Diamidophosphites from β-hydroxyamides: readily assembled ligands for Pd-catalyzed asymmetric allylic substitution

Article abstract of DOI:10.1039/d0dt00741b

Two groups of modular chiral diamidophosphite ligands were easily synthesised from accessibleN-Boc-amino alcohols and pseudodipeptides. The reaction of these compounds with [Pd(allyl)Cl]₂in the presence of AgBF₄yielded complexes [Pd(

Full text of DOI:10.1039/d0dt00741b

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Gavrilov, N. E. Borisova, A. Perepukhov, A. Maximychev, S. Zheglov, V. Gavrilov, I. Firsin, V. Zimarev, I. S.
Mikhel, V. Tafeenko, E. Murashova, V. Chernyshev and N. S. Goulioukina, Dalton Trans., 2020, DOI:
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COMMUNICATION
Douglas W. Stephen et al.
N-Heterocyclic carbene stabilized parent sulfenyl, selenenyl,
and tellurenyl cations (XH , X = S, Se, Te)
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ARTICLE
Diamidophosphites from β-Hydroxyamides: Readily Assembled
Ligands for Pd-Catalyzed Asymmetric Allylic Substitution
Received 00th January 20xx,
Accepted 00th January 20xx

a
a
b
c
Ilya V. Chuchelkin, Konstantin N. Gavrilov, Nataliya E. Borisova, Alexander M. Perepukhov,
c
a
a
a
Alexander V. Maximychev, Sergey V. Zheglov, Vladislav K. Gavrilov, Ilya D. Firsin, Vladislav S.
Zimarev, Igor S. Mikhel, Victor A. Tafeenko, Elena V. Murashova, Vladimir V. Chernyshev
DOI: 10.1039/x0xx00000x
b
d
b
b
b,d
a,b,d
and Nataliya S. Goulioukina
Abstract Two groups of modular chiral diamidophosphite ligands were easily synthesised from accessible N-Boc-amino
alcohols and pseudodipeptides. The reaction of these compounds with [Pd(allyl)Cl] in the presence of AgBF yielded
complexes [Pd(allyl)(L) ]BF . In addition, metallochelates [Pd(allyl)(L)]BF with (S)-methioninol-based P,S-bidentate ligands
2
4
2
4
4
were prepared. The structures of the novel ligands and complexes were elucidated by means of 2D-NMR and were
confirmed by single-crystal X-ray diffraction, as well as by DFT calculations. Asymmetric inducers of this type exhibited high
enantioselectivities in the Pd-mediated allylic substitution of (E)-1,3-diphenylallyl ethyl carbonate with CH
2
(CO
2
Me) (up to
2
9
8% ee) and (CH NH (up to 92% ee). Ee values of up to 86% and 73% obtained in the Pd-catalyzed allylic alkylation of
2 4
)
cinnamyl acetate with ethyl 2-oxocyclohexane-1-carboxylate and ethyl 2-oxocyclopentane-1-carboxylate, respectively. The
effects of the structural modules, such as the nature of the phosphorus-containing ring or exocyclic substituent, on the
catalytic
activity
and
enantioselectivity
were
investigated.
represents a challenging task.
Introduction
Chiral ligands derived from phosphorous acid (phosphite-
type ligands) are of considerable interest. Indeed, these
compounds with three P–O and/or P–N bonds have a number
of principal advantages: oxidation resistance, pronounced π-
acidity, easy preparation by simple condensation processes,
simplicity of variation to enable fine-tuning, good solubility of
metal complexes in a wide spectrum of catalytic reaction
media, and low cost.[
Myriads of phosphorus-containing chiral compounds were
successfully explored in various catalytic transformations and a
large number of such stereoselectors are commercially
[
1]
available. Nevertheless, the vast majority of the known
ligands are usually adjusted to a certain enantioselective
catalytic reaction or a group of related reactions. Highly
versatile and efficient (so-called «privileged») ligands are few
in number at high cost, restrains their wide practical
application. Besides, to foretell in advance a ligand structure
which would provide high activity and enantioselectivity for a
certain process is not yet possible, so the ligands design mainly
1g-k, 2c,d, 3]
Among ligands of phosphite nature, diamidophosphites
(
PON
They have significant differences from more widely used
phosphites (PO ) and phosphoramidites (PO N). In particular,
2
) constitute of a very attractive group of chiral inducers.
3
2
the trivalent nitrogen atoms bearing corresponding groups are
bulkier substituents at phosphorus atom than the bivalent
oxygen ones. In addition, the replacement of oxygen atoms in
the first coordination sphere of the phosphorus atom for
nitrogen ones increases the electron density on phosphorus.
Diamidophosphites have balanced electronic characteristics;
incorporation of the phosphorus and nitrogen atoms into the
[1h, 2]
relies on heuristic methods.
available from simple building blocks, inexpensive and
effective organophosphorus asymmetric inducers still
The synthesis of new, readily
a.
Department of Chemistry, Ryazan State University named for S. Yesenin, 46
Svoboda Street, 390000 Ryazan, Russian Federation. E-mail:
chuchelkin1989@gmail.com
Department of Chemistry, M. V. Lomonosov Moscow State University, Leninskie
1
,3,2-diazaphospholidine ring leads to a higher degree of
b.
rigidity and resistance to oxidation and hydrolysis. The
modular structure of diamidophosphites allows to vary
substituents at the phosphorus and/or nitrogen atoms in a
broad manner (thereby finely tuning the steric and electronic
parameters of the ligands), as well as the configuration of P*-
and C*-stereocenters. The presence of an asymmetric
electron-donating phosphorus atom can significantly favor an
Gory, GSP-1, 119991 Moscow, Russian Federation
Department of General Physics, Moscow Institute of Physics and Technology,
Institutskii per. 9, 141700 Dolgoprudny, Moscow Region, Russian Federation
A. N. Frumkin Institute of Physical Chemistry and Electrochemistry, Russian
Academy of Sciences, Leninsky Prospekt 31/4, 119071, Moscow, Russian
Federation
Electronic Supplementary Information (ESI) available: [details of any
supplementary information available should be included here]. See
DOI: 10.1039/x0xx00000x
c.
d.
