Metal Complexes Containing Enantiopure Bis(diamidophosphite) Ligands in Asymmetric Allylic Substitution and Hydroformylation Reactions

Article abstract of DOI:10.1021/acs.organomet.5b00457

Enantiopure bis(diamidophosphite) ligands with a heterocyclic terminal fragment derived from (R)- and (S)-N,N′-dimethyl-1,1′-binaphthyldiamine and bridging fragments derived from (S,S)-2,3-butanediol (a), (4R,5R)-4,5-di(hydroxymethyl)-2,2-dimethyl-1,3-dioxolane (b), and (R)- and (S)-1,1′-bi-2-naphthol (c) were used to prepare the palladium complexes with general formula [Pd(η³-2-CH₃-C₃H₄)(P-P)][X] (X = PF₆, 1a-(S;S_al,S_al;S), 1b-(R;R_al,R_al;R), 1b-(S;R_al,R_al;S), 1c-(R;R_al;R), 1c-(R;S_al;R); X = BPh₄, 2a-(R;S_al,S_al;R), 2c-(R;R_al;R)), which have been fully characterized. The solid-state structure for complexes 1a-(S;S_al,S_al;S) and 1b-(R;R_al,R_al;R) has been determined by X-ray diffraction. The catalytic performance of the palladium complexes has been evaluated in asymmetric allylic alkylation and amination reactions with the benchmark substrate. The influence of the nature and absolute configuration of both the terminal and bridging fragments of the bis(diamidophosphite) ligands on the asymmetric induction is discussed. The best results in terms of enantioselectivity were obtained with 1c-(R;R_al;R), affording enantiomeric excesses up to 85% in both alkylation and amination reactions. A large match-mismatch effect between the absolute configurations of stereocenters of ligand c has been observed in the allylic amination process. Preliminary results in the rhodium-catalyzed asymmetric hydroformylation of styrene by using bis(diamidophosphite) ligands a, b, and c disclosed in all cases low enantiomeric discrimination for the branched aldehyde. Both for the allylic alkylation and for the hydroformylation reaction, a related monodentate diamidophosphite d, derived from (R)-N,N′-dimethyl-1,1′-binaphthyldiamine and (S)-borneol, was also tested. Palladium complexes of this monodentate ligand showed fairly good enantioselectivity in allylic alkylation, but with very low rate, while the rhodium complex of d rendered better enantioselectivity (37% ee) than the bidentate ligands a-c in the hydroformylation of styrene. (Figure Presented).

Full text of DOI:10.1021/acs.organomet.5b00457

Article
pubs.acs.org/Organometallics
Metal Complexes Containing Enantiopure Bis(diamidophosphite)
Ligands in Asymmetric Allylic Substitution and Hydroformylation
Reactions
Maritza J. Bravo, Rosa M. Ceder,* Arnald Grabulosa, Guillermo Muller, Merce
̀
Rocamora,†
†
‡
,†
†
†
‡
J. Carles Bayon
́
, and Daniel Peral
†
Departament de Química Inorgan
Departament de Química, Universitat Auton
S Supporting Information
̀
ica, Universitat de Barcelona, Martí i Franques
̀
1-11, 08028 Barcelona, Spain
‡
̀
oma de Barcelona, Bellaterra, 08193 Barcelona, Spain
*
ABSTRACT: Enantiopure bis(diamidophosphite) ligands
with a heterocyclic terminal fragment derived from (R)- and
(
S)-N,N′-dimethyl-1,1′-binaphthyldiamine and bridging frag-
ments derived from (S,S)-2,3-butanediol (a), (4R,5R)-4,5-
di(hydroxymethyl)-2,2-dimethyl-1,3-dioxolane (b), and (R)-
and (S)-1,1′-bi-2-naphthol (c) were used to prepare the
3
palladium complexes with general formula [Pd(η -2-CH -
3
C H )(P-P)][X] (X = PF , 1a-(S;S ,S ;S), 1b-(R;R ,R ;R),
3
4
6
al al
al al
1
b-(S;R ,R ;S), 1c-(R;R ;R), 1c-(R;S ;R); X = BPh , 2a-
al al al al 4
(
R;S ,S ;R), 2c-(R;R ;R)), which have been fully character-
al al al
ized. The solid-state structure for complexes 1a-(S;S ,S ;S)
al al
and 1b-(R;R ,R ;R) has been determined by X-ray diffraction. The catalytic performance of the palladium complexes has been
al al
evaluated in asymmetric allylic alkylation and amination reactions with the benchmark substrate. The influence of the nature and
absolute configuration of both the terminal and bridging fragments of the bis(diamidophosphite) ligands on the asymmetric
induction is discussed. The best results in terms of enantioselectivity were obtained with 1c-(R;R ;R), affording enantiomeric
al
excesses up to 85% in both alkylation and amination reactions. A large match−mismatch effect between the absolute
configurations of stereocenters of ligand c has been observed in the allylic amination process. Preliminary results in the rhodium-
catalyzed asymmetric hydroformylation of styrene by using bis(diamidophosphite) ligands a, b, and c disclosed in all cases low
enantiomeric discrimination for the branched aldehyde. Both for the allylic alkylation and for the hydroformylation reaction, a
related monodentate diamidophosphite d, derived from (R)-N,N′-dimethyl-1,1′-binaphthyldiamine and (S)-borneol, was also
tested. Palladium complexes of this monodentate ligand showed fairly good enantioselectivity in allylic alkylation, but with very
low rate, while the rhodium complex of d rendered better enantioselectivity (37% ee) than the bidentate ligands a−c in the
hydroformylation of styrene.
INTRODUCTION
fine-tuning their donor−acceptor and steric properties through
incorporation of the heteroatom into the first coordination
sphere of phosphorus and a wide variation of the O- and N-
containing building blocks as well as the N-substituents.
Libraries of these chiral bidentate P−heteroatom ligands have
been applied in the allylic substitution and hydroformylation
■
Asymmetric catalysis is one of the most cost-effective and
environmentally friendly methods for the production of a large
variety of enantiomerically enriched molecules. An important
area of research within asymmetric catalysis involves the design
of enantiopure ligands and their transition metal catalysts,
which can lead to efficient and selective organic trans-
2
−6
7
8
among many other reactions. Bidentate phosphites and
9
10
mono- and bisphosphoramidites have been successfully
applied in allylic alkylation reaction. The use of diamidophos-
phites is mostly focused on the P-stereogenic bis-
(diamidophosphite) ligands with 1,3,2-diazaphospholidine
formations. In this field, chiral bidentate C -symmetric P-
donor ligands are successfully used because of their capability to
2
effectively create an asymmetric environment for the active site
1
of the catalyst. Phosphorus donor ligands with P−heteroatom
11
rings and several diols such as 1,4:3,6 dianhydro-D-manitol,
bonds, such as phosphites (3P-O), phosphoramidites (2P-O,
12
13
14
N-benzyltartarimide, N-naphthyltartarimide, binaphthol,
1
P-N), and diamidophosphites (2P-N, 1P-O) are good
1
5
resorcinol, and hydroquinone as frameworks. For the
hydroformylation a great variety of chiral ligands has been
alternatives to chiral bidentate phosphines (3P-C), because
they can be obtained in an easy way through a modular
approach by reacting alcohols or amines with phosphorus
halides, providing families with great structural and stereo-
chemical diversity. They also provide ample opportunity for
Received: May 27, 2015
©
XXXX American Chemical Society
A
DOI: 10.1021/acs.organomet.5b00457
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Organometallics
Article
assayed, with diphosphites and diphosphonites being more
Scheme 1. Synthesis of Allyl Palladium Complexes
1
6,17
widely used,
although very often the best results have been
18
achieved with hybrid diphosphorus ligands. Ligands contain-
ing the diamidophosphite moiety have been very scarcely
19,20
investigated in hydroformylation.
Bis(diamidophosphite)
ligands containing terminal P-heterocyclic rings derived from
C -diamines and C -diols as bridging fragments have been
2
2
studied and applied only to a limited range of asymmetric
transition metal catalyzed transformations. Interestingly, Pfaltz
et al. have developed a bis(diamidophosphite) ligand to study
21
the palladium-catalyzed kinetic resolution of allylic species.
Trost et al. used them in the palladium-catalyzed vinyl-
substituted trimethylenemethane asymmetric [3 + 2] cyclo-
2
2
addition. We recently described the synthesis of two families
of C -bis(diamidophosphite) ligands derived from N,N′-
2
substituted cyclohexyldiamine and N,N′-dimethyl-1,1′-binaph-
ligand d previously reported by us (Figure 1) was also assayed
in these reactions. This ligand was included in the study
because it showed a remarkable enantioselectivity in the
thyldiamine and several diols, which were applied in the Rh-
23
hydrogenation of different olefins. The best results were
obtained with the diamidophosphite ligand containing
heterocyclic terminal fragments derived from dimethylbinaph-
thyldiamine and the bridging fragment derived from dioxolane,
attaining ee’s up to 99% for all the benchmark substrates tested.
