Diphosphorus Ligands Containing a P-Stereogenic Phosphane and a Chiral Phosphite or Phosphorodiamidite – Evaluation in Pd-Catalysed Asymmetric Allylic Substitution Reactions

Article abstract of DOI:10.1002/ejic.201600550

The synthesis of 14 new optically pure C₁-symmetric phosphane–phosphinite (1–4), phosphane–phosphite (5–9) and phosphane–phosphorodiamidite (10–14) ligands is reported. The ligands were prepared through the condensation of (2-hydroxyphenyl)phenylphosphanes PPh(2-PhOH)R (R = Me, tBu and Ph) with chlorodiisopropylphosphane (1 and 2), chlorodiphenylphosphane (3 and 4), the chlorodioxaphosphepine derived from both enantiomers of 1,1′-bi-2-naphthol (5–9) and the chlorodiazaphosphepine derived from both enantiomers of N,N′-dimethyl-1,1′-binaphthyl-2,2′-diamine (10–14) in the presence of a base. With these ligands, cationic Pd complexes of the type [Pd(η³-C₄H₇)(PP′)]PF₆(Pd1–Pd14) were obtained and characterised; the crystal structures of Pd1, Pd2 and Pd13 were obtained. In solution, the complexes are present as mixtures of two diastereomers because of the lack of symmetry of the ligand and the presence of the methallyl group. The Pd complexes catalyse the allylic alkylation with dimethyl malonate and the amination with benzylamine of the model substrate rac-3-acetoxy-1,3-diphenyl-1-propene (I). For the alkylation, full conversions and good enantioselectivities (up to 96 % ee with Pd14) were observed.

Full text of DOI:10.1002/ejic.201600550

DOI: 10.1002/ejic.201600550
Full Paper
Chiral P–P Ligands
Diphosphorus Ligands Containing a P-Stereogenic Phosphane
and a Chiral Phosphite or Phosphorodiamidite – Evaluation in
Pd-Catalysed Asymmetric Allylic Substitution Reactions
Pau Clavero,[a] Arnald Grabulosa*[a] Mercè Rocamora,[a] Guillermo Muller,[a] and
Mercè Font-Bardia[b]
Abstract: The synthesis of 14 new optically pure C1-symmetric the type [Pd(η3-C4H7)(PP′)]PF6 (Pd1–Pd14) were obtained and
phosphane–phosphinite (1–4), phosphane–phosphite (5–9) characterised; the crystal structures of Pd1, Pd2 and Pd13 were
and phosphane–phosphorodiamidite (10–14) ligands is re- obtained. In solution, the complexes are present as mixtures of
ported. The ligands were prepared through the condensation two diastereomers because of the lack of symmetry of the li-
of (2-hydroxyphenyl)phenylphosphanes PPh(2-PhOH)R (R = Me, gand and the presence of the methallyl group. The Pd com-
tBu and Ph) with chlorodiisopropylphosphane (1 and 2), chloro- plexes catalyse the allylic alkylation with dimethyl malonate and
diphenylphosphane (3 and 4), the chlorodioxaphosphepine de- the amination with benzylamine of the model substrate rac-3-
rived from both enantiomers of 1,1′-bi-2-naphthol (5–9) and acetoxy-1,3-diphenyl-1-propene (I). For the alkylation, full con-
the chlorodiazaphosphepine derived from both enantiomers of versions and good enantioselectivities (up to 96 % ee with
N,N′-dimethyl-1,1′-binaphthyl-2,2′-diamine (10–14) in the pres- Pd14) were observed.
ence of a base. With these ligands, cationic Pd complexes of
Introduction
that are not phosphanes but possess one or more P–hetero-
atom bonds,[5] including many monophosphorus ligands.[6] It is
also widely accepted that the previously ubiquitous C2-symmet-
ric diphosphorus ligands (PP) are not better per se than their
C1-symmetric counterparts (PP′).[5a,5c,7] Finally, a strong resur-
gence of P-stereogenic ligands has also occurred.[4b,8] The ex-
traordinary activity in the area of ligand design is understanda-
ble for the ever-increasing demand of optically pure com-
pounds in pharmaceutical, agrochemical and other fields and is
evident from the number of recent reviews[5b,7,9] and mono-
graphs[4] about the synthesis of chiral phosphorus-based li-
gands.
Chiral phosphorus-based ligands have dominated asymmetric
transition-metal homogeneous catalysis for more than 50
years.[1] Many of the most successful ligands are C2-symmetric
diphosphanes,[2] which were initially thought to be superior li-
gands to monophosphanes or C1-symmetric ligands as the re-
duced number of intermediates and transition states in each
step of a catalytic cycle would lead to higher enantioselectivi-
ties and simpler analysis of the results.
However, a much more complicated picture has now
emerged. Although certain structural motifs lead to especially
active and enantioselective ligands,[3] there will clearly never
be a “universal ligand” suitable for all reactions and substrates.
Therefore, all possible sources of structural diversity have been
explored actively for the last two decades, and old dogmas and
preconceptions have been revised or abandoned.[3,4] Nowadays,
very active and enantioselective catalysts can contain ligands
Only a few C1-symmetric diphosphorus ligands containing
both a P-stereogenic phosphane and another phosphorus do-
nor unit with a P–heteroatom bond have been reported.[10]
We have been working on the synthesis and catalytic appli-
cations of many chiral mono- and bidentate aminophos-
phane,[11] phosphinite,[12] phosphite[13] and phosphorodiamid-
ite[14] ligands in several catalytic reactions. We have also been
working on the synthesis and catalytic applications of P-stereo-
genic ligands.[12a,12b,15]
[a] Departament de Química Inorgànica i Orgànica,
Secció de Química Inorgànica, Universitat de Barcelona,
Martí i Franquès, 1-11, 08028, Barcelona, Spain
E-mail: address: arnald.grabulosa@qi.ub.es
http://www.ub.edu/inorgani/ca/index.html
[b] Departament de Cristal·lografia, Mineralogia i Dipòsits Minerals, Univer-
sitat de Barcelona,
Therefore, it was deemed interesting to devote some effort
to merge both areas of our previous research and prepare a
few PP′ (P = P-stereogenic phosphane; P′ = phosphinite, phos-
phite or phosphorodiamidite) ligands and evaluate their cata-
lytic potential. In this paper, we describe the synthesis of these
ligands and their derived Pd complexes as well as their applica-
tion as catalyst precursors in allylic substitution reactions.
Martí i Franquès, s/n, 08028, Barcelona, Spain
Supporting information and ORCID(s) from the author(s) for this article are
available on the WWW under http://dx.doi.org/10.1002/ejic.201600550.
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Results and Discussion
commercially available. To complete the synthesis of the li-
gands, phosphinophenols C–C′′ were treated with the appropri-
ate chlorophosphorus precursors (either commercially available
or described previously)[14] in the presence of amines as de-
tailed in the Experimental Section. After the removal of the
ammonium salts by filtration and exhaustive drying under vac-
uum, the desired PP′ ligands were finally obtained as pasty sol-
ids. The ligands prepared in the present work are shown in
Figure 1.
Ligand Synthesis
Upon analysing the possible routes to obtain modular P-stereo-
genic PP′ ligands with an appropriate bridge to form bidentate
ligands, it was concluded that a relatively easy way would be
the condensation reaction between an electrophilic chloro-
phosphorus precursor and a configurationally stable P-stereo-
genic 2-hydroxyphenylphosphane in the presence of base. Such
reactions would yield PP′ ligands with rigid 2-oxyphenyl
bridges between the two phosphorus atoms (Scheme 1).
An early paper of Pringle and Baker[16] described the prepa-
ration of one such ligand (see later), whereas Pizzano and co-
workers have used this scaffold to prepare a series of phos-
phane–phosphite ligands and used them in Rh-[10f,10g,10l,17] and
Ir-catalysed[10i,18] hydrogenations and in Rh-catalysed hydro-
formylation;[10l] however, only a few of their ligands possess a
P-stereogenic phosphane moiety.
The required P-stereogenic 2-hydroxyphenylphosphanes are
accessible as optically pure compounds by the well-known
Jugé–Stephan method[19] starting from oxaphospholidine–
borane A. Therefore, we started by reproducing the work of
Stephan and co-workers,[20] who described the preparation of
2-hydroxyphenylphosphinite–borane B, and we obtained
2-hydroxyphenylphosphane C·BH3 by treatment with excess
methyllithium (Scheme 2).
A solution of B was also treated with excess tert-butyllithium
to afford the corresponding 2-hydroxyphenylphosphane–
borane C′·BH3. It has to be noted that it is very difficult[21] to
introduce the tert-butyl group to a phosphane through the
Jugé–Stephan method. However, in this case, it seems that the
presence of an oxygen-containing group at the ortho position
Figure 1. Prepared PP′ ligands 1–14.
relative to the
P atom facilitates the organolithium at-
tack.[21a,21c] Phosphane–boranes C·BH3 and C′·BH3 were debor-
To the best of our knowledge, all of the prepared ligands are
onated by treatment with tetrafluoroboric acid to yield the free new except ligand 9, which was described by Baker and
phosphinophenols C and C′ as air-sensitive semisolids. The ab- Pringle[16] and used by Pizzano and co-workers in Rh-catalysed
solute configurations of the phosphorus atoms, expected to be hydrogenation.[17b] The ligands were characterised by 1H and
S, could be verified by the crystal structures of the Pd com- 31P{1H} NMR spectroscopy, which supported the structures de-
plexes of the ligands (described below). The preparation of the picted in Figure 1. In general, two doublets (4JP, P = 0–41 Hz)
achiral phosphinophenol C′′ was not required because it is were observed in the 31P{1H} NMR spectra, and the coupling
Scheme 1. Retrosynthetic route to the PP′ ligands.
Scheme 2. Preparation of PP′ ligands 1–14.
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constants are strongly dependent on the ligand. The coupling The CCS values are approximately +40 ppm for phosphinite
constants for the phosphane–phosphinite ligands 1–4 are complexes Pd1–Pd4, +2 ppm for phosphite complexes Pd5–
rather small (0–4 Hz), but those for phosphane–phosphite li- Pd9 and –15 ppm for phosphorodiamidite complexes Pd10–
gands 5–9 are much larger (15–42 Hz), whereas those for the Pd14. The shielding of the P atom of the phosphorodiamidite
phosphane–phosphorodiamidite ligands 10–14 have interme- upon coordination is probably due to the low σ donation of
diate values (7–16 Hz). As expected,[14a] small differences in the this part of the ligand and has been reported for the complexa-
31P{1H} NMR chemical shifts for each of the members in the tion of other chiral phosphorodiamidite ligands.[14,24]
In 1H NMR spectra, two sets of peaks associated with the
aliphatic protons of each ligand are observed (see Experimental
Section and Table S1 of the Supporting Information for details).
For Pd10–Pd14 bearing the phosphane–phosphorodiamidite li-
gands, two pairs of doublets, one for each isomer, account for
the methyl groups of the diazaphosphepine part of the ligand.
diastereomeric pairs 5/7, 6/8, 10/12 and 11/13 could be spot-
ted. In the H NMR spectra of phosphane–phosphorodiamidite
1
ligands 10–14, two doublets appeared for the two inequivalent
N–Me groups coupled to the phosphorus atom, as previously
reported for related compounds.[14a] A more thorough charac-
terisation was not possible owing to the rapid degradation of
the ligands by oxidation, hydrolysis, or both if they were not
kept under a protective nitrogen atmosphere. Therefore, the
ligands were not stored but used immediately for complexation
to Pd as described in the following section.