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ARTICLE
Journal Name
efficient chirality transfer in a catalytic cycle. Therefore, known
P-monodentate, P,N- and P,P-bidentate diamidophosphite
ligands have found successful applications in the asymmetric
Pd-catalyzed allylation and cycloaddition, Rh-catalyzed
View Article Online
DOI: 10.1039/D0DT00741B
Results and discussion
Ligand Synthesis and Structure
As shown in Scheme 1, two sets of P-chirogenic
hydrogenation and hydroformylation, and in the Ni-catalyzed diamidophosphites were obtained in good yields by the
[
2e,f, 4]
hydrovinylation.
A successful strategy for the ligand design involves a accessible N-Boc-protected 1,2-amino alcohols
rational combination of a phosphacyclic moiety and an pseudodipeptides , which can be synthesized by simple
exocyclic substituent at the phosphorus atom. Phosphite condensation of N-Boc-amino acids with 1,2-amino alcohols.
ligands with hydroxyamide fragments
A-D (Fig. 1), successfully Pseudodipeptides 3a-c 3e, 3f and are novel compounds,
was characterized by X-ray crystal structure
reaction of phosphorylating reagent (5S)-5 with readily
[
11]
1,
2
or
3, 4
[
12]
L
,
4
applied in Rh- and Ir-catalyzed hydrogenation and Cu-catalyzed compound
conjugate addition, are a good case in point.[ Note that analysis (see Supplementary Information). Its worth
4
5]
recently we have developed modular P,P-bidentate mentioning that (S)-methioninol-derived chiral inducers L1d
bisdiamidophosphite stereoselectors
(
L
E
with oxalamide linkers and L3f possess an additional sulfide donor center. To evaluate
Fig. 1). It seems promising to prepare diamidophosphite the effect of relative backbone stereochemistry on the
ligands on a platform of readily accessible β-hydroxyamides, stereoinduction capability, ligand L3g (the diastereomer of
such as N-Boc-amino alcohols and pseudodipeptides (amides L3e) was prepared using (5R)- . Both enantiomers of the
of N-Boc-amino acids with amino alcohols). Pseudodipeptides phosphorylating reagent are easily available from natural
were shown to be efficient chiral inducers in Ru- and Rh- (S)- or unnatural (R)-glutamic acids.
catalyzed enantioselective transfer hydrogenation as well as synthesized the ligand L5 with the achiral phosphorus unit.
[
4r]
5
[
13]
5
[
14]
Besides, we have
pseudodipeptide-like phosphines
P
(Fig. 1) – in organocatalytic Synthesis of ligands L3a, L3d and L4 was described in our
[
6]
[15]
transformations.
Herein we describe the synthesis of two small, but
previous works.
All ligands easily purified by flash chromatography and can
structurally diverse groups of diamidophosphites with 1,3,2- be prepared on a gram-scale. They are stable enough to be
diazaphospholidine rings and β-hydroxyamide backbone. manipulated in air and stored under dry conditions at room
These ligands were employed in the Pd-catalyzed asymmetric temperature for several months with negligible degradation.
3
1
1
13
allylic substitution processes. Such catalytic transformations, Novel chiral inducers were fully characterized by P, H,
C
especially classical model reactions, are reliable methods of NMR and 2D NMR spectroscopy (COSY, NOESY, HSQC, and
new chiral inducers benchmark testing.[2d,e, 3o, 7] Additionally, HMBC), as well as by elemental analysis.
3
1
these reactions are broadly used in the asymmetric synthesis
of valuable organic and natural compounds, such as esters and narrow singlets, indicative of the stereoindividuality of these
The P NMR spectra of L1a-d and L3a-g shows single
[
8]
13
2
amides of enantioenriched unsaturated carboxylic acids, allyl ligands. In the С NMR spectra, the values of J(C,P) spin-spin
[
9]
amines and building blocks with quaternary stereocenters, coupling constants between NCH
2
CH
diaza-2-phosphabicyclo[3.3.0]octane core are in a range of
7.3-38.4 Hz corresponding to (R)- and (S)-configurations of
2
and P atoms of the 1,3-
[
10]
including those used in the medicinal chemistry.
3
E
Figure 1. Phosphites with hydroxyamide fragments LA-D, oxalamide-based bisdiamidophosphites L and pseudodipeptide-like phosphines P.
2
| J. Name., 2012, 00, 1-3
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DOI: 10.1039/D0DT00741B
Scheme 1. Synthesis of diamidophosphites L1a-d, L2, L3a-g, L4 and L5.
i
P*-stereocenters in “natural” L1a-d
,
L3a-f and “unnatural” L3g intermolecular N---H…S hydrogen bonds [N3…S1 3.609(9) Å,
ligands, respectively. [
4d,o, 13-15]
H3… S1 2.76 Å, N3---H3…S1 171 , symmetry code (i) 1+x, y, z].
i
i
o
The molecular structure of L1d was confirmed by X-ray The crystal packing is further stabilized by the weak Van der
powder diffraction. In the molecule (Figure 2), the P–O Waals interactions.
[1.670(8) Å] and P–N [1.732(12), 1.759(7) Å] bond lengths are
The structure of L3d was confirmed by single-crystal X-ray
comparable with the corresponding distances found in the diffraction analysis (Figure 3). Compound L3d crystallized from
Cambridge Structural Database (ConQuest, version 2.0.3)[16] chloroform solution in the packing mode with two symmetry-
for similar structures. In the crystal, the molecules which are independent molecules in the asymmetrical unit. These
related by translation along the a axis are linked into chains molecules, numerated as NN and NNA, are connected via
(see Supporting Information, Figure S53) via weak intermolecular hydrogen bonds (N4-H4…O4A, 2.06 Å and N3A-
H3A…O4, 2.18 Å). In both molecules, the P–O [1.618(2),
1
.620(2) Å] and P–N [1.662(3) - 1.724(2) Å] bond lengths are in
close agreement with the values retrieved from the Cambridge
Structural Database (CSD, version 5.38) for the related
structures.[
16]
In the phosphabicyclic cores both 1,3,2-
diazaphospholidine and pyrrolidine cycles have envelope
conformations with the flap atoms C5, C5A and C13, C13A,
respectively (Figure S54). Asymmetric P1 and P1A atoms have
the (R)-configuration; C2, C4, C15 and C2A, C4A, C15A atoms
have the (S)-configuration.