These results encouraged us to explore the binaphthyl-derived
diamidophosphite ligands in asymmetric Pd-catalyzed allylic
alkylation and amination and the Rh-catalyzed hydroformyla-
tion reactions. In this paper we describe the synthesis of the
24
palladium-catalyzed hydrovinylation of styrene. We report
here also a preliminary study on the hydroformylation of
styrene using bis(diamidophosphite)s a−c and the mono-
dentate ligand d. It has to be noticed that Reetz et al. have
described that monodentate ligands with a related skeleton
20
shows in this reaction unusually high ee’s. The reactions here
investigated, Pd-asymmetric allylic substitution and hydro-
formylation, provide the opportunity to test the efficiency of
the new chiral ligands, to identify the dominant chiral fragment
that determines the absolute configuration of the final product,
and to study the match−mismatch effects arising from the
combination of the different stereogenic elements.
new dimethylbinaphthyldiamine-based ligands b-(S;R ,R ;S)
al al
and c-(R;R ;R), diastereisomers of the previously reported
al
2
3
ligands (Figure 1). We also describe the synthesis and
RESULTS AND DISCUSSION
Synthesis and Characterization of Cationic Bis-
diamidophosphite) Allylpalladium Complexes. The
■
(
modular C -symmetric bis(diamidophosphite) ligands a, b,
2
and c were synthesized via two consecutive condensation
reactions from enantiomerically pure (R)- or (S)-N,N′-
dimethyl-1,1′-binaphthyl-2,2′-diamine and the corresponding
diols, namely, (S,S)-2,3-butanediol, (4R,5R)-4,5-di-
(
(
hydroxymethyl)-2,2-dimethyl-1,3-dioxolane, and (R)- and
S)-binaphthol, in the presence of a base following our
23
previously reported methods. The preparation and character-
ization of the new b-(S;R ,R ;S) and c-(R;R ;R) ligands is
al al
al
reported in the Experimental Section.
The cationic allylic complexes 1a−c of general formula
3
[
Pd(η -2-CH -C H )(P-P)][PF ] were obtained by reaction of
3
3
4
6
3
the organometallic precursor [Pd(η -2-CH -C H )(μ-Cl)]
3
3
4
2
with the stoichiometric amount of the appropriate bis-
diamidophosphite) ligand, at low temperature, in the presence
of NaPF (Scheme 1) as reported in the literature for similar
(
6
24
3
compounds. Complexes with the general formula [Pd(η -2-
CH -C H )(P-P)][BPh ] (P-P = 2a-(R;S ,S ;R) and 2c-
3
3
4
4
al al
(
R;R ;R)) were also synthesized. Complex 2a-(R;S ,S ;R)
Figure 1. Diamidophosphite ligands tested in asymmetric allylic
substitution and hydroformylation reactions.
a
l
a
l
a
l
was prepared due to its better crystallization compared to the
analogous complex with PF6− as counteranion. To study the
effect of the anion on the catalytic processes, 2c-(R;R ;R) was
synthesized in order to compare the catalytic results with those
al
3
characterization of new allyl palladium complexes [Pd(η -Me-
C H )(P-P)][PF ] (P-P = bis(diamidophosphite)s a−c in
obtained with 1c-(R;R ;R). They were prepared by addition of
3
5
6
al
Scheme 1). Very few examples of the coordination chemistry
the stoichiometric amount of NaBPh4 in MeOH to a
dichloromethane solution of the hexafluorophosphate complex.
The new compounds were obtained as white-yellow solids in
low to moderate yields. They are stable under inert atmosphere
at room temperature and soluble in common organic solvents.
11a
of this kind of ligand have been reported in the literature.
The new cationic palladium complexes have been used as
catalytic precursors in the Pd-asymmetric allylic alkylation and
amination. For comparative purposes the related monodentate
B
DOI: 10.1021/acs.organomet.5b00457
Organometallics XXXX, XXX, XXX−XXX

Organometallics
Table 1. Selected 31P{ H} and H NMR Data for Palladium Allyl Complexes
Article
1
a
1
b
1
δ H
complex
δ 31P
N-CH3
Hsyn
3.93 (bs)
3.35 (bs)
Hanti
CH (allyl)
3
c
150.2 (d, 2JPP = 84.0)
3
2
1
2
1
1
1
1
2
a-(S;S ,S ;S)
3.28 (d, J = 14.0)
2.90 (d, J = 12.4)
1.69 (s)
al al
HP
HP
3
2
1
47.4 (d, 2J = 84.0)
3.20 (d, J = 10.0)
2.44 (d, J = 12.8)
PP
HP
HP
d
3
[
176.6 (s)]
3.09 (d, J = 14.0)
HP
3
3
.04 (d, J = 10.0)
HP
139.4 (d, 2JPP = 94.9)
3.15 (d, J = 14.5)
3
3.72 (bd, J = 7.0)
2
2.68 (d, J = 13.5)
2
1.58 (s)
a-(R;S ,S ;R)
al al
HP
HP
HP
3
2
2
1
35.7 (d, 2J = 94.9)
3.00 (d, J = 9.5)
3.32 (bd, J = 7.5)
2.49 (d, J = 13.5)
PP
HP
HP
HP
d
3
[
178.3 (s)]
2.98 (d, J = 14.5)
HP
3
2
.92 (d, J = 9.5)
HP
141.6 (d, 2JPP = 85.1)
3.34 (d, J = 15.0)
3
b-(R;R ,R ;R)
al al
HP
3
e
2
1
39.4 (d, 2J = 85.1)
3.20 (d, J = 11.0)
3.85
2.98 (d, J = 14.0)
1.60 (s)
1.56 (s)
1.70 (s)
1.41 (s)
1.39 (s)
PP
HP
HP
d
3
2
[
168.9 (s)]
3.13 (d, J = 14.5)
3.42 (m)
2.48 (d, J = 13.0)
HP
HP
3
3
.04 (d, J = 11.0)
HP
f
138.7 (d, 2JPP = 85.5)
3
2.95 (d, 2JHP = 14.4)
2.35 (d, 2JHP = 13.2)
b-(S;R ,R ;S)
3.34 (d, J = 14.8)
3.98 (m)
al al
HP
3
2
1
36.7 (d, 2J = 85.5)
3.17 (d, J = 10.4)
3.42 (d, J = 9.0)
PP
HP
HP
d
3
[
163.9 (s)]
3.14 (d, J = 14.8)
HP
3
3
.03 (d, J = 10.4)
HP
149.9 (d, 2JPP = 65.8)
3.30 (d, J = 9.6)
3
c-(R;S ;R)
al
HP
3
2
1
45.6 (d, 2J = 65.8)
3.25 (d, J = 8.8)
4.44 (bs)
3.55 (bs)
2.91 (d, J = 12.8)
PP
HP
HP
d
3
2
[
174.6 (s)]
2.49 (d, J = 15.2)
2.81 (d, J = 13.6)
HP
HP
3
1
.79 (d, J = 15.2)
HP
f
152.3 (d, 2JPP = 66.4)
3
c-(R;R ;R)
3.49 (d, J = 13.6)
al
HP
3
1
49.7 (d, 2J = 67.0)
3.26 (d, J = 13.6)
2.96 (bs)
2.30 (bs)
2.49 (bs)
2.46 (bs)
PP
HP
d
3
[
173.6 (s)]
1.71 (d, J = 10.8)
HP
3
1
.56 (d, J = 10.4)
HP
g
151.1 (d, 2JPP = 67.0)
3
c-(R;R ;R)
3.46 (d, J = 13.6)
al
HP
3
1
49.7 (d, 2J = 67.0)
3.24 (d, J = 14.0)
3.00 (bs)
2.28 (bs)
2.47 (bs)
2.45 (bs)
PP
HP
d
1.71 (d, 3J = 10.4)
[
173.6 (s)]
HP
1
.56 (d, 3JHP = 10.4)
a
31
1
1
P{ H} [δ] = ppm (101.25 MHz, CDCl , 298 K), J = Hz. Complexes 1a, 1b, and 1c show one heptuplet at δ = −144 ppm and J = 715 Hz of the
3
PP
−
b
1
c
31
1
1
PF anion. H [δ] = ppm (500 MHz, CDCl , 298 K), J and J = Hz. P{ H} (121.44 MHz, CDCl , 298 K), H (400 MHz, CD Cl , 298 K).
6
3
HH
HP
3
2
2
d
e
13
1
f
31
1
1
Free bis(diamidophosphite) ligand. Assigned in the HSQC C− H spectrum. P{ H} (161.9 MHz, CDCl , 298 K), H (400 MHz, CDCl , 298
3
3
g
1
K). H (400 MHz, CDCl , 298 K).
3
They were fully characterized in the solid state and in solution
by standard methods. Suitable crystals for X-ray diffraction were
obtained from solutions of CH Cl /hexane for complexes 1a-
amine fragment. Moreover, in the 13C NMR spectra, reported
2
in the experimental part, different J coupling constants
CP
appear for the corresponding carbon atoms. All these facts
2
2
3
1
1
(
S;S ,S ;S) and 1b-(R;R ,R ;R). Multinuclear ( P, H, and
C) NMR study allowed us to characterize the complexes in
suggest different orientations of the amino substituents with
al al
al al
1
3
28
respect to the P−Pd bond as it has been previously reported.
solution. Relevant NMR data are summarized in Table 1.
Concerning the allyl moiety, there are four signals for the
terminal hydrogen atoms according to the coordination of the
chiral bidentate ligand. Complexes 1a, 1b, and 1c-(R;Sal;R)
showed two signals for the syn protons at lower field than the
two doublets corresponding to the anti ones, as reported for
3
1
1
P{ H} NMR spectra showed two sharp doublets showing an
AB pattern, revealing two different and strongly coupled
2
phosphorus atoms ( J = 66−95 Hz), indicating the loss of C
2
symmetry of bis(diamidophosphite) ligands in the allylic
palladium complex.
