This document is the Accepted Manuscript version of a Published Work that appeared in final form in Organometallics,
copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited
and published work see http://pubs.acs.org/doi/pdf/10.1021/acs.organomet.5b00962

Palladium-Based Supramolecularly Regulated Catalysts for
Asymmetric Allylic Substitutions
Laura Rovira,†,& Héctor Fernández-Pérez,†,& and Anton Vidal-Ferran*,†,&,‡
†
&

Institute of Chemical Research of Catalonia (ICIQ), Avgda. Països Catalans 16, 43007 Tarragona, Spain
The Barcelona Institute of Science and Technology, Avgda. Països Catalans 16, 43007 Tarragona, Spain

‡

Catalan Institution for Research and Advanced Studies (ICREA), Passeig Lluís Companys 23, 08010 Barcelona
Supporting Information
ABSTRACT: Herein is reported the effect of different polyether binders (alkali metal, alkaline earth metal and lanthanide salts) as
regulation agents to enhance the catalytic properties of palladium complexes derived from enantiopure bisphosphite ligands in
allylic substitutions. The addition of RbOAc or M(OTf) x (M = Mg2, La3 or Ho3) led to positive effects in enantioselectivity (by
up to 16% ee) for the allylic substitution reactions. These ligands coordinated in the usual cis-fashion or in an unprecedented transfashion to the palladium center, depending on the phosphite group, and presented different reactivity in the allylic substitutions.

INTRODUCTION
The search for efficient chiral catalysts for the broadest possible substrate scope in a given transformation is still a cuttingedge research goal, as structural changes to the substrate(s)
and or reagent(s) often translate into a loss of enantioselectivity. Within the supramolecular enantioselective catalysis arena,1 progress has been made in regulating the size and shape of
the chiral catalyst,2 or in modifying the first-sphere coordination geometry of the active metal.3 However, there are few
examples of fine-modification of the geometry of the activesite that do not imply major alteration of the principal structural features of the enantioselective catalyst. 4,5
Fan et al. pioneered the use of supramolecularly regulated
polyether-based ligands for rhodium-mediated hydrogenations.5b These authors reported the first example on the use of
rhodium complexes derived from bisphosphite-polyether
ligands in asymmetric hydrogenation, whose catalytic performance in terms of enantioselectivity was enhanced by the
addition of a regulation agent (RA, Figure 1).5b Later, we also
demonstrated that conformationally transformable bisphosphite ligands4a-c incorporating polyether groups behaved as
supramolecularly regulated ligands in asymmetric hydroformylations4a-c and hydrogenations4b (Figure 1). We showed
that enantioselectivities in the transformation of interest can be
maximized by the choice of whether or not to use an RA (and
if so, which one).4a-c Computational studies revealed that the
significant increase in enantiomeric excess provided by the
RAs in hydroformylation reactions resulted from adaptation of
the P-Rh-P bond angle ().4b
Pd-mediated allylic substitutions represent an efficient transformation to stereoselectively form CC and CX bonds.6

Palladium complexes derived from P ligands are efficient
catalysts for the reaction between allylic alcohol derivatives
and nucleophiles,7 which have often been generated in situ
from the protonated nucleophile (i.e. a malonic ester) in the
presence of N,O-bis(trimethylsilyl)-acetamide (BSA) and
catalytic amounts of an alkali metal salt.8
Herein we report our efforts in expanding our supramolecular
regulation strategy to allylic substitutions. We envisaged that
the combination of ligands 1ac with Pd(II) precursors suitable for this chemistry and an array of metal salts (for both
generating the required nucleophile and triggering the regulation mechanism in our ligands) could function as supramolecularly regulated catalysts in allylic substitutions.

Figure 1. Supramolecularly regulated bisphosphite ligands in
enantioselective catalysis (BIPOL = [1,1'-biphenyl]-2,2'-diol,
BINOL = [1,1'-binaphthalene]-2,2'-diol).

RESULTS AND DISCUSSION
Ligand Synthesis. We initially designed ligands 1ac by
combining the linker group that showed the highest regulation
ability in our hydroformylation studies4b (see blue fragment in
Figure 2) and an array of stereogenic phosphite groups (see
green fragment in Figure 2). Bisphosphites 1a and 1b had
already been described9,4b,c and compound 1c was prepared in
an analogous manner to 1a and 1b: reaction of tetraethylene
glycol with two equivalents of the corresponding chlorophosphite in the presence of a base (NEt3).