3
Interestingly, the JH,P coupling constants are clearly different
for the two methyl groups of each isomer (ca. 10 and 15 Hz),
and the same can be observed in the 13C{1H} NMR spectra, in
which 2JC,P ≈ 12 and 30 Hz. This suggests that the amino groups
have a different orientation in solution with respect to the P–
Pd bond, as observed in the solid state (vide infra) and for previ-
ously reported related compounds.[14d,24,25]
Preparation of Pd Complexes
1
The reaction of the Pd dimer D with 2 equiv. of ligand in di-
chloromethane in the presence of excess ammonium hexa-
fluorophosphate[12b,12c] yielded the expected cationic com-
plexes of the type [Pd(η3-C4H7)(PP′)]PF6 (Pd1–Pd14) as white or
pale yellow solids after workup (Scheme 3).
For the methallyl group, the H NMR spectra (Table S1) con-
firm the presence of two diastereomers. Hence, two singlets at
δ = 1.3–2.0 ppm account for the methyl group, whereas two
sets of four peak in the range δ = 2.3–4.8 ppm can be assigned
to the four protons of the methallyl group. As ex-
pected,[14a,14d,22,23] the anti protons usually appear at higher
fields (δ = 2.3–3.8 ppm) as doublets with coupling constants of
ca. 10 Hz owing to the coupling with the phosphorus atom at
the relative trans position. In a few cases, they appear as dou-
blets of doublets, also coupled to the phosphorus atom at the
cis position. At lower fields (δ = 3.6–4.8 ppm), two sets of syn
protons appear as broad singlets, doublets, doublets of dou-
blets or multiplets. For these protons, the coupling constants
are smaller, as commonly found for comparable sys-
tems.[14a,14d,22,23] In the 13C{1H} NMR spectra (Table S1), the
methylene termini of the methallyl groups appeared as dou-
blets or doublets of doublets owing to the coupling with one
or two phosphorus atoms, respectively. The difference in the
chemical shifts, which has been used to evaluate the asymme-
try of the allyl bonding,[26] ranged from 2.5 ppm for one of the
isomers of Pd3 to 13.6 ppm for one of the isomers of Pd2.
Scheme 3. Preparation of Pd complexes Pd1–Pd14.
The characterisation of solutions of the complexes by multi-
1
nuclear (31P{1H}, H, and in some cases 13C{1H}) NMR spectro-
scopy revealed duplicate peaks indicative of the existence of
two diastereoisomeric species owing to the lack of C2 symmetry
of the bidentate ligand and the presence of the η3-methallyl
moiety, as previously observed for neutral complexes of the
For Pd1, Pd2 and Pd13, single crystals suitable for X-ray dif-
fraction studies were obtained by layering hexane on solutions
of the complexes in dichloromethane. For all of these com-
plexes, the structures are composed of discrete molecules of
the cationic complex, hexafluorophosphate anions and di-
chloromethane molecules as well as adventitious water mol-
ecules for Pd13 separated by van der Waals distances. It is inter-
esting to note that only one diastereomer was found in all of
the crystals analysed. Representations of the molecular struc-
tures of Pd1 and Pd2 and a selection of bond lengths and an-
gles are given in Figure 2.
type [Pd(η3-C4H7)Cl(P)] (P
= chiral monophosphorus li-
gand).[12a,12c,14a,14c,22] The integration of the 31P{1H} and 1H NMR
spectra allowed the estimation of the diastereomeric ratio for
each complex. There does not seem to be a simple correlation
between the structures of the complexes and their diastereo-
meric ratios, which varied from 1:1 (Pd2, Pd4, Pd7, Pd12 and
Pd14) to a maximum of 1:2.7 for Pd5. In the 31P{1H} NMR spec-
tra, two sharp pairs of doublets, one for each diastereomer, are
2
indicative of AX spin systems. The JP, P′ values are in the range
previously reported for related compounds[14d,23] and follow the
4
same trends as the JP, P′ values for the free ligands. The
For both structures, the palladium atom sits in a distorted
square-planar geometry, coordinated to the two phosphorus
31P coordination chemical shifts (CCS, defined as δcomplex
–
δfree ligand) of the phosphane fragments are approximately atoms and to the terminal C atoms of the methallyl moiety.
+30 ppm for the complexes, as expected. In contrast, the other The metric parameters are in the ranges expected for cationic
phosphorus moiety shows a larger sensitivity to coordination. allylpalladium complexes.[12b,14d,22] For both structures, the Pd–
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–
Figure 2. ORTEP representations (thermal ellipsoids drawn at 50 % of probability level, H atoms and PF6 anions removed for clarity) of Pd1 (left) and Pd2
(right). Distances [Å] and angles [°] for Pd1: Pd–P(1) 2.2904(6), Pd–P(2) 2.2510(6), Pd–C(20) 2.206(3), Pd–C(21) 2.212(2), Pd–C(22) 2.159(2), C(20)–C(21) 1.402(4),
C(21)–C(22) 1.419(4), P(1)–Pd–Pd(2) 92.11(2), P(2)–Pd–C(22) 97.92(7), C(22)–Pd–C(20) 67.19(10), C(20)–Pd–P(1) 102.67(8); for Pd2: Pd–P(1) 2.232(2), Pd–P(2)
2.286(3), Pd–C(24) 2.087(10), Pd–C(25) 2.299(12), Pd–C(26) 2.552(12), C(24)–C(25) 1.366(17), C(24)–C(26) 1.447(17), C(24)–C(23) 1.365(15), P(1)–Pd–Pd(2) 94.67(9),
P(1)–Pd–C(25) 125.6(3), C(25)–Pd–C(26) 61.1(4), C(26)–Pd–P(2) 76.4(3).
Callyl distance trans to the phosphinite moiety is longer than terminal atoms of the methallyl fragment. The distances and
the Pd–Callyl distance trans to the phosphane moiety, especially angles are similar to those for comparable complexes.[14d] The
for Pd2. The same trend has been found for comparable com- Pd–Callyl distance trans to the phosphorodiamidite fragment is
plexes.[27]
The X-ray structure of the phosphane–phosphorodiamidite
complex Pd13 is depicted in Figure 3.
longer than the Pd–Callyl distance trans to the phosphane moi-
ety, as observed for complexes containing comparable phos-
phane–phosphoramidite ligands.[27] The two P–N bond lengths
are different and in the range found for similar com-
pounds.[14a,14c,14d] The values suggest a partial double-bond
character, as found in related complexes.[14d] The sums of the
bond angles around both nitrogen atoms are close to 360°;
therefore, the coordination is close to planarity, as occurs for
related complexes.[14d,25] The torsion angle of the binaphthyl
group is 59.14°.
It is interesting to note that the longest Pd–Callyl distance in
all the three crystal structures is always in the cis position with
respect to the P-stereogenic phosphane group.
Pd-Catalysed Allylic Substitution
Figure 3. ORTEP representation (thermal ellipsoids drawn at 50 % of probabil-
ity level, H atoms, water molecules and the PF6 anion removed for clarity)
The performance of the ligands 1–14 was tested in Pd-cata-
lysed asymmetric allylic substitution reactions with the model
substrate rac-3-acetoxy-1,3-diphenyl-1-propene (I) and the
cationic palladium complexes Pd1–Pd14 (Scheme 4).
The studied allylic substitutions involved alkylation with the
C-nucleophile derived from dimethyl malonate (DMM) in the
–
of Pd13. Distances [Å] and angles [°]: Pd–P(1) 2.2568(13), Pd–P(2) 2.3192(14),
Pd–C(39) 2.177(5), Pd–C(40) 2.189(6), Pd–C(41) 2.158(6), C(39)–C(40) 1.428(9),
C(40)–C(41) 1.376(8), C(40)–C(42) 1.517(9), P(1)–N(1) 1.683(4), P(1)–N(2)
1.656(5), P(1)–Pd–P(2) 91.60(5), P(2)–Pd–C(39) 104.10(18), C(39)–Pd–C(41)
66.6(2), C(41)–Pd–P(1) 97.63(16), ΣN(1) 346.7, ΣN(2) 357.1.
The complex has a distorted square-planar geometry around presence of N,O-bis(trimethylsilyl)acetamide (BSA) and potas-
the palladium atom, and the coordination positions are occu- sium acetate and amination with benzylamine. The obtained
pied by the two phosphorus atoms of the ligand and the two results are given in Table 1.
Scheme 4. Allylic substitution reactions of I catalysed by Pd1–Pd14 complexes.
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Table 1. Results of asymmetric allylic substitutions of I with Pd1–Pd14.
therefore, (Ra) ligands preferentially produce the (R)-alkylation
product (Table 1, Entries 5, 6, 10 and 11), whereas (Sa) ligands
give the (S)-alkylation product (Table 1, Entries 7–9 and 12–14).
The same fact was observed by van Leeuwen and co-work-
ers[10d] for related phosphane–phosphite ligands with a more
flexible bridge. The only relevant difference between the P-
stereogenic phosphane–phosphite (Table 1, Entries 5–9) and
phosphane–phosphorodiamidite (Table 1, Entries 10–13) com-
plexes is that the complexes bearing the tBu-containing phos-
phanes are more selective than the Me counterparts for the
former (cf. Table 1, Entries 5 vs. 6 and 7 vs. 8), whereas the trend
is the opposite for the latter (cf. Table 1, Entries 10 vs. 11 and
12 vs. 13). The best results were obtained with Pd6, Pd9 and
Pd14 (Table 1, Entries 6, 9 and 14), the latter two of which
contain an achiral phosphane moiety.
Entry[a] Pd complex Alkylation
Conv. [%][b]
Amination
Conv. [%]b
ee [%][c]
ee [%][c]
1
2
3
4
5
6
7
8
Pd1
Pd2
Pd3
Pd4
Pd5
Pd6
Pd7
Pd8
>99
>99
>99
>99
>99
>99
>99
>99
>99
>99
>99
>99
>99
>99
9 (S)
5 (S)
40
20
10
17
<5
<5
<5
<5
<5
31
40
61
70
80
<5
8 (S)
<5
18 (S)
–
–
–
–
–
18 (S)
37 (S)
42 (R)
39 (R)
70 (R)
11 (R)
45 (R)
80 (R)
94 (R)
66 (S)
81 (S)
88 (S)
82 (R)
56 (R)
73 (S)
50 (S)
96 (S)
9
Pd9
10
11
12
13
14
Pd10
Pd11
Pd12
Pd13
Pd14
Palladium complexes Pd1–Pd14 were also tested in the all-
ylic amination of I with excess benzylamine. The systems are
much slower in the allylic amination than in the alkylation, as
reported for related phosphite–phosphoramidite ligands,[29]
and the complexes with phosphane–phosphite ligands are to-
tally inactive (Table 1, Entries 5–9). The other complexes led
to low or moderate conversions at best. The complexes with
phosphane–phosphinite ligands gave very poor enantioselect-
ivities (Table 1, Entries 1–4), whereas those with phosphane–
phosphorodiamidite ligands (Table 1, Entries 10–14) were
slightly better. Complex Pd14, containing an achiral phosphane
moiety, is clearly the best of the series in terms of activity and
enantioselectivity. In this case, (Ra) ligands gave preferentially
the (S) amination product, which is the same sense of induction
as in the alkylation reaction, as the amination product has the
opposite absolute configuration to the alkylation product ow-
ing to a change of priority of the groups in the Cahn–Ingold–
Prelog (CIP) rules.
[a] Conditions for allylic alkylations with DMM: Pd complex (0.01 mmol), I
(1 mmol), dimethyl malonate (3 mmol), BSA (3 mmol) and KOAc (1 mg) in
CH2Cl2 (5 mL) at r.t. for 24 h; for allylic aminations with benzylamine: Pd
complex (0.01 mmol), I (1 mmol) and benzylamine (3 mmol) in CH2Cl2 (5 mL)
at r.t. for 72 h. [b] Conversion percentage expressed as I consumption, deter-
mined by NMR spectroscopy and HPLC. [c] Enantiomeric excesses determined
by HPLC.