The (S)-proline-derived ligands L2 and L4 exist as a mixture of
two rotamers arising from the lack of free rotation around the
[17]
urethane C(O)-N bond and reveal two sets of signals in NMR
spectra. Thus the 31P NMR spectra in CDCl
exhibit two singlets
for each compound L2 [δ 122.80 (65%), 125.09 (35%)], L4 [δ
24.96 (64%), 124.11 (36%)]. The percentage of rotamers
3
P
P
1
depends on the solvent nature and temperature. The detailed
Figure 2. The molecular structure of L1d showing the atomic numbering
scheme. Hydrogen atoms are unnumbered for clarity.
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 3
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study of L2 in d
Journal Name
8
-toluene solution and L4 in CDCl
3
by 2D NMR
View Article Online
DOI: 10.1039/D0DT00741B
1
spectroscopy at –20 °C allowed to assign all signals in the H
and 1 C spectra of both isomers (see Supporting Information,
Figures S5a,b and S12a,b). The large values of the coupling
3
2
constants J(C,P) = 38.7–39.8 Hz for each rotamer of L2 and L4
suggest that the asymmetric phosphorus atom has the (R)-
configuration in either case. Note that the similar rotamerizm
was marked for N-Boc-pyrrolidine-based phosphite
phosphine ligands.
L
D
and
DFT-calculations of the potential energy
surface along O=C-N-C(H) performed for the structures of L2
[
5f, 18]
4,
and L4 are presented in Supporting Information (see Studies of
intramolecular rotation in N-Boc-proline derivatives).
Pd(II) allylic complexes
Allylic complexes of the general formula [Pd(allyl)(
L1d L3a-g or L4) were obtained by the reaction of the
organometallic precursor [Pd(allyl)Cl] with appropriate ligand
the molar ratio L/Pd = 2) and the chloride scavenging agent resonances for the terminal carbon atoms of the allyl fragment
AgBF (Scheme 2).
are clearly identified. That, along with the evident duplication
We have made a detailed NMR analysis of these complexes of most C and H NMR signals, suggests the nonequivalence
2 4
L) ]BF (L
Figure 3. The structure of the supramolecular assembly consisting of two
molecules L3d
.
=
,
2
(
4
1
3
1
[
4m,n,
in CD
2 2
Cl
solutions. The NMR assignments were carried out using of two coordinated phosphorus ligands in the complexes.
3
1
1
13
20]
a combination of spectroscopic techniques ( P, H, C, APT,
2 4
For [Pd(allyl)(L3d) ]BF it proved possible to specifically
DEPT, C- H HSQC, C- H HMBC, H- H COSY and H- H assign all H and C signals of two diastereoisotopic ligands
1
3
1
13
1
1
1
1
1
1
13
NOESY). In accordance with the lack of symmetry in the L3d (the NMR data are given in the Supporting Information).
complexes [Pd(allyl)(
L)
2
]BF
4
,
their NMR spectra reveal
The solid-state structure of [Pd(allyl)(L3d
)
2
]BF
4
was
nonequivalence of two coordinated diamidophosphites confirmed by X-ray diffraction (Figure 4). Single crystals of this
3
nonsymmetrically placed with respect to the

-allyl ligand. In complex were obtained from chloroform solution by slow
]BF
evaporation of the solvent at room temperature. The 1,3,2-
AB patterns ( J(P,P) ≈ 82-90 Hz, Δν(P,P) diazaphospholidine and pyrrolidine rings have envelope
100-109 Hz) are observed, suggesting magnetic conformation with the flap atoms C7, C7A and C9, C11A,
the 31P NMR spectra of [Pd(allyl)(L3b
)
2
]BF
, [Pd(allyl)(L3c
)
2
4
2
4
2 4
and [Pd(allyl)(L3g) ]BF
≈
nonequivalence of two strongly coupled phosphorus atoms. respectively. Note that the structure of the phosphabicyclic
However, in the case of complexes of ligands L1d and L3a,d,e,f moieties coincides with that in the starting L3d. Disregarding
31
P signals are degenerated into a single broad line because of the Pd1 atom as a substituent, the (R)-configurations of
very similar chemical shifts. Since the difference between the asymmetric P1 and P1A are retained.
chemical shifts of P atoms is very small (Δν(P,P) << J(P,P)) and
The coordination geometry of palladium can be considered
the P-P coupling constant is much larger then other constants as slightly distorted square planar. The four coordination
involved The effect of P-C virtual coupling is observed (virtual positions are occupied by two phosphorus atoms (P1 and P1A)
1
3
triplets and more complex signals) in the C NMR spectra of of two ligands L3d and two terminal carbon atoms (C81 and
[
19]
1
13
these compounds. Generally, the H and C NMR spectra of C83) of the allyl group. The Pd-C distances involving the
the complexes [Pd(allyl)( ]BF
appeared somewhat terminal allyl carbon atoms exhibit a pronounced asymmetric
complicated. In particular, most of the signals in the spectra of coordination, the Pd-C distance trans to P1A being 0.08 Å
Pd(allyl)(L4 ]BF
are too broadened to determine their longer than trans to P1.
multiplicity. Nevertheless, in each case separate resonances
It should be noted that the Pd–P1 distance trans to C81 is
L)
2
4
[
)
2
4
for four methylene protons, as well as closely spaced slightly longer than Pd–P1A that trans to C83 (by ca. 0.018 Å)
indicating that the closer located C81 has a somewhat stronger
trans influence than C83. Our analysis of the structures
available in the CSD showed that [Pd(allyl)(L3d
)
2
]BF
4
is not only
] (where is a
3 5
H is allyl moiety), but also the
+
the first complex of the type [Pd(C
diamidophosphite ligand and C
3
H
5
)
L
2
L
first complex of this type with any kind of allyl ligands which
was studied by X-ray diffraction. However, all bond distances
and angles in the immediate coordination sphere have typical
values, although the Pd–P distances lie at the short end of the
2
.262-2.314 Å range for analogous complexes stabilized with
[
20d,
21a]
phosphoramidites
diamidophosphites.[
or
P,P-bidentate
4m,n]
Actually, the Pd–P bond lengths are
Scheme 2. Synthesis of Pd(II) allylic complexes.
| J. Name., 2012, 00, 1-3
4
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ARTICLE
Table 1. NMR-signals of MeS-fragments of ligands L1d and L3fVaienwdAcrotircrleesOponnlindeing
complexes.