2
4,26,27
similar compounds.
For 1c-(R;Ral;R) and 2c-(R;Ral;R)
1
Coupling constants are similar to those reported for related
complexes with phosphite, phosphoramidite, and diamidophos-
unusual upfield H shifts were found for one Hsyn and for two
methyl substituents of the binaphthyl amine fragments.
9
c,25−27
11a
1
13
phite ligands.
In contrast, Gavrilov described similar
Bidimensional HSQC H− C and ROESY experiments were
necessary to assign these signals. A ROESY experiment for 2c-
(R;Ral;R) showed NOE contacts between the syn protons and
the methyl allyl group, allowing an unequivocal assignment. In
its DFT-calculated lowest energy structure, one Hsyn appeared
right below a phenyl ring of a binaphthyl diamine moiety and
two methyl substituents of each binaphthyl amine fragments
below different phenyl rings of the binaphthol bridging group,
complexes with bis(diamidophosphite) ligands presenting only
one 31P NMR signal. Complexes 1a−c containing different
31
diastereoisomers of the same ligand showed different
P
chemical shifts and different coupling constants, as expected.
The coordination of the free diamidophosphite ligands to the
3
1
palladium-allyl fragment shifts the P NMR signal to higher
fields probably due to the relatively low σ-donor character of
23
1
the ligand based on their high JPSe values, previously reported.
shifting the corresponding H NMR signals upfield (Figure 2).
Accordingly with the nonequivalence of the two P-donor
atoms, the H NMR spectra of complexes 1a−c showed four
different doublets with two different coupling constant values
Bidimensional NOESY experiments were performed for 2a-
1
(R;S ,S ;R) and 1b-(R;R ,R ;R) complexes. For all of them
al al
al al
NOE contacts can be observed between one Hsyn and one NMe
group of one diamidophosphite terminal fragment and one
corresponding to the methyl substituents of the binaphthyl-
C
DOI: 10.1021/acs.organomet.5b00457
Organometallics XXXX, XXX, XXX−XXX

Organometallics
Article
Figure 4. Molecular view of the cation corresponding to the complex
1
a-(S;S ,S ;S) (ellipsoids drawn at the 50% probability level).
al al
Hydrogen atoms and the PF anion have been omitted for clarity.
6
Selected distances (Å) and angles (deg): Pd(1)−P(1) 2.2872(9),
Pd(1)−P(2) 2.2955(8), Pd(1)−C(49) 2.196(3), Pd(1)−C(50)
2.207(3), Pd(1)−C(51) 2.190(3), P(1)−N(1) 1.690(3), P(1)−N(2)
1.659(3), P(2)−N(3) 1.682(3), P(2)−N(4) 1.653(3), C(49)−C(50)
3
Figure 2. DFT-calculated lowest energy structure for the [Pd(η -2-
+
CH -C H )(P-P)] cation, (P-P) = c-(R;R ;R).
3
3
4
al
1
.407(5), C(50)−C(51) 1.405(5), P(1)−N(1) 1.690(3), P(1)−N(2)
.659(3), P(2)−N(3) 1.682 (3), P(2)−N(4) 1.653 (3); P(1)−
1
Hanti of the other carbon with a NMe group of the other
terminal fragment, showing that C symmetry of the bidentate
ligand is broken by the allylic group. Exchange signals between
Pd(1)−P(2) 105.60(3), ∑N(1) 351.2, ∑N(2) 354.4, ∑N(3) 353.8,
2
∑
N(4) 359.4.
H −H , H −H , and H −H allylic protons are also
syn
anti
syn
syn
anti
anti
observed for 1b-(R;R ,R ;R) and H −H for 2a-(R;S ,S ;R),
al al
syn
syn
al al
indicating that the dynamic behavior takes place through the
3
1
3
two well-known pseudorotation and η −η −η mechanisms.
The ROESY experiment for 2c-(R;R ;R) does not show any
al
exchange signals between allylic protons, suggesting that the
more rigid bis(diamidophosphite) ligand c-(R;R ;R) probably
al
prevents a fast exchange mechanism in the metal complex. For
all of the complexes NOE contacts between allylic H −H
syn
anti
protons of the same carbon atom are found. Figure 3
summarizes the depicted NOE contacts and exchange signals.
Figure 5. Molecular view of the cation corresponding to the complex
b-(R;R ,R ;R)-conformer A (ellipsoids drawn at the 50% probability
1
al al
level). Hydrogen atoms and the PF anion have been omitted for
6
clarity. Selected distances (Å) and angles (deg) for both isomers:
Pd(1)−P(1) 2.3143(18), Pd(1)−P(2) 2.2884(18), Pd(1)−C(52)
Figure 3. NOE contacts (blue) and exchange signals (red).
2
.14(6), 2.25(7), Pd(1)−C(53) 2.175(13), 2.270(6), Pd(1)−C(54)
.19(5), 2.22(8), P(1)−N(1) 1.680(6), P(1)−N(2) 1.652(6), P(2)−
2
1
3
C NMR showed different chemical shifts for the terminal
allylic 13C signals, whose difference is a useful tool to evaluate
N(3) 1.632(6), P(2)−N(4) 1.683(6), C(52)−C(53) 1.40(4), 1.39(4),
C(53)−C(54) 1.43(3), 1.42(3); P(1)−Pd(1)−P(2) 102.07(6),
29
∑
N(1) 353.2, ∑N(2) 355.6, ∑N(3) 358.2, N(4) 347.2.
the asymmetry of the allyl bonding. In 1a and 1b complexes
this difference is only around 1 ppm, but reaches 4.6 ppm in 1c-
(
S;R ;S) and 9 ppm in 1c-(R;R R).
al al
methyl of the allyl group (Figure 6). For 1a and 1b the three
carbon atoms of the allyl group are approximately equidistant
from the palladium atom. As a consequence, the carbon−
Single crystals of 1a-(S;S ,S ;S) and 1b-(R;R ,R ;R), suitable
al al
al al
for X-ray analysis, were obtained by slow diffusion of hexane
into saturated dichloromethane solutions of the complexes.
Their molecular structures and a selection of bond lengths and
angles are shown in Figures 4 and 5. The structures consist of
discrete units of the cationic complex, hexafluorophosphate
anions, and dichloromethane molecules separated by typical
van der Waals distances. Both complexes have a distorted
square planar structure around the palladium atom. The four
coordination positions are occupied by the two phosphorus
atoms of the bis(diamidophosphite) ligand and the two
terminal carbon atoms of the 2-methylallyl group. Bond
distances and angles in the coordination sphere are in the
range described for related cationic allyl palladium com-
3
carbon bond lengths of the η -allyl group are nearly equal for 1a
and 1b, which is in accordance with the similar chemical shifts
observed in the 13C NMR spectra. Furthermore, for 1a the
2
6,30
plexes.
In the unit cell of complex 1a-(S;S ,S ;S) there is
al al
a single molecule. In contrast, in 1b-(R;R ,R ;R) there are two
nonequivalent molecules, which differ in the orientation of the
al al
Figure 6. Two different conformations of the bridging fragment of the
bis(diamidophosphite) relative to the allyl ligand in the monocrystal of
dioxolane group of the bridging fragment with respect to the
1b-(R;R ,R ;R).
al al
D
DOI: 10.1021/acs.organomet.5b00457
Organometallics XXXX, XXX, XXX−XXX

Organometallics
Article
relative position of the three allyl carbon atoms is interesting:
Table 2. Results of the Asymmetric Allylic Substitution of
the CH allylic carbon (C51) is situated below (−0.034 Å) and
rac-3-Acetoxy-1,3-diphenyl-1-propene (rac-I) Using Sodium
Dimethyl Malonate or Benzylamine as Nucleophile
2
a
b
the central (C50) and the terminal (C49) allylic carbon atoms
are situated above (+0.777 and +0.212 Å), showing slight
rotation from the coordination plane. The same situation is
observed in one molecule of the 1b complex (+0.088 Å for
C52, −0.350 Å for C53, +0.415 Å for C54), but in the other
one the allyl group is situated symmetrically and on one side of
the coordination plane (−0.046 Å for C52, −0.727 Å for C53,
a
c
b
c
entry
catalyst precursor
NaCH(COOMe)2 ee %
BnNH2 ee %
d
1
2
3
4
5
6
7
1a-(S;S ,S ;S)
47 (S)/38 (S)
41 (R)
26 (S)
57 (S)
43 (R)
85 (S)
<5
al al
2a-(R;S ,S ;R)
10 (R)
41 (S)
al al
1b-(R;R ,R ;R)
al al
d
1b-(S;R ,R ;S)
50 (R)/25 (R)
al al
1c-(R;R ;R)
85 (R)
61 (S)
83 (R)
−
0.037 Å for C54). From the limited number of structures
al
1c-(R;S ;R)
containing the PNNO skeleton, it is to be noted that the P−N
bond distances of the bis(diamidophosphite) coordinated
ligands in complexes 1a and 1b are in the range of those
described for monodentate diamidophosphites both in neutral
al
2c-(R;R ;R)
89 (S)
al
a
3
Reaction conditions: rac-I/NaCH(COOMe)
/[Pd(η -2-Me-C H )-
3 4
b
2
(L)]PF = 1/1.5/0.01, 8 mL of CH Cl , 25 °C, 24 h. rac-I/Bn-NH /
6
2
2
2
3
24,27
[Pd(η -2-Me-C H )(L)]PF = 1/3/0.01, 4 mL of CH Cl , 25 °C, 24 h.