All of the complexes were active in the allylic alkylations and
provided complete conversions in 24 h with 1 % of complex. A
wide range of ee values (5–96 %) was obtained, in line with the
results for other C1-symmetric diphosphorus ligands.[10d,27,28]
The complexes with phosphane–phosphinite ligands, contain-
ing only the phosphorus atom as a stereogenic element
(Table 1, Entries 1–4), led to the lowest enantioselectivities, and
Pd4 achieved a moderate value of 45 % ee (Table 1, Entry 4).
The results with the other complexes with two stereogenic ele-
ments (Table 1, Entries 5–14) allow the discussion of the match–
mismatch effects between them. A general trend is that the
enantioselectivities are considerably higher than those for com-
plexes containing phosphane–phosphinite ligands, and this
highlights the efficiency of the 1,1′-binaphthyl unit as a chiral
inductor. Indeed, most of the ligands give very enantioselective
systems that afford similar or better results than those with
To help to rationalise the absolute configurations of the sub-
stitution products of I, complex Pd6′, bearing ligand 6 and the
1,3-diphenylallyl moiety, was prepared and characterised
(Scheme 5).
This complex is one of the intermediates in the substitution
other phosphane–phosphite[10d,28a] or phosphane–phosphor- of I with ligand 6. In solution, it is present as a mixture of two
amidite ligands[27] except Pd7, Pd11 and Pd13 (Table 1, En- diastereomers in a 1:3.5 ratio, whereas this ratio was 1:2.3 for
tries 7, 11 and 13). There is a match–mismatch effect between Pd6. Unfortunately, we were unable to obtain any crystals of
the absolute configurations of the 1,1′-bi-2-naphthyl fragment Pd6′ suitable for X-ray diffraction. From the crystal structure
of the phosphite or phosphorodiamidite moiety and the stereo- data of Pd1, Pd2 and Pd13, it seems that the phosphane (P)
genic phosphorus atom. Clearly, the matched combination cor- part exerts a lower trans influence than the other phosphorus
responds to the (Ra,SP) ligands (cf. Table 1, Entries 5 vs. 7, 6 vs. moiety (P′). In principle, this means that the most electrophilic
8, 10 vs. 12 and 11 vs. 13). The absolute configurations of the carbon atom of the allyl group and the one that will be prefer-
alkylation product are controlled by the absolute configuration entially attacked by the nucleophile will be the one at the cis
of the phosphite or phosphorodiamidite part of the ligand; position relative to the phosphane part. We assumed that the
Scheme 5. Preparation of complex Pd6′.
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Scheme 6. Allylic alkylation of II and III catalysed by Pd complexes.
same trends would apply to the 1,3-diphenylallyl complexes the absolute configuration of the 1,1′-binaphthyl-based phos-
and performed PM3-level calculations of the energies of the phite or phosphorodiamidite part of the ligand that dictates
diastereomers of Pd6′, Pd8′, Pd9′ and Pd14′ (see Supporting the absolute configuration of the alkylation product, but the
Information). The absolute configuration of the substitution phosphane part also has some influence on the level of enan-
product resulting from the attack of the nucleophile at the tioselection.
allylic carbon atom cis to the phosphane moiety in the most
stable isomer is coherent with the absolute configuration of the
major enantiomer obtained experimentally.
Given the results presented here and the high modularity of
the ligands, we are currently preparing new ligands of the same
type and using them and the reported ones in new catalytic
We also studied the alkylations of cyclohexen-3-yl acetate (II) reactions. The results of these studies will be reported in due
and cinnamyl acetate (III) with DMM (Scheme 6).
course.
The more enantioselective catalysts Pd6 and Pd14 were cho-
sen to study their potential in the alkylation of substrate II. As
very low conversions and enantioselectivities were found within
24 h of reaction time, no more catalytic runs with this substrate
were carried out. Finally, some of the complexes were tested in
the alkylation of III. The complexes led to full conversions at 1 h
reaction times, but, as expected,[12b] the achiral linear alkylation
product (l) was favoured over the branched isomer (b). The full
results can be found in Table S2 of the Supporting Information.
Experimental Section
General Data: All compounds were prepared under a purified
nitrogen atmosphere by standard Schlenk and vacuum-line tech-
niques. The solvents were obtained from a solvent-purification sys-
tem or purified by standard procedures[30] and kept under nitrogen.
1H, 13C{1H}, 31P{1H} and HSQC 1H–13C NMR spectra were recorded
with 300 and 400 MHz spectrometers with CDCl3 as the solvent. The
protons of the BH3 moieties of the phosphane–boranes appeared
in the aliphatic region of the spectra as very broad bands and have
not been assigned. For the Pd complexes, ma and mi refer to the
major and minor diastereomers of the complexes, respectively. The
IR spectra were recorded with samples in KBr, and the main absorp-
tion bands are expressed in cm–1. High-resolution mass spectrome-
try analyses were performed with electrospray ionisation. The opti-
cal rotations were measured at room temperature with a sodium
lamp at the sodium D-line wavelength (589.592 nm). In all cases,
the solvent was CH2Cl2, and the concentration was 1 g/100 mL.
The allylic substitution reactions of I were analysed with an HPLC
instrument equipped with a multidiode array detector and fitted
with an OD-H chiral column. The eluent was a 95:5 n-hexane/iPrOH
mixture. The allylic alkylations of II and III were analysed by GC
with a chromatograph equipped with a capillary column with He as
the carrier gas and a flame-ionisation detector (FID). Phosphinite–
borane B [prepared from 1,[19] which was prepared from (1R,2S)-
(–)-ephedrine],[20] phosphane–borane C·BH3,[20] the chlorodiaza-
phosphosphepine derived from N,N′-dimethyl-1,1′-binaphthyl-2,2′-
diamine,[14] Pd dimers D[31] and D′[32] and substrates I[33] and III[34]
were prepared by literature procedures, whereas other reagents
were used as received from commercial suppliers. CCDC 1461787
(for Pd1), 1461788 (for Pd2) and 1461789 (for Pd3) contain the sup-
plementary crystallographic data for this paper. These data can be
obtained free of charge from The Cambridge Crystallographic Data
Centre.
Conclusions
The preparation of 14 new, chiral phosphane–phosphinite,
phosphane–phosphite and phosphane–phosphorodiamidite li-
gands has been reported. Most of them bear a stereogenic
phosphorus atom and have been conveniently prepared by a
condensation reaction between a phosphinophenol and a
chlorophosphorus precursor. Many of the ligands include phos-
phite and phosphorodiamidite parts with a chiral 1,1′-bi-
naphthyl moiety. The ligands have been designed to have one
or two stereogenic elements to increase their modularity and
to study the influence of the different combinations on the ca-
talysis.
The cationic Pd complexes of the ligands with η3-methallyl
coligands have been prepared and characterised in solution by
NMR spectroscopy and also by X-ray crystallography for Pd1,
Pd2 and Pd13. They are good catalytic precursors for allylic
substitutions (alkylation with DMM and amination with benzyl-
amine) with substrates I, II and III. In the alkylation of I, all of
the complexes gave full conversion to the alkylation product
after 24 h, and very high enantioselectivities (up to 95 % ee)
were obtained with Pd6 and Pd14. The stereochemical course
of the reaction is coherent with the nucleophilic attack at the
allylic carbon atom in cis position relative to the phosphane.
(S)-(tert-Butyl)(2-hydroxyphenyl)phenylphosphane–Borane (C′·
BH3): Phosphinite–borane B (528 mg, 2.1 mmol) was dissolved in
Some match–mismatch effects have been identified, and it is diethyl ether (30 mL), and the mixture was cooled to –30 °C. A 1.6
M
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4
solution of tBuLi (3.1 mL, 5.0 mmol) was added by syringe, and the ppm. 31P{1H} NMR (162 MHz): δ = +145.9 (d, JP, P = 1.1 Hz), +2.0 (d,
mixture was stirred for 1 h and left to warm to room temperature. 4JP, P = 1.1 Hz) ppm.
Water (20 mL) was added carefully, the biphasic mixture was ex-
Compound 3: The procedure was analogous to that used to obtain
tracted with diethyl ether (3 × 10 mL), and the combined organic
1. From hydroxyphosphane C (130 mg, 0.60 mmol) and chlorodi-
phases were washed with water (20 mL). The final organic phase
phenylphosphane (0.11 mL, 0.6 mmol), the title product was ob-
was dried with anhydrous sodium sulfate and filtered, and the sol-
tained as a white, pasty solid, yield 201 mg (84 %). 1H NMR
vent was removed under vacuum to furnish the title product as an
(400 MHz): δ = 7.80–7.73 (m, 2 H), 7.72–7.68 (m, 1 H), 7.61–7.48 (m,
oil, yield 553 mg (97 %). 1H NMR (400 MHz): δ = 8.06 (s, br, 1 H),
4 H), 7.45–7.17 (m, 9 H), 7.15–7.10 (m, 1 H), 7.01 (tm, J = 7.6 Hz, 1
7.79–7.74 (m, 2 H), 7.51–7.37 (m, 4 H), 7.24–7.19 (m, 1 H), 6.98 (ddd,
2
H), 6.92 (t, br, J = 7.2 Hz, 1 H), 1.52 (d, JH,P = 4.4 Hz, 3 H) ppm.
3
J = 8.4, 5.2, 1.2 Hz, 1 H), 6.88 (tm, J = 6.8 Hz, 1 H), 1.38 (d, JH,P
=
31P{1H} NMR (162 MHz): δ = +108.2 (d, 4JP, P = 2.1 Hz), –38.2 (s) ppm.
14.8 Hz, 9 H) ppm. 13C{1H} NMR (101 MHz): δ = 161.8–109.9 (C, CH,
2
Ar), 32.2 (d, 1JC,P = 32.7 Hz, C), 26.7 (d, JC,P = 3.0 Hz, 3 × CH3) ppm.
Compound 4: The procedure was the same as that used to obtain
3. From hydroxyphosphane C′ (242 mg, 0.94 mmol), the title prod-
uct was obtained as a white, pasty solid, yield 396 mg (95 %). 1H
NMR (400 MHz): δ = 7.64–7.57 (m, 3 H), 7.37–7.33 (m, 6 H), 7.30–
7.20 (m, 8 H), 7.11 (m, 1 H), 7.04 (td, J = 7.6, 1.2 Hz, 1 H), 1.24 (d,
3JH,P = 12.4 Hz, 9 H) ppm. 31P{1H} NMR (162 MHz): δ = +108.6 (d,
31P{1H} NMR (162 MHz): δ = +26.6 (d, br, 1JB,P = 71.0 Hz) ppm. HRMS:
calcd. for C16H21BOP [M – H]+ 271.1417; found 271.1406. [α]D
=
+140.8 (CH2Cl2, c = 1). HPLC analysis with a chiral column indicated
that the compound was essentially enantiopure (see HPLC trace in
the Supporting Information).
4JP, P = 3.6 Hz), +0.8 (d, JP, P = 3.4 Hz) ppm.
4
(S)-(2-Hydroxyphenyl)methylphenylphosphane (C): Phosphane–
borane C·BH3 (310 mg, 1.2 mmol) was dissolved in dichloro-
methane, and the solution was cooled to 0 °C. HBF4·Et2O (0.87 mL,
6.3 mmol) was added rapidly by syringe, the mixture was vigorously
stirred for 1 h and deoxygenated thoroughly, and a saturated aque-
ous NaHCO3 solution (10 mL) was added carefully. The organic layer
was transferred to another flask, washed with thoroughly with de-
oxygenated water, dried with anhydrous sodium sulfate, filtered and
brought to dryness under vacuum. The title product was obtained
as an air-sensitive colourless oil, yield 200 mg (73 %). The characteri-
sation data of this compound agreed with the data reported previ-
ously.[10f,35]
Compound 5: Hydroxyphosphane C (179 mg, 0.83 mmol) was dis-
solved in toluene (20 mL), and triethylamine (0.2 mL, 1.5 mmol)
was added rapidly by syringe. To this mixture, a solution of the
chlorodioxaphosphepine derived from (R)-(+)-1,1′-bi(2-naphthol)[37]
(291 mg, 0.83 mmol) in toluene (10 mL) was added dropwise over
15 min, and the suspension was stirred for 1 h. The ammonium
salts were removed by filtration, and the filtrate was brought to
dryness to afford the title product as a white solid, yield 343 mg
4
(78 %). 31P{1H} NMR (162 MHz): δ = +143.37 (d, JP, P = 20.1 Hz),
4
–36.50 (d, JP, P = 20.2 Hz) ppm.
