509
(m), 1411 (m), 1280 (m), 1094 (s), 1004 (m), 900 (m), ◦821
[α]2D6 = −150◦, c = 1, CHCl3.
(R)-2-N,N-Dimethylaminomethylenacylamido-2ꢀ-diphenyl-
phosphanoyl-1,1ꢀ-binaphthyl (R-9)
A suspension of 0.20 g of◦R-8 (0.4 mmol) in DMFDMA
(10 mL) was heated to 130 C for 6 h. All volatiles were
removed in vacuo. The resulting solid was washed with pen-
tane and dried in vacuo. Yield: 192 mg (87 %), light-yellow
solid. – M. p. 235 – 236 ◦C. – IR (KBr): ν = 3047 (w), 2923
(w), 1650 (s), 1594 (s), 1436 (m), 1422 (m), 1324 (s), 1232
(s), 1197 (s, P=O), 1116 (m), 1099 (s), 766 (m), 750 (m), 705
(m), 694 (m), 540 (m), 519 (m) cm−1. – 1H NMR (400 MHz,
1
(m), 752 (s) cm−1. – H NMR (400 MHz, CDCl3, 25 C):
δ = 14.12 (br. s, 1 H, NH), 8.51 (s, 1 H, Hnaph), 8.31 (s, 1 H,
5-HTz), 8.07 (dd, 3JHH = 8.5 Hz, 4JHH = 1.4 Hz, 1 H, Hnaph),
7.79 (d, 3JHH = 8.5 Hz, 1 H, Hnaph), 7.75 (d, 3JHH = 8.5 Hz,
◦
3
CDCl3, 25 C): δ = 8.21 (d, JHH = 8.7 Hz, 1 H, Hnaph),
8.12 (s, 1 H, N=CH), 7.92 – 7.85 (m, 2 H, Hnaph), 7.79 – 7.74
(m, 1 H, Hnaph), 7.66 – 7.64 (m, 2 H, Hnaph), 7.48 – 7.44 (m,
1 H, Hnaph), 7.40 – 7.32 (m, 5 H, Hnaph), 7.22 – 7.17 (m, 3 H,
Hnaph), 7.14 – 7.00 (m, 7 H, Hnaph), 2.90 (s, 3 H, CH3), 2.48
3
1 H, Hnaph), 7.71 (d, JHH = 8.5 Hz, 1 H, Hnaph), 7.45 (dt,
3JHH = 7.9 Hz, 3JHH = 6.9 Hz, 4JHH = 1.2 Hz, 1 H, Hnaph),
7.40 (dt, 3JHH = 7.9 Hz, 3JHH = 6.9 Hz, 4JHH = 1.2 Hz, 1 H,
1
Hnaph) ppm. – 13C{ H} NMR (100.6 MHz, CDCl3, 25 ◦C):
(s, 3 H, CH3) ppm. – 13C{ H} NMR (100.6 MHz, CDCl3,
1
25 ◦C): δ = 178.3 (C=O), 159.8 (N=CH), 145.5, 136.3,
135.5, 134.5, 134.4, 134.2, 134.1, 134.0, 133.9, 133.7, 133.2,
132.9, 132.0, 131.9, 131.7, 131.6, 130.7, 129.1, 129.0, 128.8,
128.4, 128.1, 127.9, 127.8, 127.7, 127.6, 127.5, 126.7, 126.6,
126.0 (30 Cnaph), 41.0 (◦CH3), 34.8 (CH3) ppm. – 31P NMR
(162 MHz, CDCl3, 25 C): δ = 29.2 ppm. – MALDI-TOF
MS: m/z = 553.29 [MH]+.
δ = 159.6 (3-CTz), 147.7 (5-CTz), 134.2, 133.3, 128.9, 128.7,
127.9, 127.2, 126.8, 126.5, 126.2, 123.7 (10 Cnaph) ppm. –
C12H9N3 (195.21): calcd. C 73.83, H 4.65, N 21.53; found
C 73.61, H 4.48, N 21.64.
(R)-2-Carbamoyl-2ꢀ-diphenylphosphanoyl-1,1ꢀ-binaphthyl
(R-8)
This compound was synthesized from the nitrile R-7 ac-
cording to a published procedure [20] and obtained a◦s a light-
yellow solid in 93 % yield. M. p. decomp. > 160 C. – IR
(KBr): ν = 3447 (br, m), 3051 (m), 1669 (s), 1614 (m), 1437
(m), 1389 (w), 1178 (m, P=O), 1117 (m), 1097 (w), 822 (w),
749 (m), 724 (s), 700 (s), 636 (m), 539 (s), 524 (s) cm−1. –
1H NMR (400 MHz, CDCl3, 25 ◦C): δ = 9.45 (s, 1 H, NH2),
(S)-2-N,N-Dimethylaminomethylenacylamido-2ꢀ-
diphenylphosphanoyl-1,1ꢀ -binaphthyl (R-9)
This compound was synthesized according to the proce-
dure described for R-9 and obtained as a light-yellow solid in
92 % yield. M. p. 235 – 236 ◦C. The IR and NMR data corre-
spond to those of R-9.