Figure 2. Set of supramolecular bisphosphite ligands 1ac.

Table 1. Pd-mediated Asymmetric Allylic Alkylation of 2
with Ligands 1ac and Different Regulation Agents (RAs)a

conducted in dichloromethane (CH2Cl2) as we considered that
this solvent would provide a compromise between the solubility of the RA and its binding strength with the polyether fragment.4b,10 As illustrated in Table 1, the palladium complexes
derived from bisphosphites 1ac provided active catalysts
displaying full conversion in almost all cases (see Table 1).
Selectivity in the absence of regulation agents was moderate
and highly dependent on the nature of the phosphite fragment.
The palladium complex of ligand 1a incorporating an (Sa)BINOL-derived phosphite fragment provided the best enantioselectivity (up to 44% ee, entry 1 in Table 1). A similar ee was
observed for ligand 1c, although reactivity was lower (see
entry 7 in Table 1). Finally, the sterically more demanding
phosphite groups in ligand 1b led to a decrease in ee (see entry
4 in Table 1). As our regulation design allows new catalytic
systems to be generated by employing a set of RAs, subsequent attempts to improve enantioselectivity following this
strategy (addition of LiOAc or CsOAc) resulted in some cases
in higher ee’s for ligands 1a and 1b (increase of up to 10% ee,
compare entry 1 with 3 in Table 1).
We then studied the influence of the Pd precursor on the outcome of the allylic substitutions by incorporating [PdCl2(cod)]
to our studies (Table 2). Interestingly, [PdCl2(cod)] performed
better than [Pd(μ-Cl)(η3-C3H5)]2 in terms of enantioselectivity
(for instance, compare entries 13 in Table 1 with entries 1, 2
and 9 in Table 2). Of all the RA/ligand combinations tested,
RbOAc●1a gave the best results: full conversion and 65% ee
(increase of 6% ee with respect to when no RA was used,
compare entry 1 with 6 in Table 2). Higher amounts of RbOAc
did not bring any advantage in the result of the reaction and
lower temperatures (0 ºC) resulted in no conversion (see entries 7 and 8 in Table 2, respectively). Two different potassium
Table 2. Allylic Alkylations of 2 with Bisphosphite Ligand
1a or 1c and Different RAsa

conv.
(%)b

ee 3 (%,
config.)c

>99

44 (R)

>99

21 (R)

>99

54 (R)

>99

20 (R)

LiOAc

>99

26 (R)

CsOAc

>99

26 (R)

60

43 (S)

LiOAc

>99

24 (S)

CsOAc

90

39 (S)

entry

ligand

RA

1

1a

2

1a

LiOAc

3

1a

CsOAc

4

1b

5

1b

6

1b

7d

1c

8

1c

9d

1c

conv.
(%)b

ee 3 (%,
config.)c

>99

59 (R)

LiOAc

>99

46 (R)

1a

NaOAc

>99

62 (R)

1a

KOAc

>99

63 (R)

1a

KF

>99

62 (R)

1a

RbOAc

>99

65 (R)

1a

RbOAc

>99

65 (R)

1a

RbOAc

0

n.d.

>99

56 (R)

entry

ligand

1

1a

2

1a

3
4
5
6
d

RA

a

Reaction conditions are indicated in the above scheme unless otherwise stated. b Determined by 1H NMR spectroscopy. c Determined by
HPLC on chiral stationary phases. d Reaction performed at rt for 24h.

7

8e

Pd-mediated Asymmetric Allylic Substitutions.
With ligands 1ac in hand, we then assessed their catalytic
activity in combination with an array of RAs in allylic substitutions. Initially, we chose 1,3-diphenylallyl acetate 2 as the
substrate and dimethyl malonate (DMM) as the nucleophile.
The precatalysts were generated in situ from [Pd(μ-Cl)(η3C3H5)]2, the ligands 1ac and the RA. The reactions were

9

1a

CsOAc

f

10

1a

Mg(OTf)2

15

56 (R)

11f

1a

Ba(OTf)2

>99

4 (R)

12

1a

La(OTf)3

>99

3 (R)

13

1a

Ho(OTf)3

>99

rac

14f

1c

15f

1c

16f

1c

0
0

n.d.

CsOAc

a

n.d.