Compound 6: The procedure was the same as that used to obtain
5. From hydroxyphosphane C′ (245 mg, 0.95 mmol), the title prod-
uct was obtained as a white solid, yield 409 mg (75 %). 1H NMR
(400 MHz): δ = 7.31–7.09 (m, 10 H), 7.04 (dd, J = 8.0, 4.0 Hz, 1 H),
6.86–6.78 (m, 5 H), 6.74–6.68 (m, 2 H), 6.64–6.55 (m, 3 H), 0.88 (d,
3JH,P = 12.4 Hz, 9 H) ppm. 31P{1H} NMR (162 MHz): δ = +144.31 (d,
(S)-(tert-Butyl)(2-hydroxyphenyl)phenylphosphane (C′): The pro-
cedure was the same as that used to obtain C. From phosphane–
borane C′·BH3 (1000 mg, 3.7 mmol) and HBF4·Et2O (2.3 mL,
16.7 mmol), the title product was obtained as a colourless oil, yield
860 mg (90 %). The characterisation data of this compound agreed
with the values reported previously.[36] 1H NMR (400 MHz): δ = 7.74–
7.70 (m, 2 H), 7.67–7.64 (m, 1 H), 7.30–7.28 (m, 2 H), 7.25–7.23 (m,
4
4JP, P = 41.5 Hz), +1.30 (d, JP, P = 41.3 Hz) ppm.
3
3 H), 6.96–6.92 (m, 1 H), 1.28 (d, JH,P = 13.6 Hz, 9 H) ppm. 13C{1H}
Compound 7: The procedure was the same as that used to obtain
5 but with the chlorodioxaphosphepine derived from (S)-(–)-1,1′-
bi(2-naphthol). From hydroxyphosphane C (378 mg, 1.75 mmol), the
title product was obtained as a white solid, yield 770 mg (83 %). 1H
NMR (400 MHz): δ = 7.99 (d, J = 8.8 Hz, 1 H), 7.93 (t, J = 8.4 Hz, 1
H), 7.91 (t, J = 8.8 Hz, 1 H), 7.55 (d, J = 8.8 Hz, 1 H), 7.52 (d, J =
8.8 Hz, 1 H), 7.47–7.41 (m, 4 H), 7.38 (d, J = 6.8 Hz, 2 H), 7.31–7.25
(m, 6 H), 7.22–7.08 (m, 4 H), 1.57 (d, 2JH,P = 4.0 Hz, 3 H) ppm. 31P{1H}
1
NMR (101 MHz): δ = 161.0–115.3 (C, CH, Ar), 31.4 (d, JC,P = 7.8 Hz,
2
C), 28.5 (d, JC,P = 13.8 Hz, CH3) ppm. 31P{1H} NMR (162 MHz): δ =
–19.0 (s) ppm.
Compound 1: Hydroxyphosphane C (345 mg, 1.5 mmol) was dis-
solved in toluene (20 mL), and triethylamine (0.3 mL, 2.2 mmol) was
added rapidly by syringe. To this mixture, a solution of chlorodiiso-
propylphosphane (0.24 mL, 1.5 mmol) in toluene (15 mL) was
added dropwise over 15 min, and the suspension was stirred for
1 h. The ammonium salts were removed by filtration, and the filtrate
was brought to dryness to afford the title product as a pasty, white
4
4
NMR (162 MHz): δ = +143.45 (d, JP, P = 16.7 Hz), –37.38 (d, JP, P
=
16.7 Hz) ppm.
Compound 8: The procedure was the same as that used to obtain
7. From hydroxyphosphane C′ (379 mg, 1.47 mmol), the title prod-
uct was obtained as a white solid, yield 660 mg (78 %). 1H NMR
(400 MHz, C6D6): δ = 8.00 (d, J = 8.8 Hz, 1 H), 7.83 (t, J = 8.8 Hz, 2
H), 7.81–7.63 (m, 3 H), 7.66 (t, J = 8.8 Hz, 2 H), 7.53 (d, J = 8.8 Hz, 1
1
solid, yield 445 mg (90 %). H NMR (400 MHz): δ = 7.43–7.35 (m, 3
H), 7.30–7.27 (m, 3 H), 7.26–7.23 (m, 1 H), 7.10 (ddd, J = 7.6, 4.4,
1.6 Hz, 1 H), 6.95 (tm, J = 7.6 Hz, 1 H), 1.90 (m, 1 H), 1.68 (m, 1 H),
3
3
3
1.54 (d, JH,P = 4.4 Hz, 3 H), 1.17 (dd, JH,P, JH,H = 10.8, 6.8 Hz, 3 H),
3
3
3
3
H), 7.39 (dd, J = 8.4, 4.4 Hz, 1 H), 7.34–7.29 (m, 2 H), 7.27–7.18 (m,
1.07 (dd, JH,P, JH,H = 16.0, 7.6 Hz, 3 H), 0.94 (dd, JH,P, JH,H = 16.0,
3
7.2 Hz, 3 H), 0.82 (dd, JH,P,
3JH,H = 11.2, 6.8 Hz, 3 H) ppm. 31P{1H}
3
5 H), 7.15–7.02 (m, 3 H), 7.02 (t, J = 6.8 Hz, 1 H), 1.42 (d, JH,P
=
=
4
12.4 Hz, 9 H) ppm. 31P{1H} NMR (162 MHz): δ = +142.33 (d, JP, P
NMR (162 MHz): δ = +145.1 (s), –37.5 (s) ppm.
4
28.8 Hz), +0.80 (d, JP, P = 29.0 Hz) ppm.
Compound 2: The procedure was the same as that used to obtain
1. From hydroxyphosphane C′ (284 mg, 1.1 mmol), the title product
Compound 9: The procedure was the same as that used to obtain
7. From hydroxyphosphane C′′ (242 mg, 0.87 mmol), the title prod-
uct was obtained as a white solid, yield 480 mg (93 %). The charac-
terisation data of this compound agreed with the values reported
1
was obtained as a white, pasty solid, yield 387 mg (94 %). H NMR
(400 MHz): δ = 7.52 (dt, J = 7.6, 2.0 Hz, 1 H), 7.41–7.35 (m, 3 H),
7.27–7.22 (m, 4 H), 6.94 (td, J = 7.6, 1.2 Hz, 1 H), 2.01 (m, 1 H), 1.88
3
3
(m, 1 H), 1.23 (d, JH,P = 12.4 Hz, 9 H), 1.18 (dd, JH,P
,
3JH,H = 11.2, previously.[16] 1H NMR (400 MHz): δ = 7.87 (d, J = 8.8 Hz, 1 H), 7.84
3
3
3
7.2 Hz, 3 H), 1.05 (dd, JH,P, JH,H = 15.6, 7.2 Hz, 3 H), 0.86 (dd, JH,P
,
(d, J = 8.4 Hz, 1 H), 7.79 (d, J = 8.0 Hz, 1 H), 7.68 (d, J = 8.8 Hz, 1
H), 7.38–7.23 (m, 16 H), 7.21–7.12 (m, 4 H), 6.99 (t, J = 7.2 Hz, 1 H),
3JH,H = 15.6, 7.2 Hz, 3 H), 0.75 (dd, JH,P 3JH,H = 11.6, 7.2 Hz, 3 H)
,
3
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6.70 (ddd, J = 7.6, 4.0 Hz, 1.6 1 H) ppm. 31P{1H} NMR (162 MHz): δ = The crude product was recrystallised in dichloromethane/hexane
4
4
+143.21 (d, JP, P = 14.7 Hz), –16.00 (d, JP, P = 14.7 Hz) ppm.
to yield the title product as a white solid, yield 210 mg (71 %).
Diastereomeric ratio: 1:1.8. IR: ν = 2970, 2929, 1591, 1468, 1436,
˜
Compound 10: Hydroxyphosphane C (134 mg, 0.62 mmol) was dis-
solved in toluene (20 mL), and triethylamine (0.2 mL, 1.5 mmol) and
1267, 1207, 1028, 899, 891, 839 [ν(PF6–)], 774, 736, 558 cm–1
.
1H
NMR (400 MHz): δ = 7.61 (t, J = 7.6 Hz, 2 H), 7.51–7.30 (m, 11 H,
Ar), 7.23–7.18 (m, 5 H, Ar), 4.50 (t, J = 4.0 Hz, 1 H, ma), 4.47 (t, J =
3.6 Hz, 1 H, mi), 4.35 (t, J = 4.4 Hz, 1 H, ma), 4.31 (t, J = 4.4 Hz, 1 H,
mi), 3.39 (d, J = 10.4 Hz, 1 H, ma), 3.34 (d, J = 10.0 Hz, 1 H, mi), 2.99
(d, J = 10.0 Hz, 1 H, mi), 2.88 (d, J = 10.0 Hz, 1 H, ma), 2.46–2.23 (m,
4-dimethylaminopyridine (DMAP,
2 mg, 0.016 mmol) were
added rapidly. To this mixture, a solution of the chlorodiazaphos-
phepine derived from (R)-N,N′-dimethyl-1,1′-binaphthyldiamine[14d]
(0.62 mmol) in toluene (10 mL) was added dropwise over 15 min,
and the suspension was stirred for 1 h. The ammonium salts were
removed by filtration, and the filtrate was brought to dryness to
afford the title product as a white solid, yield 311 mg (90 %). 1H
NMR (400 MHz): δ = 7.93–7.84 (m, 4 H), 7.60 (d, J = 8.8 Hz, 1 H),
7.49 (d, J = 8.8 Hz, 1 H), 7.41–7.30 (m, 2 H), 7.27–7.10 (m, 11 H),
4 H, ma + mi), 2.29 (d, 2JH,P = 9.6 Hz, 3 H, ma), 2.24 (d, 2JH,P = 9.2 Hz,
3
3 H, mi), 1.89 (s, 3 H, ma), 1.84 (s, 3 H, mi), 1.22 (dd, JH,P
,
3JH,H
=
3
3
16.4, 7.2 Hz, 3 H, ma), 1.15 (dd, JH,P, JH,H = 18.4, 11.2 Hz, 3 H, ma),
1.08 (dd, 3JH,P, 2JH,H = 7.2, 1.6 Hz, 3 H, mi), 1.03 (dd, JH,P, 2JH,H = 7.6,
3
3
3.2 Hz, 3 H, mi), 0.98 (dd, JH,P
,
3JH,H = 19.6, 7.2 Hz, 3 H, ma), 0.91
3
3
6.98–6.95 (m, 2 H), 3.06 (d, JH,P = 13.6 Hz, 3 H), 2.89 (d, JH,P
=
3
3
(dd, JH,P
,
3JH,H = 16.8, 7.2 Hz, 3 H, mi), 0.85 (dd, JH,P
,
2JH,H = 16.0,
9.6 Hz, 3 H), 1.35 (d, 2JH,P = 4.4 Hz, 3 H) ppm. 31P{1H} NMR (162 MHz):
δ = +170.59 (d, JP, P = 7.0 Hz), –37.86 (d, JP, P = 6.8 Hz) ppm.