3 4 6 2 2
c
allylic palladium complexes
and in borane-diamidophos-
2
0
Determined by HPLC; absolute configuration was determined by
d
phite compounds. The P−N bond distances suggest partial
multiple-bond character when compared to the normally
accepted bond lengths (P−N bond 1.77 Å and PN bond
comparison with the known sign of specific rotation. Catalyst
3
generated under in situ conditions by mixing of 0.01 mmol of [Pd(η -
C H )(μ-Cl)] and 0.02 mmol of the corresponding ligand.
3
1
3
5
2
1
.57 Å). Two different P−N distances are observed in each
terminal heterocyclic fragment of the ligand in complexes 1a
and 1b. The sum of the bond angles around the nitrogen atoms
reflects that their geometry tends to planarity, as occurs in other
These results agree with the largest chemical shift difference
observed for the terminal allylic carbons in 1c complexes. The
enantioselectivity decreases with the increasing flexibility of the
bridging fragment (entries 5, 6 vs 3, 4). Shorter bridging
fragments also lead to lower enantioselectivities (entries 1, 2 vs
2
8a
32
diamidophosphite
complexes. Binaphthyl groups have torsion angles of 57.55° and
4.27° for the 1a complex and of 57.02° and 57.88° for
and phosphoramidite allyl palladium
5
complex 1b. The two methyl groups of each binaphthyldiamine
fragment are placed at opposite sides of the plane defined by
the phosphorus and the two nitrogen atoms of the heterocycle.
Asymmetric Allylic Substitution Reactions. To evaluate
the potential of diamidophosphite ligands a−c in the
asymmetric allylic substitution, the cationic palladium com-
plexes 1a−c, 2a, and 2c were tested as catalytic precursors using
the model substrate rac-3-acetoxy-1,3-diphenyl-1-propene (rac-
I), with sodium dimethyl malonate or benzylamine as
nucleophile (Scheme 2). The reactions were performed in
5
, 6). This behavior has already been reported for structurally
related bisphosphite ligands, finding that when the bridging
fragment is large, a rigid backbone is needed in order to obtain
a good enantioselectivity. We found a match effect between
the configuration of the binaphthyldiamine-derived groups and
the diol-derived bridge within each pair of the diastereoisomers
of the ligands (entries 1 vs 2, 3 vs 4, 5 vs 6). In the case of
ligand a this effect is more relevant, with a-(S;S ,S ;S) being
the matched combination. Matched and mismatched combina-
8b
al al
tions of chirality elements were found for P-stereogenic
1
4
bis(diamidophosphite)-related ligands. With the aim of
checking the effect of the catalytic precursor, we compared
the behavior of the catalyst generated under “in situ” conditions
Scheme 2. Asymmetric Allylic Substitutions Catalyzed by
Palladium Complexes
3
by mixing [Pd(μ-Cl)(η -C H )] and the appropriate amount
3
5
2
of the corresponding ligand with that of the preformed
complex. In all cases a decrease in the enantioselectivity was
observed in the “in situ” conditions (entries 1 and 4). The
cationic palladium allylic complex with the monodentate
3
diamidophosphite ligand d, [Pd(η -2-CH -C H )(d) ][PF ],
3
3
4
2
6
achieved 70% ee of the R enantiomer, but with very low
conversion (7%) under the same catalytic conditions. A similar
low conversion was obtained with a palladium complex
containing an ionic monodentate diamidophosphite ligand
derived from (R)-N,N′-dimethylbinaphthyldiamine previously
CH Cl at room temperature for 24 h. Under these conditions,
2
2
27
the allylic acetate rac-I was converted to the desired product II
or III in quantitative yields. The results are summarized in
Table 2.
described by us. Therefore, a beneficial effect for the
asymmetric allylic alkylation reaction in terms of activity is
observed for bidentate versus monodentate diamidophosphite
ligands with a binaphthyl heterocyclic fragment. We also tested
the catalytic behavior of the preformed complexes 1a−c, 2a,
and 2c in the allylic amination of rac-I using benzylamine as
nucleophile. Full conversion and moderate to high ee values
were obtained under the conditions displayed in Table 2. When
complexes with both diastereoisomers of ligand a were used, no
significant differences in activity and enantioselectivity were
observed between the amination and alkylation processes
33
Considering that some reports describe that different
counterions can affect the overall enantioselectivity of the
process, we compared the effect exerted by tetraphenylborate
and hexafluorophosphate anions on the allylic substitution
reaction. In particular with complexes 1c-(R;R ;R) and 2c-
al
(
R;R ;R) the same conversion and enantioselectivity were
al
obtained, concluding that there is no anion effect with these
catalytic precursors (entries 5, 7). In the allylic alkylation a wide
range of enantioselectivities (10−86% ee) was obtained. The
highest values were obtained with both stereoisomers of ligands
c, the most strained bis(diamidophosphite) (entries 5−7).
(entries 1, 2). Bis(diamidophosphite) c-(R;R ;R) was the best
al
ligand in terms of enantioselectivity, attaining an ee value of up
to 89% (S) at 100% conversion (entries 5, 7). In this case a
E
DOI: 10.1021/acs.organomet.5b00457
Organometallics XXXX, XXX, XXX−XXX

Organometallics
Article
lower substrate:nucleopile ratio (1:1.5) led to a conversion of
Table 3. Results of the Asymmetric Hydroformylation of
9
0% in 6 h with an excellent enantiomeric excess of 92% (S). It
Styrene Catalyzed by [Rh(acac)(CO) ] and
Bis(diamidophosphites) a−c or Diamidophosphite d
2
a
,
b
is interesting to note the complete loss of enantioselectivity
with complex 1c-(R;S ;R) that contains the other diaster-
al
c
d
entry
ligand
T °C
conversn % (t)
reg %
ee %
eoisomer of ligand c (entry 6), showing a large match−
mismatch effect between the absolute configurations of
stereocenters of the ligand. The absolute configuration of the
amination product with precursors with ligands a and c is the
same as for the alkylation reaction, although the CIP descriptor
was inverted because of the change in the priority of the groups.
Interestingly in the case of the precursors bearing both
diastereoisomers of ligand b there is a change in the sense of
the asymmetric induction between alkylation and amination
1
a-(S;S ,S ;S)
80
100
60
80
80
80
80
80
80
65
50
46(5)
37(2.5)
54(14)
37(5)
30(5)
66(5)
55(5)
94(1)
57(3)
81(1)
44(2)
68
63
77
67
62
50
18
65
68
77
82
30(R)
23(R)
21(R)
7(S)
<5
al al
2
a-(S;S ,S ;S)
al al
3
a-(S;S ,S ;S)
al al
4
a-(R,S ,S ,R)
al al
5
b-(R;R ,R ;R)
al al
6
c-(R;R ;R)
15(R)
<5
al
7
c-(R;S ;R)
al
8
d-(R;Sal)
15(S)
<5
e
9
d-(R;Sal)
(
entries 3, 4). These results are unexpected and although not
8c
10
11
d-(R;Sal)
d-(R;Sal)
31(S)
37(S)
very common are described in some reports with phosphite,
phosphoramidite, diphosphine, and also diamidophosphite
ligands. This abnormal behavior of an amine as nucleophile
3
4
35
a
1
1a
Reaction conditions: [Rh(acac)(CO) ] = 0.02 mmol, ligand = 0.04
mmol, styrene = 20.0 mmol, P(CO) = P(H ) = 10 bar, 7.7 mL of
toluene, 300 μL of dodecane as internal reference. Complete
chemoselectivity in all cases except in entry 7 (93%). Percent of
conversion in the time in h indicated between parentheses. Percent
regioselectivity to the branched aldehyde. 0.24 mmol of d was used.
2
36
is commented on an early paper by Trost. The correlation
between the stereochemistry of the diamidophosphite ligand c
and the absolute configuration of the substitution products II
and III indicates that the axial chirality of the binaphthol-
derived bridging fragment determines the absolute config-
uration of the major isomer of the alkylation and amination
products (entries 5−7). But, in the case of ligands a and b, the
absolute configuration of the major isomer is basically
controlled by the axial chirality of the binaphthyl-derived
2
b
c
d
e
major product is controlled by the axial chirality of the
binaphthyl moiety.