3
7.93 – 7.91 (m, 1 H, Hnaph), 7.87 (d, JHH = 8.4 Hz, 2 H,
(R)-2ꢀ-Diphenylphosphanoyl-2-[1H(1,2,4)triazol-3-yl]-1,1ꢀ -
binaphthyl (R-10)
H
naph), 7.74 (d, 3JHH = 8.4 Hz, 1 H, Hnaph), 7.71 – 7.68 (m,
3
2 H, Hnaph), 7.64 (d, JHH = 8.2 Hz, 1 H, Hnaph), 7.60 –
7.47 (m, 4 H, Hnaph), 7.46 – 7.41 (m, 1 H, Hnaph), 7.31 – 7.28
(m, 1 H, Hnaph), 7.19 – 7.12 (m, 5 H, Hnaph), 6.98 – 6.93 (m,
0.24 g of R-9 (0.43 mmol) and 0.03 mL of hydrazine
monohydrate were dissolved in 10 mL of acetic acid and
3
◦
2 H, Hnaph), 6.67 – 6.63 (m, 1 H, Hnaph), 6.34 (d, JHH
=
heated to 100 C for 6 h. The reaction mixture was evap-
8.5 Hz, 1 H, Hnaph), 5.51 (s, 1 H, NH2) ppm. – 13C{ H}
NMR (150.9 MHz, CDCl3, 25 ◦C): δ = 172.9 (C=O), 143.1,
136.6, 134.8, 133.7, 133.1, 133.0, 132.3, 132.2, 132.1, 131.7,
131.2, 131.0, 130.7, 129.7, 129.4, 129.1, 129.0, 128.9, 128.8,
128.5, 128.3, 128.2, 128.0, 127.9, 127.8, 127.7, 127.5, 126.7,
125.9, 124.6 (30 Cnaph) ppm. – 31P NMR (162 MHz, CDCl3,
1
orated under reduced pressure leading to an oily residue,
which was dissolved in 30 mL of dichloromethane. This so-
lution was washed with water (2 × 10 mL) and a saturated
solution of NaHCO3 (10 mL), dried with Na2CO3 and fil-
tered. The solvent was removed, and the oily residue was
again dissolved in methanol to obtain 200 mg (88 %) of R-
25 ◦C): δ = 31.5 ppm. – [α]D23 = +140◦, c = 1, CHCl3; 10 as pale-yellow crystals. M. p. decomp. > 295 C. – IR
◦
([α]2D4 = +157◦, c = 1, CHCl3) [20b].
(KBr): ν = 3430 (br, w), 3141 (w), 3051 (m), 2992 (w), 2942
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C. May et al. · A Novel Binaphthyl Ligand
1445
(m), 2849 (w), 1501 (m), 1435 (m), 1192 (s, P=O), 1120 128.4, 128.3, 128.2, 128.1, 127.8, 127.1, 127.0, 126.8, 126.1,
1
(m), 750 (s), 698 (s) cm−1. – H NMR (400 MHz, CDCl3, 126.0, 125.5 (28 Cnaph) ppm. – 31P NMR (162 MHz, CDCl3,
25 ◦C): δ = 14.59 (br, s, 1 H, NH), 7.92 – 7.84 (m, 3 H, 25 ◦C): δ = −13.7 ppm.
Hnaph), 7.82 – 7.79 (m, 2 H, Hnaph), 7.77 (s, 1 H, HTz), 7.75 –
7.74 (m, 1 H, Hnaph), 7.62 – 7.60 (m, 1 H, Hnaph), 7.58 –
7.56 (m, 1 H, Hnaph), 7.54 – 7.49 (m, 3 H, Hnaph), 7.44 – 7.40
(S)-2ꢀ-Diphenylphosphanyl-2-[1H(1,2,4)triazol-3-yl]-1,1ꢀ-
binaphthyl (S-11)
(m, 1 H, Hnaph), 7.24 – 7.14 (m, 4 H, Hnaph), 6.97 – 6.89 (m,
3 H, Hnaph), 6.79 – 6.74 (m, 2 H, Hnaph), 6.58 – 6.55 (m, 1 H,
This compound was synthesized according to the proce-
dure described for R-11 and obtained as a pale-yellow solid
in 66 % yield. The IR and NMR data correspond to those of
R-11.