LiOAc

0

n.d.

b

c

See footnotes a in Table 1. See footnotes b in Table 1. See footnotes
c in Table 1. d 1.7 equiv of RA relative to Pd precursor was used. e Reaction performed at 0 ºC for 24h. f Reaction performed at rt for 24h.

salts with different counterions (i.e. KOAc and KF) were used
as RAs, and no differences in reactivity were observed (compare entry 4 with 5 in Table 2). It should be noted that the use
of alkaline earth metal or lanthanide triflates as RAs led to
detrimental effects for both reactivity and selectivity (see
entries 1013 in Table 2). The palladium complex derived
from bisphosphite 1c led to inactive catalysts in this chemistry
since no reactivity for the allylic alkylation of 2 was observed
even in the presence of different RAs (see entries 1416 in
Table 2).
We then assessed the supramolecularly regulated catalysts
derived from the lead bisphosphite 1a in allylic substitutions
using benzylamine (BZA) as a nitrogen nucleophile. Standard
screening conditions were used and the results of this study are
shown in Table 3. Complexes derived from 1a performed as
efficient catalysts in the allylic amination of 2 in terms of
conversion (see Table 3). When no RAs were used, a low ee
was achieved (30% ee, see entry 1 in Table 3). Interestingly,
and in sharp contrast with the results using a C-nucleophile, an
improvement in ee was obtained by using group II or lanthanides triflates as RAs (increase of up to 16% ee with
Mg(OTf)2, La(OTf)3 or Ho(OTf)3; see entries 4, 7, and 8 in
Table 3) and [Pd(μ-Cl)(η3-C3H5)]2 as palladium precursor
(compare entry 4 with 5 in Table 3).

derived from bisphosphites 1 were efficient catalysts in the
alkylation of substrate 5 in terms of conversion (see Table 4).
As expected for palladium-based catalysts,7d,e and in the absence of regulation agents, either low branched-to-linear ratios
(b/l ratio, see entries 1 and 4 in Table 4) or exclusively the
linear product 7 (see entries 5 and 12 in Table 4) were
achieved depending on both the bisphosphite and the palladium precursor (see results for ligand 1b, compare entry 4 with
5 in Table 4). In terms of enantioselectivity, a respectable
value of 60% ee at a b/l ratio of 12/88 was achieved by using
the palladium complex derived from 1b and [Pd(μ-Cl)(η3C3H5)]2 (see entry 4 in Table 4). Interestingly, the use of LiOAc or CsOAc as RAs led to an increase in the regioselectivity of the reaction for the palladium complex derived of 1a (b/l
ratio up to 17/83; entries 2 and 3 in Table 4).7 Unfortunately,
the enantioselectivity could not be further improved for those
catalytic systems leading to the highest ratio of branched
product.
Table 4. Allylic Alkylation of 5 with Bisphosphite Ligands
1ac and Different RAsa

ligand

1

1a

2

1a

LiOAc

3

1a

CsOAc

Table 3. Allylic Amination of 2 with Bisphosphite Ligand
1a and Different RAsa

RA

conv.
(%)b

6/7
ratiob

ee 6 (%,
config.)c

>99

entry

14/86

28 (R)

>99

17/83

19 (R)

>99

17/83

32 (R)

12/88

60 (R)

4

1b

>99

d

1b

75

>1/99

n.d.

6

1b

LiOAc

>99

14/86

57 (R)

7

1b

CsOAc

>99

11/89

55 (R)

8

1b

Mg(OTf)2

>99

15/85

50 (R)

9

1b

Ba(OTf)2

0

n.d.

n.d.

>99

12/88

42 (R)

5

entry

ligand, Pd-precursor

1

1a, [Pd(μ-Cl)(η3-C3H5)]2

conv.
(%)b

ee 4 (%,
config.)c

10

1b

La(OTf)3

>99

RA

30 (S)

11

1b

Ho(OTf)3

1c

d

1a, [Pd(μ-Cl)(η -C3H5)]2

LiOAc

>99

33 (S)

12

3

1a, [Pd(μ-Cl)(η3-C3H5)]2

CsOAc

0

n.d.

13

1c

46 (S)

14

1c

2

4
5
6
7
8

3

3

1a, [Pd(μ-Cl)(η -C3H5)]2
1a, [PdCl2(cod)]

Mg(OTf)2

>99

Mg(OTf)2

35

29 (S)

3

Ba(OTf)2

>99

45 (S)

3

La(OTf)3

>99

Ho(OTf)3

>99

46 (S)

n.d.

n.d.

>1/99

n.d.