The low regioselectivity to the branched aldehyde achieved
1
1a,b,12,14,37
fragment (entries 1−4). Gavrilov
has applied
with ligand c-(R;S ;R) (entry 7) is unusual for the hydro-
al
38
libraries of bidentate P-stereogenic C -symmetric diamidophos-
2
formylation of styrene. This result prompted us to investigate
the regioselectivity of this catalyst with other substrates, but the
results were disappointing. For the hydroformylation of allyl
cyanide and 1-hexene, under the reaction conditions of entry 7,
the regioselectivity to the linear aldehyde was only 29% and
41%, respectively. In an attempt to investigate the origin for the
anomalous regioselectivities achieved with the catalyst of the
phite ligands with 1,3,2-diazaphospholidine rings as terminal
fragments and several chiral diol-derived bridging fragments to
the palladium-catalyzed asymmetric allylic substitution process,
achieving lower activity and better enantioselectivity than those
described in this paper. The presence of the stereogenic
phosphorus atom attached to the metallic center may enhance
the enantioselectivity of the catalytic systems.
ligand c-(R;S ;R), the structure of the resident species of the
al
Hydroformylation Reaction. Ligands a, b, c, and d were
evaluated in the Rh-catalyzed asymmetric hydroformylation of
styrene, one of the most well-studied substrates for this reaction
catalyst [RhH(CO) (c-(R;S ;R)] was investigated by NMR, by
2
al
2
reacting [Rh(acac)(η -C H ) ] with 1 equiv of c-(R;S ;R) in a
2
4 2
al
3
1
1
CO/H atmosphere. The P{ H} NMR spectrum at room
temperature showed a doublet at 185.1 ppm ( J = 171 Hz),
while the H spectrum showed a triplet of doublets at −10.18
ppm ( J = 47.3 Hz and J
observed in the P NMR spectrum suggests the presence of
two equivalent phosphorus atoms. The J coupling constant
2
1
(Scheme 3).
RhP
1
2
1
Scheme 3. Asymmetric Hydroformylation Catalyzed by
Rhodium Complexes
= 7.0 Hz). The doublet
PH
RhH
31
2
PH
found corresponds to an intermediate value between the low
coupling constants (ca. 10 Hz) reported for cis phosphorus
hydride species, in trigonal bipyramid rhodium coordination,
and that of trans phosphorus hydride species (>100 Hz),
suggesting an equatorial axial coordination of the bidentate
ligand with fast exchange between both phosphorus positions
The catalytic systems were formed in situ by addition of 2
equiv of the corresponding bis(diamidophosphite) or the
diamidophosphite ligand to a toluene solution of [Rh(acac)-
39
via a Meakin-type rearrangement or a fast exchange between
4
0,41
an equatorial−equatorial and an axial−equatorial isomer.
(
CO) ] followed by addition of the substrate and pressurization
The molecular structure in the solid state of rhodium
2
of the autoclave at 20 bar with a 1:1 mixture of syn-gas at the
working temperature. Results are collected in Table 3. All
complexes [RhH(CO) (P-P)] containing diphosphites with a
2
substituted [1,1′-biphenyl-2,2′-diyl)bis(oxy)] bridge appeared
bidentate ligands, except c-(R;S ;R) (entry 7), show chemo-
in both equatorial−equatorial and axial−equatorial positions,
al
42,43
selectivity of >99% in aldehydes, with moderate regioselectivity
reflecting similar stability.
Surprisingly, slightly better
in the branched aldehyde (from 50% to 82%), again ligand c-
enantioselectivity (37%) was achieved with the monodenate
(
R;S ;R) being the exception. As expected, by increasing the
diamidophosphite d-(R;S ) (entry 11) than with the bis-
al
al
temperature the selectivity in the branched aldehyde diminishes
(diamidophosphite) assayed. Also remarkable is the fact that
the best ee was produced when 2 equiv of the monodentate
ligand was used, since an increase of the ligand to rhodium
molar ratio yielded the racemic branched aldehyde (entries 8
and 9).
(entries 1−3). Enantioselectivities are low, showing a weak, but
measurable, match−mismatch effect in the case of the
diastereoisomers of ligand a. As in the case of the allylic
substitution reactions described above, the configuration of the
F
DOI: 10.1021/acs.organomet.5b00457
Organometallics XXXX, XXX, XXX−XXX

Organometallics
Article
white precipitate of amine hydrochloride was filtered off. The solvent
was removed under vacuum, and a white-cream solid was obtained and
used without further purification.
CONCLUDING REMARKS
Cationic allylic complexes [Pd(η -2-CH -C H )(P-P)][PF ]
with both diastereoisomers of C -symmetric bis-
diamidophosphite) ligands a, b, and c have been prepared
and fully characterized. NMR spectra showed that these ligands
create a well-defined chiral pocket. The X-ray structure for
■
3
3
3
4
6
2
b-(S;R R ;S). Yield: 409 mg (60%). HR-MS (ESI, m/z): calcd for
al al
(
+
298
C H N O P 842.3151, found 843.3237 [MH] . [α] = +513.10 (c
5
1
48
4
4 2
31
1
1.0, CH Cl ). P{ H} NMR (toluene, 101.25 MHz, δ (ppm)): 163.9
2 2
1
(s). H NMR (CDCl , 400 MHz, δ (ppm), J (Hz)): 7.90−6.94 (om,
3
complex 1b-(R;R ,R ;R) showed two different molecules
24H, CH(Ar)), 3.72- 3.66 (om, 2H, OCH), 3.65−3.58 (om, 2H,
al al
3
because the long and flexible bridge of ligand b-(R;R ,R ;R)
allowed the stabilization of two different conformers. The new
OCH
2
), 3.58−3.51 (om, 2H, OCH
2
), 2.96 (d,
J
HP = 14, 6H,
al al
3
CH (NMe)), 2.36 (d, J = 7.6, 6H, CH (NMe)), 1.43 (s, 6H, CH ).
3
HP
3
3
1
3
2
C NMR (CDCl , 100.6 MHz, δ (ppm), J (Hz)): 144.9 (d, J = 4.9,
C, C(Ar)), 142.9 (d, J = 7.0, 2C, C(Ar)), 133.0−121.0 (om, 36C,
2C(Ar) + 24CH(Ar)), 109.8 (s, 1C, O CMe ), 77.9 (d, J = 5.1,
C, OCH), 63.3 (d, J = 3.4, 2C, OCH ), 38.0 (d, J = 45.1, 2C,
CH (NMe)), 34.6 (d, J = 26.1, 2C, CH (NMe)), 27.0 (s, 2C, CH ).
1
a−c, 2a-(R;S ,S ;R), and 2c-(R;R ;R) complexes have been
3
CP
al al
al
2
2
1
2
CP
used as catalytic precursors in the allylic alkylation and
amination reaction of rac-3-acetoxy-1,3-diphenylpropene. The
best asymmetric induction has been achieved using either 1c-
3
2
2
CP
2
2
CP
2
CP
2
3
CP
3
3
(
R;R ;R) or 2c-(R;R ;R) as precursor, leading to very similar
298
al
al
c-(R;R ;R). Yield: 505 mg (66%). [α] = −216.14 (c 1.0, CH Cl ).
al
2
2
ee values for the alkylation (85% (R)) and for the amination
89% (S)) reactions. These results allow us to conclude that for
the systems presented here there is no significant anion effect
and that the more strained ligand c-(R;R ;R) has the highest
discrimination ability for this reaction. Additionally a marked
match−mismatch effect has been observed for both diaster-
eoisomers of ligand 1c. While the 1c-(R;R ;R) precursor leads
to a high ee value in the amination process, the 1c-(R;S ;R)
complex gives the racemic product. The absolute configuration
of the major product depends on the configuration of the
binaphthyldiamine-derived terminal fragments when the
bridging fragment is flexible (ligands a and b), while with a
more rigid bridging fragment (ligand c) it is the configuration
of the binaphthol bridge that dictates the product configuration.
Rhodium complexes of ligands a, b, c, and d have been assayed
in the asymmetric hydroformylation of styrene, showing low
enantiomeric excesses, with the monodentate ligand d showing
better enantioselectivity (37% ee).
31
13
1
1
P{ H} (CDCl , 121,44 MHz), H NMR (CDCl , 400 MHz), and
3
3
(
C NMR (CDCl , 100.6 MHz) were described for the enantiomer c-
3
(
S;S ;S) in ref 23.
al
3
al
General Procedure for the Synthesis of [Pd(η -2-Me-C
P)]PF (1a−c). To a solution of the appropriate ligand (0.40 mmol) in
6
3
H )(P-
3 4
toluene (10 mL) at 0 °C was added dropwise a solution of [Pd(η -2-
Me-C H )(μ-Cl)] (79 mg, 0.20 mmol) in CH Cl (5 mL). Then a
3
4
2
2
2
al
solution of NaPF (67 mg, 0.40 mmol) in THF (5 mL) was added.
6
al
After 3 h of stirring at room temperature, the solution was washed with
deoxygenated water (2 × 4 mL). The organic phase was dried over
anhydrous Na SO and filtered off, and the solvent removed under
2
4
reduced pressure. The white or yellow solid obtained was washed
several times with diethyl ether or n-pentane and dried under reduced
pressure.