DOI: 10.1039/D0DT00741B
δ 13C (ppm)a
15.42 (s)
δ H (ppm)
1
b
L1dc
Pd(allyl)(L1d)
2.09 (s)
d
2.04 (s), 2.06 (s)e
2.31 (br.s), 2.43 (br.s)f
2.08 (s)
[
2
]BF
4
16.05 (s)
20.65 (br.s), 21.35 (br.s)f
d
[
Pd(allyl)(L1d)]BF
4
L3fc
15.46 (s)
d
[
2
Pd(allyl)(L3f) ]BF
4
16.05 (s)
2.04 (s)
d
21.14 (br.s), 22.06 (br.s)f
[
Pd(allyl)(L3f)]BF
4
2.30-2.55 (br.m)
[a] 125.7 MHz, ambient temperature. [b] 499.9 MHz, ambient temperature. [c]
Used CDCl as a solvent. [d] Used CD Cl as a solvent. [e] Separate signals of two
3
2
2
nonequivalent phosphorus ligands in the complex. [f] Separate signals of exo-
and endo- complexes.
2 4
spectroscopy, suggest that complex [Pd(allyl)(L3d) ]BF has the
same structure in solution and in the solid state.
As mentioned above, the peculiarity of ligands L1d and L3d
is the presence of an additional thioether structural moiety. To
get some insight into the coordination mode of these ligands,
Figure 4. The molecular structure of [Pd(allyl)(L3d
)
2
]BF
4
showing the atomic
are omitted for
numbering scheme. Hydrogen atoms and molecules of CHCl
3
clarity. Selected distances (Å) and angles (deg): Pd(1)-C(82) 2.06(3), Pd(1)-
C(81) 2.11(2), Pd(1)-C(83) 2.19(2), C(81)-C(82) 1.24(3), C(82)-C(83) 1.19(4),
Pd(1)-P(1A) 2.265(6), Pd(1)-P(1) 2.283(6), P(1)-O(1) 1.621(17), P(1A)-O(1A)
1
.609(17), P(1)-N(2) 1.618(19), P(1A)-N(2A) 1.64(2), P(1)-N(1) 1.719(18),
P(1A)-N(1A) 1.703(18), P(1A)-Pd(1)-P(1)107.4(2), C(81)-Pd(1)-C(83) 65.5(10),
C(83)-Pd(1)-P(1) 90.6(8), C(81)-Pd(1)-P(1A) 96.5(8), C(81)-Pd(1)-P(1)
56.1(8), C(83)-Pd(1)-P(1A) 161.9(8), C(82)-Pd(1)-P(1) 121.9(9), C(82)-Pd(1)-
P(1A) 129.9(10), C(82)-Pd(1)-C(81) 34.6(9), C(82)-Pd(1)-C(83) 32.3(11), ∑N(1)
58.8, ∑N(1A) 360.0, ∑N(2) 357.3, ∑N(2A) 352.8.
1
the cationic Pd-allyl complexes [Pd(allyl)(L1d)]BF
4
and
were prepared by the reaction of
and the appropriate diamidophosphite (molar
(Scheme 2). Due to a
and [Pd(allyl)(L3f)]BF , no
3
[
[
Pd(allyl)(L3f)]BF
Pd(allyl)Cl]
4
2
alike to a phosphite phosphorus atom bonded to a Pd(allyl)
ratio L/Pd = 1) in the presence of AgBF
dynamic nature of [Pd(allyl)(L1d)]BF
4
[
21b-d]
fragment with P,P-bidentate coordination.
The most intriguing geometric
Pd(allyl)(L3d ]BF is the remarkable shortening of the C–C
bonds in the coordinated allyl ligand. The C82–C83 distance is
.19(4) Å, which is more than ~0.15 Å shorter than the lengths
4
4
feature
of
detailed assignments were made. However, some conclusions
[
)
2
4
can be drawn.
The recognizable 13C and 1H resonances for the MeS
1
fragments in these complexes are evidently shifted downfield
compared to those of corresponding ligands L1d, L3f and
of the same bonds in other cationic Pd(allyl) complexes with
bis-(P-monodentate) or P,P-bidentate derivatives of
complexes [Pd(allyl)(L1d
)
2
]BF
4
, [Pd(allyl)(L3f
)
2
]BF
4
, suggesting
[
4m,n,21]
phosphorous acid.
We have no real explanation for this
[22]
the coordination of S atom to the metal center (Table 1).
Besides, the chemical shifts of terminal C atoms located in the
cis and trans orientations to the P atom differ significantly in
fact. The P−N bond lengths are both shorter than the normally
accepted bond distance (1.77 Å) and than the corresponding P-
N distances observed for the free L3d ligand, suggesting a
partial multiple bond character. The sum of the bond angles
around the nitrogen atoms is also consistent with a significant
4 4
the π-allyl ligand in of [Pd(allyl)(L1d)]BF and [Pd(allyl)(L3f)]BF
and this is in good agreement with well-known examples of
[23a,b]
P,S-chelate Pd(II) allylic complexes (Table 2).
2
sp character (∑N ~ 352.8-360°).