LiOAc

>99

>1/99

n.d.

CsOAc

>99

>1/99

n.d.

b

c

See footnotes a in Table 1. See footnotes b in Table 1. See footnotes
c in Table 1.. d [PdCl2(cod)] (5.0 mol%) was used as metal precursor and
the reaction was performed at rt for 6h.

46 (S)

3

a

0
>99

1a, [Pd(μ-Cl)(η -C3H5)]2
1a, [Pd(μ-Cl)(η -C3H5)]2
1a, [Pd(μ-Cl)(η -C3H5)]2

a

See footnotes a in Table 1. b See footnotes b in Table 1. c See footnotes
c in Table 1. d Reaction performed at rt for 72h.

Finally, we tested our set of supramolecular bisphosphite
ligands in the Pd-mediated allylic substitution of cinnamyl
acetate 5 using DMM as nucleophile under standard screening
conditions (Table 4). In general terms, palladium complexes

Coordination studies. After having studied bisphosphite
ligands 1ac in Pd-mediated allylic substitutions, we carried
out coordination studies in order to gain insight into the reactivity of the palladium precatalysts derived from 1a and 1c
(see Table 2) as well as into the regulation mechanism. The
reaction of bisphosphites 1a and 1c with [PdCl2(cod)] proceeded smoothly to provide the corresponding palladium
complexes [PdCl2(1a)] (8a) and [PdCl2(1c)] (8c), which were
isolated and characterized. The 31P{1H} NMR spectra for

compounds 8a and 8c showed single resonances at 109.8 and
90.2 ppm, respectively.11 It is interesting to note that the signal
of TADDOL-based bisphosphite 8c was shielded upfield with
respect to the signal of 8a (Δδ ≈ 20 ppm), which might hint at
important structural differences between palladium complexes
8a and 8c. Interestingly, compounds 8a and 8c could be crystallized, and X-ray analysis unambiguously established their
structures.12 For 8a, the palladium center had a distorted
square-planar geometry in which the two phosphorus groups
of ligand 1a were coordinated in a cis-fashion (see Figure 3
and Table 5). Meanwhile in complex 8c, the palladium center
also displayed a square-planar geometry but with the phosphorus groups of ligand 1c occupying trans-binding sites (see
Figure 3 and Table 5). To the best of our knowledge, this is
the first reported example of a trans-chelating bisphosphite in
Pd complexes, which appears to be bound to a lack of reactivity in this chemistry (see entries 1416 in Table 2). Finally, to
support our hypothesis on the regulation mechanism, we studied the interaction of RbOAc with the regulation site of the
highest-performing palladium complex 8a. NMR analysis
qualitatively demonstrated the binding of RbOAc within the
polyethyleneoxy moieties: the addition of incremental
amounts of RbOAc to a solution of 8a (up to 1.7 equiv.)
caused significant changes to the chemical shift, multiplicity,
and signal width of the polyethyleneoxy fragments.12 These
results suggest that binding of RbOAc within the polyethyleneoxy moieties is involved in the regulation effects mediated by the RA in the described allylic substitutions.

Figure 3. Crystal structures of 8a and 8c (ORTEP drawings
showing in both cases thermal ellipsoids at 30% probability).

Table 5. Selected Bond Lengths (Å) and Angles () for
Palladium Complexes 8a and 8c.
Compound 8a

Compound 8c

Atoms

Lengths (Å)
or Angles ()

Atoms

Lengths (Å)
or Angles ()

Pd1-P1

2.2141(17)

Pd1-P1

2.287(2)

Pd1-P2

2.2191(16)

Pd1-Cl1

2.291(2)

Pd1-Cl2

2.3113(17)

Pd1-Cl2

2.291(2)

Pd1-Cl1

2.3450(16)

Pd1-P2

2.301(2)

P1-Pd1-P2

92.45(6)

P1-Pd1-Cl1

91.30(7)

P1-Pd1-Cl2

172.10(6)

P1-Pd1-Cl2

88.36(8)

P2-Pd1-Cl2

93.27(6)

Cl1-Pd1-Cl2

174.58(10)

P1-Pd1-Cl1

83.41(6)

P1-Pd1-P2

177.39(8)

P2-Pd1-Cl1

171.04(5)

Cl1-Pd1-P2

91.30(7)

Cl2-Pd1-Cl1

91.66(6)

Cl2-Pd1-P2

89.07(8)