6.8 Hz, 3 H, ma) ppm. 13C{1H} NMR (101 MHz): δ = 158.3–123.0 (C,
4
4
CH, Ar), 73.7 (dd, 2JC,P = 30.5, 3.1 Hz, CH2, ma), 73.3 (dd, 2JC,P = 31.4,
2
Compound 11: The procedure was the same as that used to obtain
10. From hydroxyphosphane C′ (206 mg, 0.80 mmol), the title prod-
uct was obtained as a white solid, yield 450 mg (94 %). 1H NMR
(400 MHz): δ = 8.07–7.82 (m, 5 H), 7.71–7.58 (m, 3 H), 7.49–7.32 (m,
2.2 Hz, CH2, mi), 64.6 (dd, JC,P = 30.2, 2.1 Hz, CH2, mi), 64.2 (d,
2JC,P = 30.2 Hz, CH2, ma), 32.5 (d, JC,P = 11.3 Hz, CH, mi), 32.3 (d,
1
1JC,P = 10.3 Hz, CH, ma), 30.5 (d, JC,P = 24.1 Hz, CH, mi), 30.2 (d,
1
1JC,P = 25.3 Hz, CH, mi), 24.2 (s, CH3, mi), 24.1 (s, CH3, Ma), 17.8–16.5
5 H), 7.29–6.98 (m, 8 H), 3.09 (d, 3JH,P = 12.0 Hz, 3 H), 3.03 (d, 3JH,P
=
1
(m, 8 × CH3, ma + mi), 16.1 (d, JC,P = 28.3 Hz, CH3, mi), 15.0 (d,
3
14.0 Hz, 3 H), 1.03 (d, JH,P = 12.4 Hz, 9 H) ppm. 31P{1H} NMR
1JC,P = 29.1 Hz, CH3, ma) ppm. 31P{1H} NMR (162 MHz): δ = +190.81
4
(162 MHz): δ = +172.16 (d, 4JP, P = 16.0 Hz), +0.23 (d, JP, P = 15.9 Hz)
2
2
(d, JP, P = 63.7 Hz, ma), +190.41 (d, JP, P = 63.8 Hz, mi), –6.49 (d,
2
2JP, P
= 63.7 Hz, ma), –7.49 (d, JP, P = 63.7 Hz, mi) ppm.
ppm.
C
5.69.
23H33F6OP3Pd (638.82): calcd. C 43.24, H 5.21; found C 42.81, H
Compound 12: The procedure was the same as that used to obtain
10 but with the chlorodiazaphosphepine derived from (S)-N,N′-di-
methyl-1,1′-binaphthyldiamine. From
hydroxyphosphane
C
Complex Pd2: The procedure was the same as that used to prepare
Pd1. From ligand 2 (180 mg, 0.48 mmol) and Pd dimer D (76 mg,
0.19 mmol), the product was obtained as a white solid, yield 230 mg
(162 mg, 0.75 mmol), the title product was obtained as a white
solid, yield 371 mg (89 %). 1H NMR (400 MHz): δ = 8.00 (dd, J = 8.8,
2.4 Hz, 1 H), 7.96–7.92 (m, 2 H), 7.88 (d, J = 3.2 Hz, 1 H), 7.86 (d, J = (89 %). Diastereomeric ratio: 1:1. IR: ν = 2966, 2873, 1591, 1466,
˜
2.8 Hz, 1 H), 7.81 (d, J = 8.8 Hz, 1 H), 7.67 (d, J = 8.8 Hz, 1 H), 7.62
(d, J = 9.2 Hz, 1 H), 7.46–7.32 (m, 4 H), 7.28–7.10 (m, 6 H), 7.07–6.95
1434, 1265, 1201, 1097, 1074, 1028, 899, 878, 839 [ν(PF6–)], 773, 747,
699, 558, 518 cm–1. H NMR (400 MHz): δ = 7.76–7.42 (m, 2 H, Ar),
1
(m, 3 H), 3.09 (d, 3JH,P = 9.6 Hz, 3 H), 3.05 (d, 3JH,P = 14.0 Hz, 3 H), 1.47
7.59–7.42 (m, 10 H, Ar), 7.22–6.99 (m, 6 H, Ar), 4.36 (d, J = 3.6 Hz, 2
(d, JH,P = 4.0 Hz, 3 H) ppm. 31P{1H} NMR (162 MHz): δ = +172.71 H), 4.34 (m, 1 H), 3.64 (t, J = 4.4 Hz, 1 H), 3.42 (d, J = 10.0 Hz, 1 H),
2
4
4
(d, JP, P = 11.0 Hz), –37.38 (d, JP, P = 11.0 Hz) ppm.
2.90 (d, J = 10.0 Hz, 1 H), 2.87 (d, J = 10.0 Hz, 1 H), 2.61 (m, 1 H),
2.48 (m, 2 H), 2.38 (d, J = 11.6 Hz, 1 H), 2.36 (m, 2 H), 1.86 (s, 3 H),
Compound 13: The procedure was the same as that used to obtain
12. From hydroxyphosphane C′ (206 mg, 0.80 mmol), the title prod-
uct was obtained as a white solid, yield 380 mg (79 %). 1H NMR
(400 MHz): δ = 7.57 (dd, J = 8.8, 0.8 Hz, 1 H), 7.45–7.39 (m, 4 H),
7.26–7.21 (m, 4 H), 7.12 (dd, J = 8.4, 1.2 Hz, 1 H), 7.08 (dd, J = 8.4,
1.2 Hz, 1 H), 6.93 (ddt, J = 8.0, 4.4, 0.8 Hz, 1 H), 6.90–6.61 (m, 8 H),
3
1.54 (s, 3 H), 1.48–1.26 (m, 12 H), 1.42 (d, JH,P = 16.8 Hz, 9 H), 1.35
(d, JH,P = 16.4 Hz, 9 H), 1.19–1.07 (m, 12 H) ppm. 13C{1H} NMR
3
(101 MHz): δ = 159.2–115.0 (C, CH, Ar), 77.8 (dd, 2JC,P = 31.8, 3.1 Hz,
CH2), 76.1 (dd, 2JC,P = 31.1, 2.9 Hz, CH2), 64.2 (dd, 2JC,P = 28.3, 1.7 Hz,
2
1
CH2), 62.9 (dd, JC,P = 28.5, 1.6 Hz, CH2), 35.6 (d, JC,P = 22.0 Hz, C),
1
1
34.8 (d, JC,P = 22.6 Hz, C), 32.5 (d, JC,P = 12.6 Hz, 2CH), 31.2 (d,
3
6.58 (td, J = 7.2, 1.2 Hz, 1 H), 2.73 (d, JH,P = 9.2 Hz, 3 H), 2.62 (d,
1JC,P = 27.3 Hz, CH), 30.8 (d, JC,P = 27.1 Hz, CH), 28.4 (d, JC,P
=
1
2
3JH,P = 14.0 Hz, 3 H), 0.91 (d, 3JH,P = 12.0 Hz, 3 H) ppm. 31P{1H} NMR
2.3 Hz, 3 × CH3), 28.3 (d, 2JC,P = 2.5 Hz, 3 × CH3), 23.72 (s, CH3), 23.69
4
4
(162 MHz): δ = +171.34 (d, JP, P = 8.9 Hz), –0.67 (d, JP, P = 8.9 Hz)
2
2
(s, CH3), 18.2 (d, JC,P = 5.6 Hz, CH3), 18.0 (d, JC,P = 4.9 Hz, CH3),
17.8 (s, CH3), 17.5 (d, JC,P = 5.5 Hz, CH3), 17.4 (d, JC,P = 6.6 Hz,
ppm.
2
2
2
Compound 14: The procedure was the same as that used to obtain
12. From hydroxyphosphane C′′ (223 mg, 0.80 mmol), the title prod-
uct was obtained as a white solid, yield 408 mg (82 %). 1H NMR
(400 MHz): δ = 7.92 (d, J = 8.8 Hz, 1 H), 7.88 (d, J = 8.0 Hz, 1 H),
7.86 (d, J = 8.0 Hz, 1 H), 7.81 (d, J = 8.4 Hz, 1 H), 7.61 (d, J = 8.8 Hz,
1 H), 7.41–7.10 (m, 19 H), 6.97 (t, J = 6.8 Hz, 1 H), 6.75 (dd, J = 6.8,
CH3), 17.1 (s, CH3), 16.7 (d, JC,P = 2.7 Hz, CH3), 16.2 (s, CH3) ppm.
31P{1H} NMR (162 MHz): δ = +186.54 (d, JP, P = 59.6 Hz), +185.67 (d,
2
2JP, P = 59.8 Hz), +25.06 (d, 2JP, P = 59.6 Hz), +23.72 (d, 2JP, P = 59.6 Hz)
ppm. C26H39F6OP3Pd (680.90): calcd. C 45.86, H 5.77; found C 47.13,
H 6.61.
Pd3: The procedure was the same as that used to prepare Pd1.
From ligand 3 (200 mg, 0.50 mmol) and Pd dimer D (78 mg,
0.20 mmol), the product was obtained as a white solid, yield 215 mg
3
3
4.8 Hz, 1 H), 2.92 (d, JH,P = 13.2 Hz, 3 H), 2.89 (d, JH,P = 8.8 Hz, 3
H) ppm. 31P{1H} NMR (162 MHz): δ = +170.48 (d, JP, P = 10.2 Hz),
–17.51 (d, JP, P = 10.5 Hz) ppm.
4
4
(76 %). Diastereomeric ratio: 1:1.3. IR: ν = 3064, 3009, 2916, 1590,
˜
Complex Pd1: Phosphane–phosphinite 1 (195 mg, 0.59 mmol), Pd
1466, 1437, 1386, 1265, 1199, 1128, 1103, 1079, 1027, 999, 894, 839
dimer D (92 mg, 0.23 mmol) and NH4PF6 (191 mg, 1.17 mmol) were [ν(PF6–)], 777, 741, 693, 587, 558, 518, 475 cm–1. 1H NMR (400 MHz):
suspended in dichloromethane (20 mL), and the suspension was
δ = 7.62–7.23 (m, Ar), 6.74 (m, Ar), 4.58 (t, J = 3.6 Hz, 1 H, mi), 4.55
stirred vigorously for 2 h. Water (20 mL) was added, and the mixture (t, J = 4.0 Hz, 1 H, ma), 4.37 (t, J = 4.0 Hz, 1 H, mi), 4.30 (t, J = 4.0 Hz,
was extracted with dichloromethane (3 × 10 mL). The combined
organic phase was washed with water, dried with anhydrous
Na2SO4 and filtered, and the solvent was removed under vacuum.
1 H, ma), 3.48 (d, J = 10.0 Hz, 1 H, ma), 3.41 (d, J = 10.8 Hz, 1 H,
mi), 3.21 (d, J = 10.0 Hz, 1 H, ma), 2.97 (d, J = 10.0 Hz, 1 H, mi), 2.35
(d, JH,P = 9.6 Hz, 3 H, ma), 2.34 (d, JH,P = 9.6 Hz, 3 H, mi), 1.96 (s,
2
2
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2
3 H, mi), 1.79 (s, 3 H, ma) ppm. 13C{1H} NMR (101 MHz): δ = 155.7– 2JC,P = 46.4, 2.3 Hz, CH2, ma), 75.9 (d, JC,P = 48.5 Hz, CH2, mi), 70.1
2
2
2
2
119.1 (C, CH, Ar), 72.4 (d, JC,P = 34.0 Hz, CH2, ma), 72.0 (d, JC,P
=
=
=
(dd, JC,P = 27.4, 7.5 Hz, CH2, mi), 69.5 (dd, JC,P = 25.9, 7.1 Hz, CH2,
23.8 Hz, CH2, mi), 69.45 (d, 2JC,P = 26.3 Hz, CH2, mi), 69.37 (d, 2JC,P
ma), 36.0 (d, JC,P = 21.3 Hz, C, ma), 35.4 (d, JC,P = 22.9 Hz, C, mi),
1
1
28.3 Hz, CH2, ma), 24.2 (s, CH3, mi), 24.1 (s, CH3, ma), 15.2 (d, 1JC,P
28.3 (d, JC,P = 6.5 Hz, 3 × CH3, mi), 28.2 (d, JC,P = 6.6 Hz, 3 × CH3,
2
2
27.1 Hz, CH3, mi), 14.3 (d, JC,P = 28.4 Hz, CH3, ma) ppm. 31P{1H}
ma), 23.7 (s, CH3, ma), 23.6 (s, CH3, mi) ppm. 31P{1H} NMR (162 MHz):
1
2
2
2
NMR (162 MHz): δ = +151.53 (d, JP, P = 68.5 Hz, mi), +150.56 (d, δ = +144.42 (d, JP, P = 97.8 Hz, ma), +143.67 (d, JP, P = 98.7 Hz, mi),
2JP, P = 68.2 Hz, ma), –5.06 (d, JP, P = 68.0 Hz, ma), –5.87 (d, JP, P
=
+29.52 (d, JP, P = 98.8 Hz, mi), +28.76 (d, JP, P = 97.2 Hz, ma) ppm.