The P- resonances and most of H and 13C signals for
31
1
So, the complete asymmetry of the two coordinated
diamidophosphite ligands L3d and allyl ligand, revealed by X-
ray analysis, and the presence of two sets of resonances for
almost all carbon atoms and protons, established by NMR
[
4
Pd(allyl)(L1d)]BF are doubled due to the presence of different
exo- and endo-forms of the allylic ligand capable of
interconversion.
in the case of [Pd(allyl)(L3f)]BF
[23a,b]
The spectral pattern is more complicated
, the NMR spectrum of which
4
Table 2. 13C NMR-signals of allylic ligands and P NMR-signals of phosphorus ligands of complexes based on thiol-contained diamidophosphites L1d and L3f.
a
31
b
δ (ppm)
CH
CH
2
P
2
[
Pd(allyl)(L1d)
Pd(allyl)(L1d)]BF
Pd(allyl)(L3f) ]BF
Pd(allyl)(L3f)]BF
2
]BF
4
124.16 (t, J(С,P) = 8.4 Hz)
70.95-71.23 (br.m), 71.09-71.41 (br.m)
69.37-69.77 and 71.84-72.35 (br.m),c,d 81.25-82-10 (br.m)e
70.59-71.20 (br.m), 71.20-71.67 (br.m)
117.20 (s)
116.16 and 117.65 (s)c
[
4
124.03 and 124.23 (br.s)c
2
[
2
4
124.03 (t, J(С,P) = 8.6 Hz)
116.85 (s)
116.07 and 116.72 (s),c,f
17.38 and 117.80 (br.s)
d
e
[
4
124.31 (br.s)
71.51-72.51 (br.m) , 81.35-82.16 (br.m)
c,f
1
[a] 125.7 MHz, CD Cl , ambient temperature. [b] 202.4 MHz, CD Cl , ambient temperature. [c] Separate signals of exo- and endo- complexes. [d] Cis to P atom. [e] Trans
2 2 2 2
to P atom. [f] Separate signals of two diastereomers.
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ARTICLE
Journal Name
Table 3. Pd-catalyzed allylic alkylation of 7 with dimethyl malonate.[a]
displays two pairs of 31P resonances with different intensities.
This can be explained by the presence of two diastereomers
according to the configuration of the sulfur chiral center in the
View Article Online
DOI: 10.1039/D0DT00741B
[
23b-i]
thioether group coordinated to the Pd atom
with each
isomer existing in the exo- and endo- forms.
It should be mentioned that our attempts to lower the
temperature of NMR experiments for complexes of both types
Entry
Compound
L/Pd
Conversion [%]
ee [%][b,c]
4 2 4
([Pd(allyl)(L)]BF and [Pd(allyl)(L) ]BF ) led to an increase in the
signal broadening. This is likely due to a slowdown of proton
exchanges and/or the formation of inter- and intramolecular
hydrogen bonds between pseudodipeptide substituents.
Examples of such interactions in complexes with amide-
bearing ligands are well known. [
1
2
L1a
1
2
1
2
1
2
1
2
1
2
1
2
1
2
2
1
2
2
1
2
2
1
2
2
1
2
2
1
2
1
2
1
2
2
1
2
2
1
2
100
100
>99
99
97 (S)
98 (S)
96 (S)
97 (S)
88 (S)
94 (S)
92 (S)
91 (S)
90 (S)
91 (S)
88 (S)
90 (S)
84 (S)
90 (S)
93 (S)
60 (S)
67 (S)
74 (S)
83 (S)
86 (S)
84 (S)
69 (S)
82 (S)
82 (S)
76 (S)
87 (S)
88 (S)
80 (S)
85 (S)
88 (S)
89 (S)
59 (R)
71 (R)
66 (R)
95 (S)
97 (S)
96 (S)
23 (R)
41 (R)
L1a
3
L1b
4
L1b
5a,b, 24]
5
L1c
>99
>99
100
100
98
Pd-catalyzed allylic substitution
6
L1c
L1d
The efficiency of the novel diamidophosphites as chiral
inducers was explored in the standard test reaction of
enantioselective Pd-catalyzed allylic alkylation of (E)-1,3-
7
8
L1d
diphenylallyl ethyl carbonate (
7) with dimethyl malonate as a
9
[Pd(allyl)(L1d)]BF
4
C-nucleophile (Table 3). The catalysts were generated in situ
from allylpalladium(II) chloride dimer and a corresponding
ligand at a molar ratio L/Pd = 1 and 2 or used as pre-prepared
10
[Pd(allyl)(L1d)
2
]BF
4
98
11
12
13
14
15
16
17
18
19
L2
L2
>99
98
4 2 4
complexes [Pd(allyl)(L)]BF or [Pd(allyl)(L) ]BF . Quantitative or
L3a
L3a
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
>99
>99
99
nearly quantitative conversion of the starting substrate
observed in all cases.
7 was
[Pd(allyl)(L3a)
2
]BF
4
The sign of the enantioselectivity was mainly governed by
the absolute configuration at the phosphorus donor atom. The
L3b
L3b
(
S)-enantiomer of product 8a predominated in all cases, when
ligands with R-absolute configuration at the phosphorus atom
were used. In contrast, the L3g ligand with (S )-configuration
[Pd(allyl)(L3b)
2
]BF
4
L3c
L3c
P
afforded (S)-8a (Table 3, entries 32-34). The impact of the
chiral β-carbon atom of the exocyclic substituent was less
significant. Ligand L5 with the achiral phosphorus moiety led to
poor enantiocontrol (Table 3, entries 38, 39). A remarkable
cooperative effect between the configurations at phosphorus
and β-carbon atoms was observed, the opposite absolute
configurations resulting in a matched combination (Table 3,
entries 25-27 and 32-34). The influence of the size of the β-
substituent in ligands L1b-d was also noticed (Table 3, entries
20
21
22
[Pd(allyl)(L3c)
2
]BF
4
L3d
L3d
23
24
25
26
27
28
29
30
31
[Pd(allyl)(L3d)
2
]BF
4
L3e
L3e
[Pd(allyl)(L3e)
2
]BF
4
L3f
L3f
4
, 6, 8), and the bulky tert-butyl group provided a better result.
The conformationally constrained ligand L2 bearing N-Boc-
pyrrolidine moiety was less effective compared to the acyclic
analogues L1b-d (cf. entries 12 and 4, 6, 8). Somewhat
unexpectedly, ligand L1a with the achiral β-carbon atom
turned out to be the best asymmetric inductor providing up to
[Pd(allyl)(L3f)]BF
4
[Pd(allyl)(L3f)
2
]BF
4
98
32
33
34
L3g
L3g
100
100
100
100
100
>99
100
100
9
8% ee (Table 3, entry 2).