1
H
naph) ppm. – 13C{ H} NMR (150.9 MHz, CDCl3, 25 ◦C):
δ = 154.9 (3-CTz), 142.2 (5-CTz), 134.8, 134.0, 133.2, 132.9,
132.5, 132.3, 132.2, 132.1, 131.8, 130.9, 130.5, 130.4, 129.9,
129.4, 129.3, 128.9, 128.8(5), 128.8(2), 128.7, 128.6, 128.0,
127.9, 127.8, 127.7, 127.5, 127.4, 127.0, 126.9, 126.8, 126.4
(30 Cnaph) ppm. – 31P NMR (162 MHz, CDCl3, 25 ◦C): δ =
31.7 ppm. – C34H24N3OP (521.52): calcd. C 78.30, H 4.64,
N 8.06; found C 77.79, H 4.58, N 7.93. – [α]2D1 = −49◦, c =
0.5, CHCl3.
Synthesis of the palladium complexes rac-12, R-12 and
S-12
45.5 mg of PdCl2(PhCN)2 (0.12 mmol) were added to
60.0 mg of a solution of R-11 or S-11 (0.12 mmol) in 10 mL
of degassed chloroform. The resulting yellow solution was
heated to reflux for 4 h. After all volatiles were removed
in vacuo, the resulting yellow solid was washed with di-
ethyl ether (5 mL), methanol (5 mL) and pentane (5 mL)
and was dried in vacuo. rac-10: Yield: 82 %, bright-yellow
solid. – IR (KBr, cm−1): ν = 3437 (m), 3056 (m), 1621 (w),
1497 (m), 1481 (m), 1459 (w), 1437 (s), 1313 (w), 1099
(m), 869 (w), 818 (s), 746 (s), 693 (s), 639 (w), 530 (s),
500 (s). – 1H NMR (CDCl3, 400.1 MHz): δ = 9.08 (br, 1H,
NH), 8.11 (d, 3JHH = 8.4 Hz, 1H, Har), 6.73 – 7.90 (m, 21H,
(S)-2ꢀ-Diphenylphosphanoyl-2-[1H(1,2,4)triazol-3-yl]-1,1ꢀ -
binaphthyl (S-10)
This compound was synthesized according to the proce-
dure described for R-10 and obtained as pale-yellow crys-
tals in 86 % yield. M. p. decomp. > 295 ◦C. – IR (KBr): see
R-8. – NMR data: see R-8. – C34H24N3OP (521.52): calcd.
C 78.30, H 4.64, N 8.06; found C 77.67, H 4.63, N 7.81. –
[α]2D1 = +46◦, c = 0.5, CHCl3.
3
20 × Har, 1 × Htz), 6.16 (d, JHH = 8.4 Hz, 1H, Har). –
(R)-2ꢀ-Diphenylphosphanyl-2-[1H(1,2,4)triazol-3-yl]-1,1ꢀ -
binaphthyl (R-11)
1H NMR (CD3OD, 400.1 MHz): δ = 8.63 (br, 1H, NH),
8.25 (d, 3JHH = 8.4 Hz, 1H, Har), 8.01 (br, 2H, Har), 7.87 –
7.91 (m, 4H, 3 × Har, 1 × Htz), 7.37 – 7.61 (m, 8H, Har),
7.23 – 7.27 (m, 2H, Har), 6.80 – 6.93 (m, 5H, Har), 6.24 (d,
3JHH = 8.4 Hz, 1H, Har). – 31P NMR (CDCl3, 162.0 MHz):
δ = 24.9 (s). – 31P NMR (CD3OD, 162.0 MHz): δ = 25.7
(s). – MS (MALDI-TOF): m/z = 647.23 [M–Cl]+, 611.24
[M–2Cl]+. – C34H24Cl2N3PPd·(CHCl3)0.5 (742.53): calcd.
C 55.80, H 3.33, N 5.66; found C 55.44, H 3.44, N 5.67.