C40H37F6O3P3Pd (879.04): calcd. C 54.65, H 4.24; found C 54.23, H
5.06.
2
2
2
2
68.8 Hz, mi) ppm. C29H29F6OP3Pd (706.86): calcd. C 49.28, H 4.14;
found C 49.64, H 4.58.
Complex Pd4: The procedure was the same as that used to prepare
Complex Pd7: The procedure was the same as that used to prepare
Pd1. From ligand 4 (150 mg, 0.34 mmol) and Pd dimer D (53 mg, Pd1. From ligand 7 (400 mg, 0.75 mmol) and Pd dimer D (123 mg,
0.13 mmol), the product was obtained as a white solid, yield 157 mg
0.31 mmol), the product was obtained as a white solid, yield 398 mg
(81 %). Diastereomeric ratio: 1:1. IR: ν = 3061, 2960, 2865, 1590,
(77 %). Diastereomeric ratio: 1:1. IR: ν = 3066, 2957, 2924, 1619,
˜
˜
1567, 1466, 1436, 1398, 1369, 1310, 1264, 1197, 1104, 1073, 1026,
1591, 1509, 1464, 1437, 1322, 1264, 1224, 1185, 1128, 1068, 958,
1
999, 831 [ν(PF6–)], 773, 746, 694, 588, 558, 519, 481 cm–1. H NMR
919, 832 [ν(PF6–)], 774, 741, 695, 608, 558, 500 cm–1 1H NMR
.
(400 MHz): δ = 7.78–7.32 (m, 31 H, Ar), 7.17–7.07 (m, 4 H, Ar), 6.91–
6.84 (m, 3 H, Ar), 4.44–4.40 (m, 2 H), 4.14 (t, J = 4.0 Hz, 1 H), 3.91
(dd, J = 5.6, 4.0 Hz, 1 H), 3.48 (d, J = 12.4 Hz, 1 H), 3.45 (d, J =
10.4 Hz, 1 H), 2.95 (d, J = 10.8 Hz, 1 H), 2.81 (d, J = 9.6 Hz, 1 H), 1.81
(400 MHz): δ = 8.24–8.02 (m, 4 H, Ar), 7.73–7.18 (m, 17 H, Ar), 4.79
(d, J = 7.6 Hz, 1 H), 4.53 (d, J = 8.0 Hz, 1 H), 3.79–3.64 (m, 3 H), 3.32
(d, J = 15.6 Hz, 1 H), 3.07 (d, J = 9.6 Hz, 1 H), 2.69 (d, J = 7.2 Hz, 1
2
2
H), 2.43 (d, JH,P = 9.6 Hz, 3 H), 2.35 (d, JH,P = 9.6 Hz, 3 H), 1.97 (s,
3
3
(s, 3 H), 1.75 (s, 3 H), 1.49 (d, JH,P = 16.8 Hz, 9 H), 1.43 (d, JH,P
=
3 H), 1.68 (s, 3 H) ppm. 31P{1H} NMR (162 MHz): δ = +146.20 (d,
16.8 Hz, 9 H) ppm. 13C{1H} NMR (101 MHz): δ = 156.6–116.9 (C, CH,
2JP, P = 103.2 Hz), +145.87 (d, JP, P = 102.7 Hz), –3.99 (d, JP, P
=
2
2
2
2
2
Ar), 74.6 (dd, JC,P = 33.5, 3.0 Hz, CH2), 70.8 (dd, JC,P = 28.0, 2.9 Hz,
103.2 Hz), –5.42 (d, JP, P = 102.9 Hz) ppm. HRMS: calcd. for
2
1
CH2), 68.4 (dd, JC,P = 28.0, 2.5 Hz, CH2), 35.0 (d, JC,P = 21.7 Hz, C),
C
37H31O3P2Pd [M – PF6]+ 691.0777; found 691.0793.
1
2
34.2 (d, JC,P = 22.0 Hz, C), 28.17 (d, JC,P = 6.9 Hz, 3 × CH3), 28.11
Complex Pd8: The procedure was the same as that used to prepare
Pd1. From ligand 8 (285 mg, 0.50 mmol) and Pd dimer D (72 mg,
0.18 mmol), the product was obtained as a white solid, yield 207 mg
(d, 2JC,P = 6.9 Hz, 3 × CH3), 23.96 (s, CH3), 23.86 (s, CH3) ppm. 31P{1H}
2
2
NMR (162 MHz): δ = +148.71 (d, JP. P = 65.8 Hz), +148.45 (d, JP. P
65.9 Hz), +29.74 (d, JP. P = 65.8 Hz), +28.39 (d, JP. P = 65.8 Hz) ppm.
32H35F6OP3Pd (748.94): calcd. C 51.32, H 4.71; found C 53.15, H
=
2
2
(65 %). Diastereomeric ratio: 1:2.3. IR: ν = 3065, 2961, 2869, 1619,
˜
C
1590, 1509, 1464, 1435, 1400, 1368, 1322, 1263, 1223, 1184, 1068,
5.47.
958, 836 [ν(PF6–)], 774, 750, 696, 603, 558, 515 cm–1 1H NMR
.
Complex Pd5: The procedure was the same as that used to prepare
(400 MHz): δ = 8.26–8.13 (m, Ar), 8.13–7.87 (m, Ar), 7.78–7.71 (m,
Pd1. From ligand 5 (300 mg, 0.57 mmol) and Pd dimer D (86 mg, Ar), 7.61–7.29 (m, Ar), 7.09–7.01 (m, Ar), 4.43 (d, J = 8.8 Hz, 1 H, ma),
0.22 mmol), the product was obtained as a white solid, yield 270 mg
4.21 (dd, J = 9.2, 2.4 Hz, 1 H, mi), 3.67 (s, br, 1 H, Ma), 3.47 (s, br, 1
(73 %). Diastereomeric ratio: 1:2.7. IR: ν = 3068, 1619, 1591, 1509,
H, mi), 3.36 (d, J = 16.4 Hz, 1 H, mi), 3.29 (d, J = 17.2 Hz, 1 H, ma),
˜
1464, 1437, 1321, 1264, 1223, 1184, 1068, 959, 841 [ν(PF6–)], 774, 3.09 (d, J = 10.0 Hz, 1 H, ma), 2.57 (dd, J = 10.0, 3.6 Hz, 1 H, mi),
1
3
750, 695, 608, 558, 500 cm–1. H NMR (400 MHz): δ = 8.17–8.13 (m,
1.83 (s, 3 H, mi), 1.63 (s, 3 H, Ma), 1.54 (d, JH,P = 17.2 Hz, 9 H, mi),
3
Ar), 8.09–7.98 (m, Ar), 7.79–7.75 (m, Ar), 7.62–7.30 (m, Ar), 7.24–7.15
(m, Ar), 7.07–6.98 (m, Ar), 4.45 (d, J = 9.6 Hz, 1 H, mi), 4.25 (d, J =
8.8 Hz, 1 H, ma), 3.73 (d, J = 4.4 Hz, 2 H, ma + mi), 3.62 (d, J = 70.7 (d, JC,P = 20.9 Hz, CH2, ma), 68.6 (d, JC,P = 19.9 Hz, CH2, mi),
1.49 (d, JH,P = 16.8 Hz, 9 H, ma) ppm. 13C{1H} NMR (101 MHz): δ =
2
153.8–118.2 (C, CH, Ar), 75.4 (d, JC,P = 50.1 Hz, 2 × CH2, ma + mi),
2
2
1
1
16.8 Hz, 1 H, ma), 3.12 (d, J = 8.8 Hz, 1 H, mi), 3.00 (dd, J = 10.4,
34.5 (d, JC,P = 20.5 Hz, C, mi), 34.2 (d, JC,P = 21.0 Hz, C, ma), 28.0
2
2
2
2.8 Hz, 1 H, ma), 2.63 (d, br, J = 11.6 Hz, 1 H, mi), 2.39 (d, JH,P
=
(d, JC,P = 6.9 Hz, 3 × CH3, ma), 27.8 (d, JC,P = 6.5 Hz, 3 × CH3, mi),
2
10.0 Hz, 3 H, ma), 2.38 (d, JH,P = 10.0 Hz, 3 H, mi), 1.91 (s, 3 H, mi),
23.82 (s, CH3, mi), 23.77 (s, CH3, ma) ppm. 31P{1H} NMR (162 MHz):
1.66 (s, 3 H, ma) ppm. 13C{1H} NMR (101 MHz): δ = 153.5–119.2 (C, δ = +146.99 (d, JP, P = 95.9 Hz, ma), +146.75 (d, JP, P = 96.7 Hz, mi),
2
2
CH, Ar), 75.5 (dd, 2JC,P = 46.0, 3.7 Hz, CH2, ma), 73.2 (dd, 2JC,P = 47.9,
+32.10 (d, JP, P = 96.6 Hz, mi), +32.01 (d, JP, P = 96.1 Hz, ma) ppm.
C40H37F6O3P3Pd (879.04): calcd. C 54.65, H 4.24; found C 54.53, H
4.71.
2
2
3.8 Hz, CH2, mi), 69.8–69.4 (m, 2 × CH2, ma + mi), 24.0 (s, CH3, ma),
1
1
23.8 (s, CH3, mi), 14.0 (d, JC,P = 28.9 Hz, CH3, mi), 13.2 (d, JC,P
=
28.8 Hz, CH3, ma) ppm. 31P{1H} NMR (162 MHz): δ = +145.71 (d,
Complex Pd9: The procedure was the same as that used to prepare
Pd1. From ligand 9 (320 mg, 0.54 mmol) and Pd dimer D (81 mg,
0.21 mmol), the product was obtained as a white solid, yield 303 mg
2JP, P = 102.5 Hz, mi), +145.64 (d, JP, P = 102.9 Hz, ma), –4.21 (d,
2
2JP, P = 102.9 Hz, ma), –4.90 (d, JP, P = 102.7 Hz, mi) ppm.
2
C37H31F6O3P3Pd (836.96): calcd. C 53.10, H 3.73; found C 52.78, H
4.46.