[Pd(allyl)(L3g)
2
]BF
4
In general, ligands based on pseudopeptides exhibited
lower enantioselectivity in comparison with their counter
partners based on N-Boc-amino alcohols (cf. entries 2 and 14,
35
36
37
38
39
L4
L4
[Pd(allyl)(L4)
2
]BF
4
4
and 23, 6 and 26, 8 and 29). In this series of ligands, the
L5
L5
restriction of conformational flexibility of the pseudopeptide
backbone was beneficial. The enantioselectivity up to 97% ee
was achieved by using the L4 ligand bearing a proline residue.
The efficiency of amino alcohol derivatives L1a-d and L2
was found to be almost insensitive to the molar ratio L/Pd
2 2 2
[a] All reactions were carried out with 2 mol% of [Pd(allyl)Cl] in CH Cl at room
temperature for 48 h (BSA, KOAc). [b] The conversion of substrate 7 and
enantiomeric excess of 8a were determined by HPLC (Kromasil 5-CelluCoat,
C H14/iPrOH = 99/1, 0.6 mL/min, 254 nm, t(R) = 17.7 min, t(S) = 19.0 min). [c] The
6
absolute configuration was assigned by comparison of the HPLC retention times
reported in the literature.[
(
Table 3, entries 1-12). In contrast, in the case of
25]
6
| J. Name., 2012, 00, 1-3
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Journal Name
ARTICLE
Table 4. Pd-catalyzed allylic amination of 7 with pyrrolidine.[a]
DOI: 10.1039/D0DT00741B
pseudopeptide-based ligands L3a-g and L4 the increase in L/Pd
molar ratio had a positive effect (Table 3, entries 13-37). In
general, individual cationic palladium complexes and
View Article Online
corresponding catalytic systems, formed in situ from L1d
or L4 and [Pd(allyl)Cl] , demonstrated comparable efficiency.
Both types of complexes [Pd(allyl)( )]BF and [Pd(allyl)( ]BF
, L3a-
g
2
L
4
L)
2
4
with sulfur-containing ligands L1d and L3f afforded practically
identical results (Table 3, entries 9, 10 and 30, 31).
ee [%][b,c]
Entry
Compound
L/Pd
Conversion [%]
The catalytic performance of the novel ligands in the Pd-
catalyzed allylic amination of compound
7
with pyrrolidine as
1
2
L1a
1
2
1
2
1
2
1
2
1
2
1
2
1
2
2
1
2
2
1
2
2
1
2
2
1
2
2
1
2
1
2
1
2
2
1
2
2
1
2
100
100
100
100
>99
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
95
85 (R)
92 (R)
90 (R)
91 (R)
90 (R)
89 (R)
84 (R)
90 (R)
58 (R)
57 (R)
88 (R)
88 (R)
84 (R)
83 (R)
72 (R)
60 (R)
62 (R)
40 (R)
83 (R)
78 (R)
84 (R)
54 (R)
63 (R)
75 (R)
76 (R)
74 (R)
82 (R)
76 (R)
74 (R)
58 (R)
86 (R)
58 (S)
60 (S)
69 (S)
86 (R)
90 (R)
73 (R)
10 (R)
8 (R)
the N-nucleophile mostly followed the same trends (Table 4).
The reaction proceeded with a quantitative conversion. The
P*-chiral diamidophosphites L1a-d and L2 with N-Boc-amino
alcohol side arm provided amine (R)-8b with 88-92% ee, while
L3a-g and L4 based on pseudodipeptides afforded 62-90% ee,
the opposite enantiomer (S)-8b prevailing in the case of L3g
Again, ligands L1a and L4 turned out to be the best asymmetric
inducers, whereas L5 furnished a virtually racemic product
L1a
3
L1b
4
L1b
5
L1c
6
L1c
L1d
.
7
8
L1d
(Table 4, entries 2, 36 and 38, 39). Similarly to the allylic
9
[Pd(allyl)(L1d)]BF
4
alkylation, ligand L3a provided considerably higher
a
10
[Pd(allyl)(L1d)
2
]BF
4
enantioselectivity than its bulkier analog L3b (Tables 3 and 4,
entries 13-18). Unlike the alkylation reaction in the allylic
amination the effect of the L/Pd molar ratio on the asymmetric
induction was not unidirectional and depended on the nature
of a ligand. This was also true for the replacement of in situ
generated catalytic systems with corresponding individual
palladium cationic complexes. Noteworthy, the complexes
11
12
13
14
15
16
17
18
19
L2
L2
L3a
L3a
[Pd(allyl)(L3a)
2
]BF
4
L3b
L3b
[Pd(allyl)(L1d)]BF
4
and [Pd(allyl)(L1d
)
2
]BF
4
revealed equally
]BF was more
(Table 4,
[Pd(allyl)(L3b)
2
]BF
4
moderate stereocontrol, while [Pd(allyl)(L3f
effective than the metallochelate [Pd(allyl)(L3f)]BF
entries 9, 10 and 30, 31).
Next, the novel diamidophosphites were studied in the Pd-
catalyzed allylic alkylation reaction of a non-symmetric
)
2
4
L3c
L3c
4
20
21
22
[Pd(allyl)(L3c)
2
]BF
4
L3d
L3d
substrate, cinnamyl acetate (
9), with ethyl 2-oxocyclohexane-
23
24
25
26
27
28
29
30
31
100
100
100
100
100
100
100
100
100
100
100
97
1
-carboxylate (10) as the C-nucleophile (Table 5). In this
[Pd(allyl)(L3d)
2
]BF
4
valuable process, a quaternary C*-stereocenter is formed on
the carbon atom belonging to the nucleophile. With the
ligands L1a-d and L2 a good to excellent conversion and a
moderate to good enantioselectivity of 60–86% ee (S) were
obtained, the molar ratio L/Pd = 2 being noticeably preferred
L3e
L3e
[Pd(allyl)(L3e)
2
]BF
4
L3f
L3f
(Table 5, entries 1-13). In the case of L3a-g and L4, the
[Pd(allyl)(L3f)]BF
4
enantioselectivity dropped to 45–82% ee, and L5 with achiral
phosphacycle was virtually ineffective. Surprisingly, the use of
[Pd(allyl)(L3f)
2
]BF
4
cationic
Pd(allyl)(
cases, gave product 11 with inverted absolute configuration
complexes
[Pd(allyl)(
L)]BF
4
and
especially
32
33
34
L3g
L3g
[
L)
2
]BF dramatically decreased ee values and, in some
4
[Pd(allyl)(L3g)
2
]BF
4
(Table 5, entries 22, 25, 28).