R-10: Yield: 78 %, bright-yellow solid. – IR (KBr): ν =
3430 (m), 3054 (m), 1620 (w), 1498 (m), 1480 (w), 1459
(s), 1437 (s), 1316 (w), 1099 (m), 869 (w), 819 (s), 744
(s), 696 (s), 640 (w), 5◦30 (s), 499 (s) cm−1. – 1H NMR
0.81 g of Cl3SiH (5.9 mmol) were added to a mixture of
0.25 mg of R-10 (0.48 mmol) and 3 mL of degassed Et3N
◦
in 10 mL of dry and degassed toluene at 0 C. The reaction
mixture was stirred at 120 ◦C for 40 h. After cooling to r. t.,
the mixture was diluted with 5 mL of degassed Et2O and
quenched with small amounts of a saturated and degassed
solution of NaHCO3 (overall: 5 mL). The resulting suspen-
R
ꢀ
sion was filtered through Celite , and the solid filter cake
was washed with 5 mL of degassed Et2O and 5 mL of de-
gassed CHCl3. The organic phase was dried over Na2SO4,
filtered and evaporated under reduced pressure. The resulting
solid was washed with degassed pentane and dried in vacuo
to obtain 190 mg (78 %) of R-11 as a pale-yellow solid. – IR
(KBr): ν = 3422 (br, w), 3054 (m), 2939 (m), 2603 (m), 2495
3
(400 MHz, CDCl3, 25 C): δ = 8.11 (d, JHH = 8.4 Hz,
1 H, Hnaph), 7.91 – 7.83 (m, 3 H, Hnaph), 7.83 (s, 1 H, HTz),
7.71 (d, 3JHH = 8.4 Hz, 1 H, Hnaph), 7.60 (d, 3JHH = 8.4 Hz,
3
(m), 1498 (m), 1478 (m), 1434 (m), 822 (m), 814 (m), ◦743 1 H, Hnaph), 7.55 (d, JHH = 8.4 Hz, 1 H, Hnaph), 7.43 –
(s), 697 (s) cm−1. – 1H NMR (400 MHz, CDCl3, 25 C): 7.28 (m, 5 H, Hnaph), 7.18 – 7.14 (m, 3 H, Hnaph), 7.03 –
3
3
δ = 8.46 (d, JHH = 8.7 Hz, 1 H, Hnaph), 8.12 (d, JHH
=
6.99 (m, 1 H, Hnaph), 6.94 – 6.81 (m, 4 H, Hnaph), 6.64 –
3
3
8.7 Hz, 1 H, Hnaph), 8.01 (d, JHH = 8.5 Hz, 1 H, Hnaph), 6.60 (m, 1 H, Hnaph), 5.86 (d, JHH = 8.4 Hz, 1 H, Hnaph
)
7.95 (t, 3JHH = 9.1 Hz, 2 H, Hnaph), 7.67 (s, 1 H, HTz), 7.56 – ppm. – 13C{ H} NMR (100.6 MHz, CDCl3, 25 C): δ =
1
◦
7.44 (m, 3 H, Hnaph), 7.31 – 7.11 (m, 9 H, Hnaph), 7.01 – 161.8, 152.6, 142.0, 136.2, 134.9, 133.6, 133.5, 133.3, 133.2,
6.94 (m, 5 H, Hnaph) ppm. – 13C{ H} NMR (150.9 MHz,
1
132.1, 131.4, 131.3, 129.8, 129.4, 129.2, 129.1, 128.8, 128.2,
128.1, 127.9, 127.8, 127.7, 127.6, 127.2, 127.1, 127.0, 126.8,
126.7, 126.3, 126.0, 124.9, 124.3 (30 Cnaph + 2 CTz) ppm. –
◦
CDCl3, 25 C): δ = 155.1 (3-CTz), 142.7 (5-CTz), 136.8,
135.7, 135.4, 133.9, 133.8, 133.6, 133.4, 133.3, 133.1, 132.5,
130.8, 129.3, 129.2, 128.5(9), 128.5(7), 128.5(5), 128.5, 31P NMR (162 MHz, CDCl3, 25 ◦C): δ = 22.5 ppm. –
Unauthenticated
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1446
C. May et al. · A Novel Binaphthyl Ligand
Table 1. Summary of the crystallographic data and details of data collection and refinement for compounds 7, 8, S-10 and
R-12.