1a-(S;S ,S ;S). Yield: 267 mg (62%). Mp: 210−218 °C dec.
al al
31
1
2
P{ H} NMR (121.4 MHz, CDCl , δ (ppm), J (Hz)): 150.2 (d, J
=
3
PP
2
1
84.0), 147.4 (d, J = 84.0). H NMR (400 MHz, CD Cl , δ (ppm), J
PP
2
2
(Hz)): 8.20−6.90 (om, 24H, CH(Ar)), 4.85−4.65 (om, 2H, OCH),
3
3
3
=
(
1
.93 (bs, 1H, CH (syn)), 3.35 (bs, 1H, CH (syn)), 3.28 (d, J = 14.0,
2 2 HP
3
3
H, CH (NMe)), 3.20 (d, J = 10.0, 3H, CH (NMe)), 3.09 (d, J
HP
14.0, 3H, CH (NMe)), 3.04 (d, J = 10.0, 3H, CH (NMe)), 2.90
3
HP
3
3
EXPERIMENTAL SECTION
3
HP
3
■
2
2
d, J = 12.4, 1H, CH (anti)), 2.44 (d, J = 12.8, 1H, CH (anti)),
HP 2 HP 2
General Information. All manipulations were performed under a
dry nitrogen atmosphere using standard vacuum-line Schlenk
techniques. Anhydrous dichloromethane, tetrahydrofuran, and toluene
were obtained from a solvent purification system. Et N and i-Pr EtN
3
.69 (s, 3H, CH (allyl)), 1.10 (pt, J = 6.0, 6H, CH ). HR-MS (ESI,
3 HH 3
m/z): calcd for C H N O P Pd 931.2522, found 931.2524 [M] .
b-(R;R ,R ;R). Yield: 78 mg (17%). Mp: 234−242 °C dec.
NMR (161.9 MHz, CDCl , 298 K, δ (ppm), J (Hz)): 141.6 (d, J
+
+
52
51
4
2 2
31
1
P
=
al al
3
2
2
3
PP
were distilled from CaH and collected over 4 Å molecular sieves
2
1
2
8
5.1), 139.4 (d, J = 85.1). H NMR (500 MHz, CDCl , δ (ppm), J
P
P
3
before use. The diols, (S,S)-2,3-butanediol, (4R,5R)-4,5-di-
(
4
Hz)): 8.10−6.95 (om, 24H, CH(Ar)), 4.18−4.11 (m, 2H, OCH),
(
hydroxymethyl)-2,2-dimethyl-1,3-dioxolane, (R)- and (S)-1,1′-bi-2-
2
.08−3.82 (om, 5H, 4OCH + 1CH (syn)), 3.42 (d, J = 9.0, 1H,
2
2
HP
naphthol, (R)- and (S)-N,N′-dimethyl-1,1′-binaphthyl-2,2′-diamine,
3
3
CH (syn)), 3.34 (d, J = 15.0, 3H, CH (NMe)), 3.20 (d, J = 10.0,
3H, CH
= 11.0, 3H, CH
(
CH ), 1.40 (s, 3H, CH ). C{ H} NMR (125.7 MHz, CDCl , δ
(
C(allyl)), 133.2−130.5 (12C, C(Ar)), 130.5−121.0 (24C, CH(Ar)),
1
6
6
1
2
HP
3
HP
and PCl were used as supplied. The dimeric palladium complex
3
3
3
3
3
(NMe)), 3.13 (d, JHP = 14.5, 3H, CH
3
(NMe)), 3.04 (d, JHP
(NMe)), 2.98 (d, JHP = 14.0, 1H, CH (anti)), 2.48
d, J = 13.0, 1H, CH (anti)), 1.61 (s, 3H, CH (allyl)), 1.41 (s, 3H,
[
Pd(η -2-Me-C H )(μ-Cl)] was prepared as described in the
3
4
2
2
44
3
2
literature. Ligands a-(R;S ,S ;R), a-(S;S ,S S), b-(R;R ,R ;R), c-
al al
al al,
al al
2
HP
2
3
(
us.
R;S ;R), and d-(R;S ) were prepared as previously described by
al
3,24
al
13
1
2
1
13
31
3
3
3
H and C (standard SiMe ) and P (standard H PO ) NMR
4 3 4
2
ppm), J (Hz)): 141.5−140.6 (4C, C(Ar)), 135.9 (pt, J = 8.1, 1C,
CP
spectra were recorded on 400 or 500 MHz spectrometers. High-
resolution mass spectra were obtained on a time-of-flight instrument
using electrospray ionization.
3
3
10.7 (s, 1C, O CMe ), 80.3 (d, J = 7.5, 1C, OCH), 80.0 (d, J
=
2
2
CP
CP
2
2
.3, 1C, OCH), 67.8 (dd, J
= 40.0, J
= 2.5, 1C, CH (allyl)),
CPtrans
CPcis 2
Synthesis of Bis(diamidophosphite) Ligands b-(S;R ,R ;S)
al al
2
2
2
6.6 (dd, J
= 40.0, J
= 2.5, 1C, CH (allyl)), 65.6 (d, J
7.5, 1C, OCH ), 65.5 (d, J = 17.5, 1C, OCH ), 40.4 (d, J
=
=
and c-(R;R ;R). (S)- or (R)-N,N′-Dimethyl-1,1′-binaphthyldiamine
CPtrans
CPcis
2
CP
al
2
2
(
0.5 g, 1.6 mmol) and N-ethyldiisopropylamine (2.20 mL, 12.6 mmol)
2
CP
2
CP
2
1
5.0, 1C, CH (NMe), 40.1 (d, J = 16.5, 1C, CH (NMe), 36.2 (d,
were dissolved in 10 mL of toluene at 0 °C. PCl (0.30 mL, 3.4 mmol)
3 CP 3
3
2
2
JCP = 7.5, 1C, CH (NMe)), 36.0 (d, J = 7.5, 1C, CH (NMe)), 26.8
dissolved in 5 mL of toluene was added dropwise at 0 °C. The mixture
was allowed to warm to room temperature and was stirred for 20 h.
The formation of the chlorodiazaphosphepine was monitored by
phosphorus NMR spectroscopy (δ = 205.0 ppm), being complete after
3
CP
3
(s, 1C, CH
), 26.7 (s, 1C, CH
), 23.8 (s, 1C, CH
(allyl)). HR-MS
3
3
3
+
(ESI, m/z): calcd for C55
H
55
N
O
4
P
Pd 1003.2733, found 1003.2734
2
4
+
[M] .
1b-(S;Ral,Ral;S). Yield: 138 mg (30%). Mp: 228−230 °C dec. 31P
this period. The solvent and the excess PCl and ethyldiisopropyl-
3
2
amine were thoroughly removed under reduced pressure to afford a
viscous oil. This oil was dissolved in toluene (10 mL), and DMAP (2.4
mg, 0.02 mmol) was added. The corresponding diol (0.8 mmol)
NMR (161.9 MHz, CDCl
3
, 298 K, δ (ppm), J (Hz)): 138.7 (d, JPP
=
2
1
85.8), 136.7 (d, JPP = 85.8). H NMR (400 MHz, CDCl
(Hz)): 8.15−6.90 (om, 24H, CH(Ar)), 4.55−4.45 (m, 2H, OCH),
4.20−4.00 (om, 2H, OCH ), 3.98 (m, 1H, CH (syn)), 3.75−3.60 (m,
2H, OCH ), 3.35 (m, 1H, CH (syn)), 3.34 (d, J = 14.8, 3H,
, δ (ppm), J
3
(
1
1
(4R,5R)-4,5-di(hydroxymethyl)-2,2-dimethyl-1,3-dioxolane or (R)-
2
2
3
,1′-bi-2-naphthol) in THF (10 mL) and triethylamine (2.2 mL,
2
2
HP
3
3
5.8 mmol) were added in three portions at 0 °C. After stirring
CH (NMe), 3.17 (d, J = 10.4, 3H, CH (NMe)), 3.14 (d, J =
3
HP
3
HP
3
overnight at room temperature, the mixture was cooled at 4 °C. The
14.8, 3H, CH (NMe)), 3.03 (d, J = 10.4, 3H, CH (NMe)), 2.95 (d,
3
HP
3
G
DOI: 10.1021/acs.organomet.5b00457
Organometallics XXXX, XXX, XXX−XXX

Organometallics
Article
2JHP = 14.4, 1H, CH (anti)), 2.35 (d, J = 13.2, 1H, CH (anti)), 1.56
2
(125.7 MHz, CDCl , δ(ppm), J (Hz)): 164.2 (q, J = 48.8 Hz, 4C,
3 CB
1
2
HP
2
13
1
2
2
(
s, 3H, CH (allyl)), 1.44 (s, 6H, CH ). C{ H} NMR (100.6 MHz,
CB(Ar)), 140.8 (d, J = 5.0, 1C, C(Ar)), 140.6 (d, J = 6.3, 1C,
3
3
CP CP
2
2
2
CDCl , δ (ppm), J (Hz)): 141.6 (d, J = 7.9, 1C, C(Ar)), 141.5 (d,
C(Ar)), 140.3 (d, J = 3.8, 1C, C(Ar)), 140.2 (d, J = 6.3, 1C,
CP CP
3
CP
2
2
2
C(Ar)), 137.9 (pt, 2JCP = 8.1, 1C, C(allyl)), 136.7−121.2 (56C,
2 2
JCP = 7.9, 1C, C(Ar)), 140.9 (d, J = 2.5, 1C, C(Ar)), 140.4 (d, J
CP
CP
2
=
2.5, 1C, C(Ar)), 135.3 (pt, J = 7.7, 1C, C(allyl)), 134.0−131.0
44CH(Ar) + 12C(Ar)), 80.4 (d, J = 2.5, 1C, OCH), 79.7 (d, J
=
CP
CP
CP
2
2
(
12C, C(Ar)), 130.0−121.0 (24C, CH(Ar)), 111.7 (s, 1C, O CMe ),
2
2
6.3, 1C, OCH), 67.0 (dd, J
= 39.4, J
= 4.4, 1C, CH (allyl)),
CPtrans
CPcis 2
3
2
7
6
8.3 (d, J = 7.4, 2C, OCH), 68.0 (d, J
= 38.3, 1C, CH (allyl)),
2
2
2
CP
CPtrans
2
66.4 (dd, J
= 40.6, J
= 4.4, 1C, CH (allyl)), 39.2 (d, J
=
CP
CPtrans
CPcis
2
6.9 (d, 2JCP = 14.1, 1C, OCH ), 65.2 (d, JCPtrans = 40.3, 1C,
2
2
2
2
7.5, 1C, CH (NMe)), 39.0 (d, J = 27.5, 1C, CH (NMe)), 36.2 (d,
2
2
3 CP 3
CH (allyl)), 40.4 (d, J = 13.1, 1C, CH (NMe), 40.1 (d, J = 14.0,
C, CH (NMe), 36.5 (d, J = 7.2, 1C, CH (NMe)), 36.3 (d, J
.8, 1C, CH (NMe)), 26.9 (s, 2C, CH ), 23.8 (s, 1C, CH (allyl)). HR-
2
2
2
CP
3
CP
JCP = 10.0, 1C, CH (NMe)), 35.9 (d, J = 10.0, 1C, CH (NMe)),
3.8 (s, 1C, CH (allyl)), 20.6 (d, J = 2.5, 1C, CH ), 20.2 (d, J
2
2
3
CP
3
1
=
3
CP
3
CP
3
3
2
=
3
CP
3
CP
7
3
3
3
+
+
2.5, 1C, CH ). HR-MS (ESI, m/z): calcd for C H N O P Pd
3 52 51 4 2 2
MS (ESI, m/z): calcd for C H N O P Pd 1003.2733, found
55
55
4
4 2
+
+
931.2522, found 931.2538 [M] .