35
36
37
38
39
L4
L4
100
100
97
Five-membered ketoesters are known to be more
challenging C-nucleophiles in asymmetric allylic alkylation than
their six-membered analogues.[28] Our data on the reaction of
[Pd(allyl)(L4)
2
]BF
4
L5
L5
100
100
9
with ethyl 2-oxocyclopentane-1-carboxylate
summarized in the Table 6. Product 13 was proved to have the
S)-configuration, with the exception of the usage of the
unnatural” ligand L3g. At room temperature the catalysts
(12) are
(
“
[a] All reactions were carried out with 2 mol% of [Pd(allyl)Cl]
temperature for 48 h. [b] The conversion of substrate 7 and enantiomeric excess
of 8b were determined by HPLC (Daicel Chiralcel OD-H, C 14/iPrOH/Et NH =
00/1/0.1, 0.4 mL/min, 254 nm, t(R) = 13.1 min, t(S) = 14.8 min). [c] The absolute
configuration was assigned by comparison of the HPLC retention times reported
in the literature.[
2 2 2
in CH Cl at room
6
H
2
based on diamidophosphites L1a,b,d and L2 showed excellent
activity and moderate enantioselectivity of 55-67% ee, which
2
4o, 26]
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Table 5. Pd-catalyzed allylic alkylation of 9 with 10.[a]
was slightly dependent on the molar ratio L/Pd. In the case of
L2, the decrease in the
View Article Online
DOI: 10.1039/D0DT00741B
reaction temperature to –30°C resulted in an increase in the
asymmetric induction up to 73% ee (Table 6, entries 9 and 10).
In both cinnamyl acetate alkylation reactions, the N-Boc-
pyrrolidine derived ligand L2 was the best stereoselector.
Compounds L3a-g and L4 with pseudodipeptide fragments
provided up to 66% ee. As in the case of nucleophile 10, the
increase in the L/Pd molar ratio improved the conversion of
ee [%][b,c]
Entry
Compound
L/Pd
Conversion [%]
1
2
3
4
5
6
L1a
L1a
L1b
L1b
L1c
L1c
1
2
1
2
1
2
75
98
73 (S)
80 (S)
52 (S)
60 (S)
64 (S)
76 (S)
the starting substrate 9 (Table 6, entries 12-27).
98
Conclusions
100
99
In summary, two sets of diamidophosphites, which
combine the advantages of the 1,3,2-diazaphospholidine ring
and the N-Boc-amino alcohol or pseudodipeptide moieties,
were prepared. These ligands of modular architecture are easy
to handle, simple to synthesize and modify with the well-
studied chemistry of amino alcohols/amino acids. Note that
100
7
8
9
L1d
L1d
1
2
1
91
100
78
57 (S)
71 (S)
53 (S)
[Pd(allyl)(L1d)]BF
4
10
[Pd(allyl)(L1d)
2
]BF
4
2
1
2
2
1
2
2
1
2
2
1
2
2
1
2
2
1
2
2
75
>99
100
100
51
22 (S)
70 (S)
84 (S)
86 (S) [d]
82 (S)
80 (S)
67 (S)
76 (S)
78 (S)
60 (S)
67 (S)
66 (S)
4 (R)
compounds L1d and L3f are representatives of scarcely studied
P,S-bidentate diamidophosphite ligands.[29]
11
12
13
14
L2
L2
The novel diamidophosphites, differing in the relative
stereochemistry of the phosphacycle and the nature of the
exocyclic β-hydroxyamide fragment, were evaluated in four
test reactions of Pd-catalyzed asymmetric allylic substitution,
and high enantioselectivities (ee's up to 98%) were achieved.
Generally, N-Boc-amino alcohol derivatives were found to be
noticeably more efficient. The ligands L1a and L2 provided the
best results in the allylic substitution involving prochiral
electrophilic or nucleophilic reaction partners, respectively.
Among the pseudodipeptide-based set, L3a and L4 are the top
ones. It's interesting that ligands L2 and L4 with the N-Boc-
pyrrolidine fragment are efficient stereoselectors, despite of
their existence in two rotameric forms. This is in good
agreement with the fact that a large variety of chiral inducers
have been demonstrated to benefit from their conformational
L2
L3a
L3a
15
16
17
18
19
20
21
22
23
100
56
[Pd(allyl)(L3a)
2
]BF
4
L3b
66
L3b
100
92
[Pd(allyl)(L3b)
2
]BF
4
L3c
19
L3c
100
70
[Pd(allyl)(L3c)
L3d
2
]BF
4
19
62 (S) [e]
68 (S) [e]
5 (R)
24
25
26
L3d
60
[Pd(allyl)(L3d)
2
]BF
4
99
[
30]
multiplicity. Taking the Pd-mediated asymmetric synthesis
of compound 8a as a test case, it is clear that the new
stereoselectors are much superior to complex peptide-based
macromolecular P,P- and P,S-bidentate phosphines, which
provided no more than 63% ee.[31]
L3e
48
62 (S)
72 (S)
25 (R)
2
7
8
L3e
100
100
2
[Pd(allyl)(L3e)
2
]BF
4
29
30
31
32
33
34
35
L3f
L3f
1
2
1
2
1
2
2
1
2
2
1
2
19
53
17
49
0
27 (S)
45 (S)
40 (S)
12 (S)
-
Palladium allylic complexes of the general formula
[Pd(allyl)(L3f)]BF
4
[
Pd(allyl)(
L
)
2
]BF
4
were obtained. The nonequivalence of two
]BF is the
2
[Pd(allyl)(L3f) ]BF
4
P*-monodentate ligands was shown. [Pd(allyl)(L3d
)
2
4
L3g
L3g
first Pd(II) allylic complex with two diamidophosphite ligands
which was studied by X-ray diffraction. Besides, P,S-chelate
complexes of the general formula [Pd(allyl)(L)]BF were
4
synthesized based on diamidophosphite-thioether ligands.
Additional studies revealing the potential of novel
diamidophosphites in other transition metal-catalyzed
asymmetric transformations are currently in progress in our
laboratories.