7
8
S-10
R-12
Empirical formula
Formula weight
Crystal size, mm3
T, K
C33H22NOP
479.49
C33H24NO2P
497.50
C34H24N3OP
521.53
C68H46Cl2N6P2Pd2
1292.75
0.46 × 0.41 × 0.32
0.17 × 0.08 × 0.07
0.13 × 0.10 × 0.10
0.27 × 0.26 × 0.15
293(2)
150(2)
150(2)
150(2)
˚
λ, A
0.71073
1.54184
1.54184
0.71073
Crystal system
Space group
monoclinic
P21/n
11.9257(8)
13.4298(7)
15.5358(11)
90
90.109(8)
90
2488.2(3)
4
1.28
0.1
2.62 – 26.73
22915 / 5233
0.0728
monoclinic
P21/c
13.4340(2)
15.2644(1)
12.1904(1)
90
102.907(1)
90
2436.63(5)
4
1.36
1.3
4.72 – 62.66
11853 / 3817
0.0206
orthorhombic
P212121
9.5824(1)
14.9789(1)
18.3523(2)
90
orthorhombic
P212121
16.3352(1)
18.2290(2)
24.6564(2)
90
˚
a, A
˚
b, A
˚
c, A
α, deg
β, deg
90
90
90
90
γ, deg
3
˚
V, A
2634.18(4)
4
1.32
7342.04(11)
4
1.17
Z
ρcalcd., g cm−3
µ, mm−1
1.2
0.6
θ range, deg
3.81 – 62.65
8968 / 3842
0.0187
3.99 – 32.51
95455 / 24530
0.0420
Refl. coll. / indep.
Rint
Data / restr. / ref. param.
Final indices R1 / wR2 [I ≥ 2 σ(I)]a
R1 / wR2 indices (all data)a
GooFb
5233 / 0 / 325
0.0374 / 0.1010
0.0449 / 0.1047
1.046
3817 / 1 / 342
0.0301 / 0.0815
0.0369 / 0.0843
1.047
3842 / 1 /355
0.0263 / 0.0648
0.0300 / 0.0661
0.989
0.005(16)
0.119 / −0.199
24530 / 0 / 721
0.0367 / 0.1009
0.0500 / 0.1142
1.126
Flack parameter
–
–
−0.052(17)
−3
˚
∆ρmax/min, e·A
0.289 / −0.307
0.262 / −0.322
0.676 / −0.472
R1 = ΣꢁFo|−|Fcꢁ/Σ|Fo|, wR2 = [Σw(Fo −Fc2)2/Σw(Fo2)2]1/2, w = [σ2(Fo2)+(AP)2 +BP]−1, where P = (Max(Fo2,0)+2Fc2)/3;
a
2
GoF = [Σw(Fo −Fc2)2/(nobs −nparam)]1/2
.
b
2
C68H46Cl2N6P2Pd2·(CHCl3)0.5 (1352.54): calcd. C 60.80, gen atoms positions were calculated in ideal positions (riding
H 3.47, N 6.21; found C 60.31, H 3.38, N 6.05. – [α]D23
=
model) except for the hydrogen atoms (H1A and H1B) bound
+1180◦, c = 0.1, CHCl3. S-12: Yield: 80 %, bright yellow to nitrogen atom N1 in 8 and the hydrogen (H2N) bound to
solid. The IR and NMR data correspond to those of R-12. – nitrogen atom N2 in S-10, which were located in the differ-
C68H46Cl2N6P2Pd2·(CHCl3)0.5 (1352.54): calcd. C 60.80,
ence Fourier synthesis. H1A and H1B in 8 were refined with
H 3.47, N 6.21; found C 60.56, H 3.84, N 6.21. – [α]D23
−1260◦, c = 0.1, CHCl3.
=
individual isotropic displacement parameters, while H2N in
S-10 was refined with the help of a distance restraint, while
constraining its U value to 1.2 times the Ueq value of N2, the
bonding atom. Due to the presence of severely disordered
solvent molecules, the SQUEEZE routine as implemented in
PLATON [29] has been performed for compound R-12.
CCDC 754536 (7), 754537 (8), 754538 (S-10) and
754539 (R-12) contain the supplementary crystallographic
data for this paper. These data can be obtained free of
charge from The Cambridge Crystallographic Data Centre
via www.ccdc.cam.ac.uk/data request/cif.
X-Ray crystal structure analyses
Crystal data and refinement parameters are summarized
in Table 1. The structures were solved using Direct Meth-
ods (for compound 7 SIR97 [25] and for compounds 8, S-
10, and R-12 SIR92 [26]), completed by subsequent dif-
ference Fourier syntheses, and refined by full-matrix least-
squares procedures [27]. Semi-empirical absorption correc-
tions from equivalents (Multiscan) were carried out for 8,
S-10, and R-12 [28], whereas for compound 7 no absorp-
tion correction was applied. All non-hydrogen atoms were
refined with anisotropic displacement parameters. All hydro-
Acknowledgement
The authors wish to thank the Deutsche Forschungsge-
meinschaft for financial support.
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Unauthenticated
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C. May et al. · A Novel Binaphthyl Ligand
1447
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