(80 %). Diastereomeric ratio: 1:1.7. IR: ν = 3061, 1619, 1590, 1509,
˜
1463, 1437, 1323, 1265, 1224, 1184, 1068, 958, 921, 841 [ν(PF6–)],
774, 749, 695, 609, 558, 517 cm–1. 1H NMR (400 MHz): δ = 8.24–8.19
Complex Pd6: The procedure was the same as that used to prepare
Pd1. From ligand 6 (380 mg, 0.66 mmol) and Pd dimer D (105 mg, (m, Ar), 8.14–7.91 (m, Ar), 7.72–7.49 (m, Ar), 7.43–7.24 (m, Ar), 7.21–
0.27 mmol), the product was obtained as a white solid, yield 331 mg
7.10 (m, Ar), 6.93–6.86 (m, Ar), 4.28 (d, J = 8.8 Hz, 1 H, mi), 4.10 (d,
J = 8.8 Hz, 1 H, ma), 3.80 (d, J = 16.4 Hz, 1 H, ma), 3.74 (s, br, ma),
3.67 (s, br, mi), 3.33 (d, J = 16.4 Hz, 1 H, mi), 3.17 (dd, J = 10.4,
2.0 Hz, 1 H, ma), 2.78 (dd, J = 10.0, 2.0 Hz, 1 H, mi), 1.96 (s, 3 H, mi),
1.70 (s, 3 H, ma) ppm. 13C{1H} NMR (101 MHz): δ = 153.5–117.9 (C,
(70 %). Diastereomeric ratio: 1:1.8. IR: ν = 3068, 2957, 2869, 1619,
˜
1590, 1509, 1464, 1434, 1400, 1322, 1264, 1225, 1184, 1068, 958,
1
927, 842 [ν(PF6–)], 773, 696, 609, 558 cm–1. H NMR (400 MHz): δ =
8.25–8.02 (m, Ar), 7.89–7.87 (m, Ar), 7.78–6.80 (m, Ar), 4.29 (d, J =
8.8 Hz, 1 H, mi), 3.83 (d, J = 17.2 Hz, 1 H, Ma), 3.68–3.59 (m, 3 H,
2
2
CH, Ar), 75.2 (d, JC,P = 47.9 Hz, CH2, mi), 70.4 (dd, JC,P = 28.0,
6.5 Hz, CH2, ma), 70.0 (dd, 2JC,P = 28.6, 7.5 Hz, CH2, mi), 24.06 (s, CH3,
ma), 23.95 (s, CH3, mi) ppm. 31P{1H} NMR (162 MHz): δ = +145.93
2 × ma + mi), 3.10 (d, J = 8.0 Hz, 1 H, ma), 2.65 (d, J = 8.8 Hz, 1 H,
3
mi), 2.47 (d, J = 16.4 Hz, 1 H, mi), 1.93 (s, 3 H, mi), 1.57 (d, JH,P
=
3
2
2
17.2 Hz, 9 H, ma), 1.49 (d, JH,P = 16.4 Hz, 9 H, mi), 1.48 (s, 3 H, ma)
(d, JP, P = 100.9 Hz, ma), +145.66 (d, JP, P = 101.3 Hz, mi), +12.31 (d,
ppm. 13C{1H} NMR (101 MHz): δ = 154.7–115.7 (C, CH, Ar), 78.9 (dd,
2JP, P = 101.4 Hz, mi), +11.48 (d, JP, P = 100.9 Hz, ma) ppm.
2
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3
C42H33F6O3P3Pd (899.03): calcd. C 56.11, H 3.70; found C 55.47, H 10.4 Hz, 1 H), 2.86 (d, JH,P = 14.8 Hz, 3 H), 2.68 (d, JH,P = 14.4 Hz,
3
3.5.
3 H), 2.54 (d, JH,P = 10.4 Hz, 3 H), 2.51 (d, J = 8.0 Hz, 1 H), 2.39 (d,
3JH,P = 10.4 Hz, 3 H), 2.36 (d, JH,P = 10.0 Hz, 3 H), 2.30 (d, JH,P
=
2
2
Complex Pd10: The procedure was the same as that used to pre-
pare Pd1. From ligand 10 (320 mg, 0.57 mmol) and Pd dimer D
(94 mg, 0.24 mmol), the product was obtained as a white solid,
9.6 Hz, 3 H), 2.07 (s, 3 H), 1.66 (s, 3 H) ppm. 13C{1H} NMR (101 MHz):
2
δ = 154.6–121.3 (C, CH, Ar), 71.3 (d, JC,P = 39.9 Hz, CH2), 71.2 (d,
2JC,P = 40.3 Hz, CH2), 67.2 (d, JC,P = 35.0 Hz, CH2), 65.0 (d, JC,P
=
2
2
yield 315 mg (76 %). Diastereomeric ratio: 1:2.4. IR: ν = 3195, 3063,
˜
2
2
34.6 Hz, CH2), 39.6 (d, JC,P = 31.8 Hz, CH3), 39.4 (d, JC,P = 29.7 Hz,
2957, 1619, 1591, 1507, 1466, 1437, 1329, 1263, 1198, 1131, 1090,
2
2
CH3), 35.03 (d, JC,P = 11.8 Hz, CH3), 35.00 (d, JC,P = 12.1 Hz, CH3),
1
1026, 944, 901, 843 [ν(PF6–)], 751, 697, 633, 606, 558, 499 cm–1. H
1
24.2 (s, CH3), 24.1 (s, CH3), 16.3 (d, JC,P = 28.8 Hz, CH3), 14.8 (d,
NMR (400 MHz): δ = 8.16–8.07 (m, Ar), 8.02–7.91 (m, Ar), 7.84–7.82
(m, Ar), 7.71–7.38 (m, Ar), 7.32–7.13 (m, Ar), 7.10–7.05 (m, Ar), 6.88–
6.79 (m, Ar), 4.08 (d, J = 6.4 Hz, 1 H, mi), 3.78 (d, J = 4.8 Hz, 1 H,
ma), 3.73 (m, 1 H, mi), 3.59 (d, J = 13.6 Hz, 1 H, ma), 3.38 (s, br, 1 H,
1JC,P = 26.3 Hz, CH3) ppm. 31P{1H} NMR (162 MHz): δ = +158.83 (d,
2JP, P = 84.6 Hz), +158.66 (d, 2JP, P = 85.2 Hz), –3.16 (d, 2JP, P = 84.7 Hz),
2
–4.95 (d, JP, P = 85.1 Hz) ppm. HRMS: calcd. for C39H37N2OP2Pd
[M – PF6]+ 717.1410; found 717.1437.
3
3
ma), 3.31 (d, JH,P = 10.4 Hz, 3 H, ma), 3.14 (d, JH,P = 10.8 Hz, 3 H,
3
mi), 3.05 (d, J = 10.4 Hz, 1 H, ma), 2.89 (d, JH,P = 14.8 Hz, 3 H, mi), Complex Pd13: The procedure was the same as that used to pre-
3
2.84 (s, br, 1 H, mi), 2.73 (d, JH,P = 14.8 Hz, 3 H, ma), 2.49 (d, J =
pare Pd1. From ligand 13 (150 mg, 0.25 mmol) and Pd dimer D
2
2
9.6 Hz, 1 H, mi), 2.25 (d, JH,P = 9.2 Hz, 3 H, ma), 2.14 (d, JH,P
=
(40 mg, 0.10 mmol), the product was obtained as a white solid,
9.2 Hz, 3 H, mi), 1.95 (s, 3 H, mi), 1.57 (s, 3 H, ma) ppm. 13C{1H} NMR yield 122 mg (67 %). Diastereomeric ratio: 1:2. IR: ν = 3064, 2963,
˜
(101 MHz): δ = 155.1–120.4 (C, CH, Ar), 73.8 (d, 2JC,P = 43.6 Hz, CH2,
mi), 65.16 (dd, 2JC,P = 30.0, 5.8 Hz, CH2, ma), 65.11 (d, 2JC,P = 31.1 Hz,
CH2, mi), 39.58 (d, 2JC,P = 31.9 Hz, CH3, ma), 39.54 (d, 2JC,P = 30.2 Hz,
CH3, mi), 35.92 (d, 2JC,P = 12.2 Hz, CH3, ma), 35.84 (d, 2JC,P = 12.6 Hz,
1619, 1591, 1507, 1467, 1435, 1329, 1262, 1199, 1090, 943, 842
[ν(PF6–)], 774, 750, 697, 601, 557, 518 cm–1. H NMR (400 MHz): δ =
1
8.15–8.05 (m, Ar), 7.99–7.90 (m, Ar), 7.86–7.81 (m, Ar), 7.73–7.66 (m,
Ar), 7.58–7.41 (m, Ar), 7.31–7.07 (m, Ar), 4.57–4.53 (m, 2 H, ma +
mi), 3.68 (d, J = 14.0 Hz, 1 H, ma), 3.33 (d, J = 14.0 Hz, 1 H, mi),
3.20–3.12 (m, 3 H, 2 × ma + mi), 2.84 (d, JH,P = 14.8 Hz, 3 H, mi),
2.65 (d, JH,P = 14.4 Hz, 3 H, ma), 2.38 (d, JH,P = 10.0 Hz, 3 H, ma),
1
CH3, mi), 24.0 (s, CH3, ma), 23.9 (s, CH3, mi), 13.4 (d, JC,P = 29.2 Hz,
1
3
CH3, mi), 12.5 (d, JC,P = 28.6 Hz, CH3, ma) ppm. 31P{1H} NMR
2
2
3
3
(162 MHz): δ = +156.57 (d, JP, P = 85.2 Hz, mi), +155.95 (d, JP, P
=
2
2
3
87.2 Hz, ma), –4.25 (d, JP, P = 87.2 Hz, ma), –5.92 (d, JP, P = 85.2 Hz,
2.22 (d, JH,P = 9.6 Hz, 3 H, mi), 2.03 (s, 3 H, mi), 1.61 (s, 3 H, ma),
mi) ppm. HRMS: calcd. for C39H37N2OP2Pd [M – PF6]+ 717.1410; 1.50 (d, JH,P = 16.4 Hz, 9 H, mi), 1.47 (d, JH,P = 16.4 Hz, 9 H, ma)
3
3
found 717.1435.
ppm. 13C{1H} NMR (101 MHz): δ = 155.2–120.1 (C, CH, Ar), 73.4 (d,
2JC,P = 44.0 Hz, CH2, ma), 67.5 (d, JC,P = 22.6 Hz, CH2, ma), 39.2 (d,
2
Complex Pd11: The procedure was the same as that used to pre-
pare Pd1. From ligand 11 (450 mg, 0.75 mmol) and Pd dimer D
(118 mg, 0.30 mmol), the product was obtained as a white solid,
2JC,P = 30.9 Hz, CH3, ma), 35.1 (d, JC,P = 10.8 Hz, CH3, ma), 32.9 (d,
2
1JC,P = 19.6 Hz, C, mi), 32.3 (d, 1JC,P = 19.4 Hz, C, ma), 27.4 (d, 2JC,P
=
2
6.3 Hz, 3 × CH3, mi), 27.1 (d, JC,P = 6.9 Hz, 3 × CH3, ma), 23.9 (s,
yield 375 mg (69 %). Diastereomeric ratio: 1:2.1. IR: ν = 3063, 2959,
˜
CH3, ma), 23.8 (s, CH3, mi) ppm. 31P{1H} NMR (162 MHz): δ = +157.80
2870, 1619, 1591, 1507, 1466, 1434, 1329, 1262, 1198, 1091, 944,
2
2
(d, JP, P = 77.6 Hz, ma), +154.36 (d, JP, P = 78.2 Hz, mi), +35.38 (d,
876, 842 [ν(PF6–)], 771, 748, 697, 633, 606, 558, 517 cm–1. H NMR
1
2JP, P = 78.2 Hz, mi), +35.34 (d, JP, P = 77.4 Hz, ma) ppm.