2c-(R;R ;R). Yield: 69 mg (12%). Mp: 198−205 °C dec. P{ H}
NMR (121.4 MHz, CDCl , δ (ppm), J (Hz)): 151.1 (d, J = 67.0),
1
003.2733 [M] .
3
1
1
c-(R;S ;R). Yield: 158 mg (31%). Mp: 215−225 °C dec. 31P NMR
101.2 MHz, CDCl , 298 K, δ (ppm), J (Hz)): 149.9 (d, J = 65.8),
1
al
al
2
2
(
1
3
PP
3
PP
2
1
2
1
45.6 (d, J = 65.8). H NMR (500 MHz, CDCl , 298 K): 8.34−
149.7 (d, JPP = 67.0). H NMR (400 MHz, CDCl
3
, δ (ppm), J (Hz)):
PP
3
3
3
6
.93 (m, 34H, CH(Ar)), 5.84 (d, J = 7.5, 1H, CH(Ar)), 5.23 (d,
8.22−6.81 (om, 56H, CH(Ar)), 3.46 (d, JHP = 13.6, 3H, CH
3.24 (d, J = 14.0, 3H, CH (NMe)), 3.00 (bs, 1H, CH (syn)), 2.47
(bs, 1H, CH (anti)), 2.45 (bs, 1H, CH (anti)), 2.28 (bs, 1H,
2 2
CH (syn)), 1.71 (d, J = 10.4, 3H, CH (NMe)), 1.56 (d, J
10.4, 3H, CH (NMe)), 1.39 (s, 3H, CH (allyl)). C{ H} NMR
(125.7 MHz, CDCl , δ (ppm), J (Hz)): 164.4 (q, J = 48.8, 4C,
CB(Ar)), 146.1 (d, J = 1.3, 1C, C(Ar)), 146.0 (d, J = 2.5, 1C,
C(Ar)), 145.7 (bs, 1C, C(Ar)), 141.3 (d, J = 5.0, 1C, C(Ar)), 140.8
3
(NMe)),
HH
3
3
JHH = 7.5, 1H, CH(Ar)), 4.44 (bs, 1H, CH (syn)), 3.55 (bs, 1H,
CH (syn)), 3.30 (d, J = 9.6, 3H, CH (NMe)), 3.25 (d, J = 8.8,
H, CH (NMe)), 2.91 (d, J = 12.8, 1H, CH (anti)), 2.81 (d, J
2
HP
3
2
3
3
2
HP
3
HP
2
2
3
3
3
=
=
3
HP
2
HP
2
HP
3
HP
3
1
3
1
1
3.6, 1H, CH (anti)), 2.49 (d, J = 15.02 3H, CH (NMe)), 1.79 (d,
2 HP 3
3
3
3
13
1
JHP = 15.2, 3H, CH (NMe)), 1.70 (s, 3H, CH (allyl)). C{ H} NMR
1
3
3
3
2
CB
2
2
(
125.7 MHz, CDCl , δ (ppm), J (Hz)): 150.2 (d, J = 2.5, 1C,
3
C
P
CP
CP
2
2
C(Ar)), 149.4 (d, J = 6.3, 1C, C(Ar)), 141.4 (d, J = 3.8, 1C,
C(Ar)), 140.8 (d, J = 3.8, 1C, C(Ar)), 139.8 (d, J = 7.5, 1C,
C(Ar)), 139.3 (d, J = 7.5, 1C, C(Ar)), 138.0 (pt, JCP = 7.5, 1C,
C(allyl)), 133.9−121.5 (54C, 18C(Ar) + 36CH(Ar)), 72.8 (d, J
2
CP
CP
CP
2
2
2
2
CP
CP
(
d, J = 5.0, 1C, C(Ar)), 140.2 (d, J = 7.5, 1C, C(Ar)), 140.0 (d,
JCP = 7.5, 1C, C(Ar)), 138.5 (pt, J = 7.5, 1C, C(allyl)), 136.5−
2
CP CP
CP
2
2
2
CP
CPtrans
2
2
2
111.8 (73C, 17C(Ar) + 56CH(Ar)), 77.5 (dd, JCPtrans = 37.5, JCPcis =
=
(
38.8, 1C, CH (allyl)), 68.2 (d, J
= 37.5, 1C, CH (allyl)), 40.0
2
CPtrans 2
1.3, 1C, CH (allyl)), 68.5 (dd, JCPtrans= 37.5, 2JCPcis = 1.3, 1C,
2
2
4
2
2
dd, J = 33.1, J = 3.1, 1C, CH (NMe)), 38.3 (d, J = 32.5, 1C,
CP CP 3 CP
2
2
CH (allyl)), 40.2 (bs, 1C, CH (NMe)), 40.0 (bs, 1C, CH (NMe)),
2 3 3
CH (NMe)), 37.5 (d, J = 12.6, 1C, CH (NMe)), 37.4 (d, J =
.8, 1C, CH (NMe)), 23.1 (s, 1C, CH (allyl)). HR-MS (ESI, m/z):
3
CP
3
CP
2
3
4.6 (pt, J = 13.0, 2C, CH (NMe)), 22.4 (s, 1C, CH (allyl)). HR-
8
CP 3 3
3
3
+
+
+
calcd for C H N O P Pd 1127.2835, found 1127.2843 [M] .
MS (ESI, m/z): calcd for C68
1127.2832 [M] .
H
55
N
4
O
2
P
2
Pd 1127.2835, found
6
8
55
4
2 2
1
c-(R;R ;R). Yield: 168 mg (33%). Mp: 260−263 °C dec. 1P NMR
3
+
al
2
(
1
6
161.9 MHz, CDCl , 298 K, δ (ppm), J (Hz)): 152.3 (d, J = 66.4),
General Procedure for Pd-Catalyzed Allylic Substitutions of
rac-I. Allylic Alkylation. Reactions were carried out in a Schlenk tube
under N at 25 °C. A 0.01 mmol amount of the palladium complex
3
PP
2
1
49.7 (d, J = 66.4). H NMR (400 MHz, CDCl , 298 K): 8.25−
PP
3
3
.81 (m, 36H, CH(Ar)), 3.49 (d, J = 13.6, 3H, CH (NMe)), 3.26
HP
3
2
3
(
d, J = 13.6, 3H, CH (NMe)), 2.96 (bs, 1H, CH (syn)), 2.49 (bs,
(1a−c, 2a, or 2c) was dissolved in 8 mL of CH Cl . Then, 1 mmol of
HP
3
2
2
2
1
1
H, CH (anti)), 2.46 (bs, 1H, CH (anti)), 2.30 (bs, 1H, CH (syn)),
2
2
2
rac-3-acetoxy-1,3-diphenyl-1-propene and 1.5 mmol of Na(CH-
3
3
.71 (d, J = 10.8, 3H, CH (NMe)), 1.56 (d, J = 10.4, 3H,
CH (NMe)), 1.41 (s, 3H, CH (allyl)). C{ H} NMR (100.6 MHz,
CDCl , δ (ppm), J (Hz)): 146.3 (bs, 1C, C(Ar)), 146.2 (bs, 1C,
C(Ar)), 141.5 (d, J = 4.0, 1C, C(Ar)), 141.0 (d, J = 4.3, 1C,
C(Ar)), 140.5 (d, J = 7.9, 1C, C(Ar)), 140.1 (d, J = 7.4, 1C,
C(Ar)), 137.5 (pt, JCP = 7.6, 1C, C(allyl)), 134.0−119.4 (54C,
CPtrans 2
d, JCPtrans = 37.4, 1C, CH (allyl)), 40.4 (d, JCP = 5.2, 1C,
HP
3
HP
(COOMe) ) were added to the solution. The mixture was stirred at
2
13
1
3
3
room temperature for 24 h. At the end of the reaction, the mixture was
diluted with diethyl ether and washed with ammonium chloride
solution (3 × 10 mL) and water (2 × 10 mL). The organic phase was
dried over anhydrous Na SO and filtered off. After partially removing
the solvent under reduced pressure, the solution was eluted through a
short silica column with ethyl acetate. Conversions were determined
by H NMR. Enantiomeric excesses were determined by HPLC on a
Chiralcel-OD-H chiral column, using hexane/2-propanol = 95/5 as
eluent and a flow rate of 0.5 mL/min.