100
96
60 (R)
23 (R)
74 (S)
76 (S)
60 (S)
15 (R)
26 (R)
2
[Pd(allyl)(L3g) ]BF
4
36
37
38
L4
37
L4
100
90
[
Pd(allyl)(L4)
2
]BF
4
3
9
0
L5
67
4
L5
100
[
a] All reactions were carried out with 2 mol% of [Pd(allyl)Cl]
temperature for 48 h (BSA, Zn(OAc) ). [b] The conversion of substrate 9 and
enantiomeric excess of 11 were determined by HPLC (Kromasil 5-CelluCoat,
14/i-PrOH = 95/5, 0.4 mL/min, 254 nm, t(R) = 14.5 min, t(S) = 16.9 min). [c]
The absolute configuration was assigned by comparison of the HPLC retention
2
in toluene at room
2
6
C H
times reported in the literature.[ [d] at – 30 °C. [e] Ref.
27]
[15]
8
| J. Name., 2012, 00, 1-3
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Journal Name
ARTICLE
Table 6. Pd-catalyzed allylic alkylation of 9 witn 12.[a]
View Article Online
DOI: 10.1039/D0DT00741B
Notes and references
1
a) J. M. Brown in Comprehensive Asymmetric Catalysis, Vol.
1
(Eds.: E. N. Jacobsen, A. Pfaltz, Y. Yamamoto), Springer,
Berlin, 1999, pp. 121–182; b) T. Ohkuma, M. Kitamura, R.
Noyori in Catalytic Asymmetric Synthesis (Ed.: I. Ojima),
Wiley-VCH, New York, 2000, pp. 1–110; c) M. J. Burk, Acc.
Chem. Res., 2000, 33, 363–372; d) A. Börner (Ed.) in
Phosphorus Ligands in Asymmetric Catalysis, Wiley-VCH,
Weinheim, 2008; e) C. A. Falciola, A. Alexakis, Eur. J. Org.
Chem., 2008, 3765–3780; f) H.-U. Blaser, H.-J. Federsel (Eds.)
in Asymmetric Catalysis on Industrial Scale, 2nd ed., Wiley-
VCH, Weinheim, 2010; g) P. W. N. M. van Leeuwen, P. C. J.
ee [%][b,c]
Entry
Compound
L/Pd
Conversion [%]
1
2
3
4
5
6
7
8
9
L1a
L1a
L1b
L1b
L1c
L1c
L1d
L1d
L2
1
2
1
2
1
2
1
2
1
1
2
1
2
1
2
1
2
1
2
1
2
1
2
1
2
1
2
100
97
65 (S)
66 (S)
62 (S)
64 (S)
-
Kamer, C. Claver, O. Pamies, M. Diéguez, Chem. Rev., 2011
,
100
100
0
1
11, 2077–2118; h) S. Luhr, J. Holz, A. Börner,
ChemCatChem, 2011, 3, 1708–1730; i) P. C. J. Kamer, P. W.
N. M. van Leeuwen (Eds.) in Phosphorus(III) Ligands in
Homogeneous Catalysis: Design and Synthesis, Wiley,
Chichester, 2012; j) W. Fu, W. Tang, ACS Catal., 2016, 6,
31
57 (S)
50 (S)
55 (S)
4
2
6
814–4858; k) O. Pamies, M. Diéguez, Chem. Rec., 2016, 16,
460–2481; l) B. V. Rokade, P. J. Guiry, ACS Catal., 2018, 8,
24–643.
100
100
100
100
100
77
67 (S)
73 (S) [d]
2
a) M. Diéguez, A. Ruiz, C. Claver, Dalton Trans., 2003, 2957–
2963; b) A. G. Tolstikov, T. B. Khlebnikova, O. V. Tolstikova,
G. A. Tolstikov, Russ. Chem. Rev., 2003, 72, 803–822; c) K.
Barta in Synthesis and application of chiral phosphorous
triamide ligands, PhD. Thesis RWTH Aachen University,
Germany, 2008; d) J. F. Teichert, B. L. Feringa, Angew. Chem.,
Int. Ed., 2010, 49, 2486–2528; e) Q.-L. Zhou (Ed.) in Privileged
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10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
L2
L2
64 (S)
60 (S)
32 (S)
60 (S)
64 (S)
50 (S)
34 (S)
12 (S)
40 (S)
42 (S)
20 (S)
18 (S)
50 (S)
24 (R)
44 (R)
66 (S)
66 (S)
L3a
L3a
L3b
L3b
L3c
L3c
L3d
L3d
L3e
L3e
L3f
L3f
L3g
L3g
L4
99
29
89
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[
a] All reactions were carried out with 2 mol% of [Pd(allyl)Cl]
temperature for 48 h (BSA, Zn(OAc) ). [b] The conversion of substrate 9 and
enantiomeric excess of 13 were determined by HPLC (Daicel Chiralcel OD-H,
14/i-PrOH = 99/1, 0.6 mL/min, 254 nm, t(R) = 24.0 min, t(S) = 27.0 min). [c]
2
in toluene at room
2
6
C H
The absolute configuration was assigned by comparison of the HPLC retention
times reported in the literature.[ [d] at – 30 °C.
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Conflicts of interest
There are no conflicts to declare.
Acknowledgements
This work was financially supported by the Russian Science
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(regarding chemistry of L1d and L3f)).
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,
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BocHN
Asymmetric Palladium
*
Ph
N
H
Catalysis
N
View Article Online
DOI: 10.1039/D0DT00741B
N
P*
Nu
O
R1 R2
amide
Ph
*
Ph
up to 98% ee (Nu = CH(CO2Me)2)
up to 95% ee (Nu = (CH2)4NH)
O
NHBoc
NHBoc
NNP
L
O
OEt
Ph
O
N
P
Ph
N
N
*
H
Ph
R3 R4
O
(
)
n
up to 86% ee (n = 1)
up to 73% ee (n = 0)
[
2
Pd(allyl)L ]BF4 and [Pd(allyl)L]BF4
Novel diamidophosphites based on β-hydroxyamides were prepared, their individual and in situ formed
complexes were tested in the Pd-mediated allylations.