2
(400 MHz): δ = 8.19–7.86 (m, Ar), 7.71–7.40 (m, Ar), 7.39–7.11 (m,
Ar), 7.06–6.95 (m, Ar), 4.34 (d, J = 6.0 Hz, 1 H, mi), 3.91 (s, br, 1 H,
C42H43F6N2OP3Pd (905.12): calcd. C 55.73, H 4.79, N 3.09; found C
53.22, H 5.01, N 3.08.
mi), 3.68 (d, J = 15.2 Hz, 1 H, ma), 3.64 (dd, J = 9.2, 3.2 Hz, 1 H, ma),
3
3.34 (s, br, 1 H, ma), 3.28 (d, JH,P = 10.0 Hz, 3 H, ma), 3.17 (d, J = Complex Pd14: The procedure was the same as that used to pre-
3
3
10.0 Hz, 1 H, ma), 3.11 (d, JH,P = 10.4 Hz, 3 H, mi), 3.01 (d, JH,P
=
pare Pd1. From ligand 14 (320 mg, 0.52 mmol) and Pd dimer D
(81 mg, 0.21 mmol), the product was obtained as a white solid,
3
15.2 Hz, 3 H, mi), 2.82 (d, JH,P = 14.4 Hz, 3 H, ma), 2.45 (d, J =
9.2 Hz, 1 H, mi), 2.36 (d, J = 14.0 Hz, 1 H, mi), 1.97 (s, 3 H, mi), 1.52
yield 303 mg (78 %). Diastereomeric ratio: 1:1. IR: ν = 3063, 1618,
˜
3
3
(d, JH,P = 16.8 Hz, 9 H, ma), 1.43 (d, JH,P = 16.8 Hz, 9 H, mi), 1.33 1591, 1507, 1465, 1437, 1329, 1263, 1200, 1090, 944, 842 [ν(PF6–)],
(s, 3 H, ma) ppm. 13C{1H} NMR (101 MHz): δ = 156.3–121.8 (C, CH,
Ar), 74.9 (d, CH2, mi), 65.4 (dd, 2JC,P = 27.3, 5.2 Hz, CH2, ma), 64.6 (d,
2JC,P = 27.8 Hz, CH2, mi), 39.85 (d, 2JC,P = 30.1 Hz, CH3, mi), 39.75 (d,
749, 697, 607, 558, 519 cm–1 1H NMR (400 MHz): δ = 8.14 (d, J =
.
7.2 Hz, 1 H), 8.12 (d, J = 6.4 Hz, 2 H), 8.09 (d, J = 6.4 Hz, 1 H), 8.00
(d, J = 3.6 Hz, 1 H), 7.98 (d, J = 4.0 Hz, 1 H), 7.96 (d, J = 8.4 Hz, 1
H), 7.91 (d, J = 8.4 Hz, 1 H), 7.85 (d, J = 8.8 Hz, 1 H), 7.70 (q, J =
2
2JC,P = 31.9 Hz, CH3, ma), 36.49 (d, JC,P = 11.3 Hz, CH3, mi), 36.28
2
1
(d, JC,P = 11.2 Hz, CH3, ma), 35.9 (d, JC,P = 21.1 Hz, C, ma), 35.2 (d, 8.0 Hz, 2 H), 7.73–7.36 (m, 20 H, Ar), 7.32–7.16 (m, 17 H, Ar), 7.12–
2
1JC,P = 22.4 Hz, C, mi), 28.6 (d, JC,P = 7.0 Hz, 3 × CH3, mi), 28.2 (d,
7.08 (m, 2 H, Ar), 6.79 (m, 2 H, Ar), 4.31 (d, J = 6.0 Hz, 1 H), 3.99 (dd,
J = 7.2, 2.4 Hz, 1 H), 3.86 (d, J = 13.6 Hz, 1 H), 3.61 (t, J = 4.4 Hz, 1
H), 3.41 (s, br, 1 H), 3.32 (d, J = 13.6 Hz, 1 H), 3.22 (d, J = 10.4 Hz, 1
2JC,P = 6.6 Hz, 3 × CH3, ma), 23.73 (s, CH3, mi), 23.70 (s, CH3, ma)
ppm. 31P{1H} NMR (162 MHz): δ = +153.98 (d, JP, P = 81.0 Hz, ma),
2
3
3
+153.09 (d, 2JP, P = 80.7 Hz, mi), +27.73 (d, 2JP, P = 80.7 Hz, mi), +26.96
H), 2.99 (d, JH,P = 15.2 Hz, 3 H), 2.80 (d, JH,P = 14.8 Hz, 3 H), 2.74
2
3
(d, JP, P = 81.0 Hz, ma) ppm. C42H43F6N2OP3Pd (905.12): calcd. C (dd, J = 10.4, 2.0 Hz, 1 H), 2.56 (d, JH,P = 10.8 Hz, 3 H), 2.35 (d,
55.73, H 4.79, N 3.09; found C 55.96, H 5.19, N 3.02.
3JH,P = 10.4 Hz, 3 H), 2.02 (s, 3 H), 1.70 (s, 3 H) ppm. 13C{1H} NMR
(101 MHz): δ = 147.8–121.0 (C, CH, Ar), 39.8 (d, 2JC,P = 28.0 Hz, CH3),
Complex Pd12: The procedure was the same as that used to pre-
pare Pd1. From ligand 12 (300 mg, 0.54 mmol) and Pd dimer D
(84 mg, 0.21 mmol), the product was obtained as a white solid,
2
2
39.6 (d, JC,P = 31.2 Hz, CH3), 34.7 (d, JC,P = 17.0 Hz, CH3), 34.6 (d,
2JC,P = 17.0 Hz, CH3), 24.2 (s, CH3), 24.0 (s, CH3) ppm. 31P{1H} NMR
2
2
(162 MHz): δ = +158.84 (d, JP, P = 84.7 Hz), +158.62 (d, JP, P
=
yield 210 mg (58 %). Diastereomeric ratio: 1:1. IR: ν = 3064, 2962,
˜
2
2
83.3 Hz), +13.21 (d, JP, P = 83.3 Hz), 12.65 (d, JP, P = 84.7 Hz) ppm.
C44H39F6N2OP3Pd (925.11): calcd. C 57.12, H 4.25, N 3.03; found C
56.14, H 4.56, N 3.03.
1619, 1592, 1507, 1467, 1438, 1329, 1275, 1200, 1090, 944, 843
1
[ν(PF6–)], 740, 697, 633, 605, 558, 509 cm–1. H NMR (400 MHz): δ =
8.18–7.04 (m, 4 H, Ar), 8.03–7.88 (m, 4 H, Ar), 7.83–7.67 (m, 5 H, Ar),
7.62–7.33 (m, 16 H, Ar), 7.31–7.05 (m, 13 H, Ar), 4.76 (d, J = 6.0 Hz,
Complex Pd6′: The procedure was the same as that used to pre-
1 H), 4.50 (d, J = 4.0 Hz, 1 H), 3.67 (d, J = 14.0 Hz, 1 H), 3.53 (t, J = pare Pd1. From ligand 6 (300 mg, 0.52 mmol) and Pd dimer D′
4.4 Hz, 1 H), 3.38 (s, 1 H), 3.34 (d, J = 14.0 Hz, 1 H), 3.15 (d, J =
(135 mg, 0.2 mmol), the product was obtained as a white solid,
Eur. J. Inorg. Chem. 0000, 0–0
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Full Paper
Noyori, H. Takaya, Acc. Chem. Res. 1990, 23, 345–350; e) R. Noyori, Angew.
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a) A. Börner (Ed.), Phosphorus Ligands in Asymmetric Catalysis: Synthesis
and Applications, Wiley-VCH, Weinheim, Germany, 2008; b) A. Grabulosa,
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yield 253 mg (62 %). Diastereomeric ratio: 1:3.5. IR: ν = 3057, 2957,
˜
1
1596, 1470, 1430, 1183, 1070, 957, 848 [ν(PF6–)], 745, 561 cm–1. H
[3]
[4]
NMR (400 MHz): δ = 8.47–6.18 (m, 40 H, Ar), 6.06–5.90 (m, 4 H,
3
2 × ma + 2 × mi), 5.24–5.19 (m, 2 H, ma + mi), 1.43 (d, JH,P
=
17.2 Hz, 9 H, ma), 1.08 (d, JH,P = 16.8 Hz, 9 H, mi) ppm. 13C{1H}
3
NMR (101 MHz): δ = 154.8–118.5 (C, CH, Ar), 112.73 (d, 2JC,P = 7.9 Hz,
2
2
CH), 112.60 (d, JC,P = 8.2 Hz, CH), 100.22 (d, JC,P = 4.5 Hz, CH),
2
2
99.86 (d, JC,P = 4.8 Hz, CH), 86.36 (d, JC,P = 10.5 Hz, CH), 86.13 (d,
2JC,P = 10.7 Hz, CH), 36.79 (d, JC,P = 19.7 Hz, C, mi), 36.72 (d, 1JC,P
=
1
2
18.6 Hz, C, ma), 27.9 (d, JC,P = 6.2 Hz, 6 × CH3, ma + mi) ppm.
[5]
[6]
31P{1H} NMR (162 MHz): δ = +139.57 (d, JP, P = 138.0 Hz, ma),
2
2
2
+137.27 (d, JP, P = 144.5 Hz, mi), +29.87 (d, JP, P = 138.0 Hz, ma),
+26.75 (d, 2JP, P = 144.3 Hz, mi) ppm. HRMS: calcd. for C51H43O3P2Pd
[M – PF6]+ 871.1716; found 871.1733.
Allylic Alkylations with Dimethyl Malonate: Under a nitrogen at-
mosphere, the appropriate Pd complex (0.01 mmol), the precursor
I, II or III (1 mmol), dimethyl malonate (3 mmol), BSA (3 mmol) and
KOAc (1 mg) were dissolved in dichloromethane (5 mL) in this pre-
cise order. The flask was covered with aluminium foil, and the mix-
ture was stirred for the allotted time. To quench the reaction, di-
ethyl ether (20 mL) and aqueous 10 % ammonium chloride solution
(20 mL) were added. After extraction, the organic phase was dried
with anhydrous sodium sulfate and filtered, and the solvent was
removed in vacuo. The crude product was analysed by 1H NMR
spectroscopy to estimate the conversion. The crude product was
dissolved in ethyl acetate, and the solution was passed through a
column of silica to remove the metallic impurities. The eluent was
removed in vacuo, and the residue was analysed by NMR spectro-
scopy and HPLC (alkylations of I) or GC (alkylations of II and III).
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Allylic Amination of I with Benzylamine: Under a nitrogen atmos-
phere, the Pd complex (0.01 mmol), I (1 mmol) and benzylamine
(3 mmol) were dissolved in dichloromethane (5 mL) in this precise
order. The flask was covered with aluminium foil, and the mixture
was stirred for 72 h. To quench the reaction, diethyl ether (20 mL)
and aqueous 10 % ammonium chloride solution (20 mL) were
added. After extraction, the organic phase was dried with anhy-
drous sodium sulfate and filtered, and the solvent was removed in
vacuo. The crude product was analysed by 1H NMR spectroscopy to
estimate the conversion. The crude product was dissolved in ethyl
acetate, and the solution was passed through a column of silica to
remove the metallic impurities. The eluent was removed in vacuo,
and the residue was analysed by NMR spectroscopy and HPLC.
Acknowledgments
The authors thank the Ministerio de Economía y Competitividad
(MEC) (grant number CTQ2015-65040-P) for the financial sup-
port of this work.
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Keywords: Asymmetric catalysis · Allylic substitution ·
Palladium · P ligands
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Received: May 10, 2016
Published Online: ■
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Full Paper
Chiral P–P Ligands
P. Clavero, A. Grabulosa,*
M. Rocamora, G. Muller,
M. Font-Bardia ................................. 1–13
Diphosphorus Ligands Containing a
P-Stereogenic Phosphane and a Chi-
ral Phosphite or Phosphorodiamid-
ite – Evaluation in Pd-Catalysed
Asymmetric Allylic Substitution Re-
actions
A series of C1-symmetric diphosphorus methallyl Pd complexes are used in
ligands containing
a P-stereogenic catalytic allylic substitutions and pro-
phosphane moiety are synthetized vide good conversions and enantio-
and characterized. The derived π- selectivities.
DOI: 10.1002/ejic.201600550
Eur. J. Inorg. Chem. 0000, 0–0
www.eurjic.org
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