Allylic Amination. The procedure was analogous to that described
for allylic alkylation, using 3 mmol of benzylamine as nucleophile and
4 mL of CH Cl . Conversions and enantiomeric excesses were
determined by HPLC on a Chiralcel-OD-H chiral column, using
hexane/2-propanol = 99/1 as eluent and a flow rate of 0.3 mL/min.
General Procedure for Rh-Catalyzed Hydroformylation of
Styrene. A solution was prepared in a Schlenk flask dissolving
3
2
2
CP
CP
2
2
CP
CP
2
4
2
1
(
8C(Ar) + 36CH(Ar)), 77.2 (d, J
= 38.8, 1C, CH (allyl)), 68.8
2
2
2
1
2
2
CH (NMe)), 40.1 (d, J = 9.4, 1C, CH (NMe)), 34.6 (d, J =
3
CP
3
CP
2
1
1
1
3.1, 1C, CH (NMe)), 34.5 (d, J = 13.7, 1C, CH (NMe)), 22.3 (s,
3 CP 3
+
C, CH (allyl)). HR-MS (ESI, m/z): calcd for C H N O P Pd
3
68 55
4
2 2
+
127.2835, found 1127.2839 [M] .
General Procedure for the Synthesis of [Pd(η -2-Me-
C H )(P−P)]BPh (2a,c). To a solution of diamidophosphite a-
3
3
4
4
2
2
(
R;S ,S ;R) or c-(R;R ;R) (0.40 mmol) in toluene (10 mL) at 0 °C
al al al
3
was added dropwise a solution of [Pd(η -2-Me-C H )(μ-Cl)] (79 mg,
3
4
2
0
0
.20 mmol) in CH Cl (5 mL). Then a solution of NaPF (67 mg,
2
2
6
.40 mmol) in THF (5 mL) was added. After 1 h of stirring at room
temperature, a solution of NaBPh (204 mg, 0.60 mmol) in 20 mL of
MeOH was added. The white solid formed on standing was filtered off
and washed with deoxygenated water.
4
[
Rh(acac)(CO) ] (5.2 mg, 0.02 mmol), the corresponding ligand
0.04 mmol), 20.0 mmol of substrate, and 300 μL of n-dodecane as
2
(
internal standard in dry and degassed toluene up to a volume of 10
mL. The solution was transferred to a Parr autoclave. This was charged
to 20 bar of syn-gas and heated to the required temperature, while the
mechanical stirring was kept at 700 rpm. At the end of the reaction the
conversion and selectivity were analyzed by GC, while the ee was
analyzed by GC, using a Supelcoβ-Dex 120 chiral column, after
oxidation of the aldehydes to the corresponding carboxylic acids with
KMnO /MgSO in acetone. The [RhH(CO) (c-(R;Sal;R)] complex
was prepared in a Fischer−Porter tube, by reacting [Rh(acac)(η -
C H ) ] with 1 equiv of the ligand in CO/H atmosphere.
2
a-(R;S ,S ;R). Yield: 125 mg (25%). Mp: 174−177 °C dec.
al al
3
1
1
2
P{ H} NMR (101.2 MHz, CDCl , δ (ppm), J (Hz)): 139.4 (d, J
=
PP
3
2
1
9
(
4.9), 135.7 (d, J = 94.9). H NMR (500 MHz, CDCl , δ (ppm), J
P
P
3
Hz)): 8.05−6.75 (om, 44H, CH(Ar)), 4.87 (m, 1H, OCH), 4.60 (m,
2
2
1
1
H, OCH), 3.72 (bd, J = 7.0, 1H, CH (syn)), 3.32 (bd, J = 7.5,
HP 2 HP
3
3
H, CH (syn)), 3.15 (d, J = 14.5, 3H, CH (NMe)), 3.00 (d, J =
2
HP
3
HP
3
9
.5, 3H, CH (NMe)), 2.98 (d, J = 14.5, 3H, CH (NMe)), 2.92 (d,
3 HP 3
3
2
JHP = 9.5, 3H, CH (NMe)), 2.68 (d, J = 13.5, 1H, CH (anti)),
.49 (d, J = 13.5, 1H, CH (anti)), 1.58 (s, 3H, CH (allyl)), 1.47 (d,
JHH = 6.5, 3H, CH ), 1.43 (d, J = 6.5, 3H, CH3). C{ H} NMR
4
4
2
3
HP
2
2
2
2
HP
2
3
3
3
13
1
3
HH
2
4
2
2
H
DOI: 10.1021/acs.organomet.5b00457
Organometallics XXXX, XXX, XXX−XXX

Organometallics
Article
Tetrahedron: Asymmetry 2012, 23, 1052−1057. (c) Calabro, G.;
Drommi, D.; Bruno, G.; Faraone, F. Dalton Trans. 2004, 81−89.
ASSOCIATED CONTENT
■
*
S
Supporting Information
Figures, text, tables, and CIF files giving NMR spectra for
(
11) (a) Gavrilov, K. N.; Zheglov, S. V.; Vologzhanin, P. A.;
Rastorguev, E. A.; Shiryaev, A. A.; Maksimova, M. G.; Lyubimov, S. E.;
Benetsky, E. B.; Safronov, A. S.; Petrovskii, P. V.; Davankov, V. A.;
ligands b-(S;R R ;S), c-(R;R ;R), complexes 1a−c, 2a, and 2c,
al al
al
and the intermediate [RhH(CO) (c-(R;S ;R)] species, crys-
2
al
Schaf
(b) Gavrilov, K. N.; Zheglov, S. V.; Vologzhanin, P. A.; Maksimova, M.
G.; Safronov, A. S.; Lyubimov, S. E.; Davankov, V. A.; Schaffner, B.;
Borner, A. Tetrahedron Lett. 2008, 49, 3120−3123.
(12) Gavrilov, K. N.; Zheglov, S. V.; Benetsky, E. B.; Safronov, A. S.;
Rastorguev, E. A.; Groshkin, N. N.; Davankov, V. A.; Schaffner, B.;
Borner, A. Tetrahedron: Asymmetry 2009, 20, 2490−2496.
13) Gavrilov, K. N.; Rastorguev, E. A.; Zheglov, S. V.; Groshkin, N.
̈ ̈
fner, B.; Borner, A. Russ. Chem. Bull. 2008, 57, 2311−2319.
tallographic data and experimental details of the structure
determination for 1a-(S;S ,S ;S) and 1b-(R;R ,R ;R). The
̈
al al
al al
Supporting Information is available free of charge on the ACS
Publications website at DOI: 10.1021/acs.organomet.5b00457.
̈
̈
̈
AUTHOR INFORMATION
■
*
(
Corresponding Author
Tel: +34 934039132. Fax: +34 934021273. E-mail: rosa.
ceder@qi.ub.es.
N.; Boyko, V. E.; Safronov, A. S.; Petrovskii, P. V.; Davankov, V. A.
Russ. Chem. Bull. 2010, 59, 1242−1247.
(14) Gavrilov, K. N.; Zheglov, S. V.; Rastorguev, E. A.; Groshkin, N.
N.; Maksimova, M. G.; Benetsky, E. B.; Davankov, V. A.; Reetz, M. T.
Adv. Synth. Catal. 2010, 352, 2599−2610.
Notes
The authors declare no competing financial interest.
(15) Gavrilov, K. N.; Zheglov, S. V.; Shiryaev, A. A.; Groshkin, N. N.;
Rastorguev, E. A.; Benetskiy, E. B.; Davankov, V. A. Tetrahedron Lett.
2011, 52, 964−968.
ACKNOWLEDGMENTS
■
This work was supported by the Spanish Ministerio de Ciencia
(16) (a) Perandones, B. F.; Godard, C.; Claver, C. Top. Curr. Chem.
2013, 342, 79−115. (b) Klosin, J.; Landis, C. R. Acc. Chem. Res. 2007,
́
y Tecnologia (CTQ2010-15292/BQU) and by the Generalitat
4
́
0, 1251−1259. (c) Gual, A.; Godard, C.; Castillon, S.; Claver, C.
de Catalunya Departament d’Universitats, Recerca i Societat de
la Informacio (2009SGR1164). M.J.B. is grateful to the
́
IFARHU-SENACYT program for a Ph.D. grant.
Tetrahedron: Asymmetry 2010, 21, 1135−1146. (d) Franke, R.; Selent,
D.; Borner, A. Chem. Rev. 2012, 112, 5675−5732.
17) (a) Freixa, Z.; Bayon, J. C. J. Chem. Soc., Dalton Trans. 2001,
, S.; Claver, C.; Gomez,
̈
(
2
́
067−2068. (b) Sanhes, D.; Gual, A.; Castillon
́
́
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