CONCLUSIONS
In summary, we designed and prepared supramolecularly
regulated ligands for Pd-mediated asymmetric allylic substitutions. The selectivity (both regio- and stereoselectivity) of the
allylic substitutions mediated by bisphosphites 1 could be
regulated by using several alkali metal, alkaline earth metal or
lanthanide salts as regulation agents. Positive increments in
the regio- and enantioselectivity were achieved in the allylic
substitutions of benchmark substrates using carbon and nitrogen nucleophiles. The distinct reactivity between 8a and 8c in
allylic substitution reactions may be attributed to the different
coordination mode of bisphosphite ligands 1a and 1c with
[PdCl2(cod)] (in a cis- or trans-fashion, respectively), as
demonstrated by X-ray single crystal analysis.

EXPERIMENTAL SECTION
General considerations. All syntheses were carried out using
chemicals as purchased from commercial sources unless otherwise
cited. All manipulations and reactions were performed under inert
atmosphere. Glassware was dried in vacuo before use with a hot air
gun. All solvents were dried and deoxygenated by using a Solvent
Purification System (SPS). Silica gel 60 (230400 mesh) or
C18SiO2 (200400 mesh) was used for column chromatography.
NMR spectra were recorded in CDCl3 unless otherwise cited. 1H
NMR and 13C NMR chemical shifts were quoted in ppm relative to
residual solvent peaks, whereas 31P{1H} NMR chemical shifts were
quoted in ppm relative to 85% phosphoric acid in water. Highresolution mass spectra (HRMS) were recorded by using an electrospray ionization (ESI) method in positive mode or matrix-assisted
laser desorption/ionization (MALDI) method, respectively. Melting
points were determined in open capillaries and are uncorrected. Enantiomeric excesses were determined by HPLC equipped with a diode
array detector using chiral stationary phases.
General synthetic procedure for bisphosphite ligands
(1ac). Under inert atmosphere, the chlorophosphites (1 equiv) were
dissolved in anhydrous toluene (25 mL per mmol of the chlorophosphites) and NEt3 (3 equiv). A solution of tetraethylene glycol (0.46
equiv., in 50 mL of toluene per mmol of tetraethylene glycol) was
slowly added to the previous solution and allowed to react overnight
at rt. The reaction mixture was filtered and the solvent evaporated in
vacuo. The resulting crude mixtures were purified by column chromatography on C18SiO2 using acetonitrile/ethyl acetate 1:1 as elution
solvent to provide the expected bisphosphites 1 as white solids.
Compound 1c. Compound 1c was synthesised from TADDOLderived chlorophosphite13 (1.44 g, 2.71 mmol) and a slow addition of
tetraethylene glycol (243.0 mg, 1.25 mmol) with NEt3 (0.52 mL, 3.75
mmol) as base. Purification by C18SiO2 column chromatography
afforded the expected bisphosphite ligand 1c as a white solid (1.05 g,
71% yield). mp 90.395.3 °C. []D24 162.4 (c 0.39 in CH2Cl2). 1H
NMR (400 MHz, CDCl3)  0.57 (6H, s), 0.91 (6H, s), 3.403.48 (4H,
m), 3.533.61 (8H, m), 3.854.02 (4H, m), 5.06 (2H, dd, 3JH,H  8.3
Hz, 4JH,P  1.8 Hz), 5.19 (2H, d, 3JH,H  8.3 Hz), 7.197.36 (24H, m),
7.427.45 (4H, m), 7.507.60 (12H, m). 13C{1H,31P} NMR (125
MHz, CDCl3)  26.3, 27.0, 61.9, 70.7, 70.8, 81.2, 82.3, 82.9, 85.0,
112.8, 127.2, 127.29, 127.33, 127.4, 127.5, 127.8, 128.0, 128.3,
128.9, 129.2, 141.5, 141.7, 146.2, 146.3. 31P{1H} NMR (162 MHz,
CDCl3)  134.6 (s). HRMS (ESI) m/z calcd for C70H72O13P2Na [M 
Na] 1205.4340, found 1205.4339. Anal. Calcd. for C70H72O13P2: C,
71.05; H, 6.13. Found: C, 71.85; H, 6.25.
General synthetic procedure for Pd-complexes based on
bisphosphite ligands (8a and 8c). A solution of enantiomerically pure bisphosphite ligand 1a or 1c (0.059 mmol) in dry CH2Cl2 (1.8
mL) was slowly added to a solution of [PdCl 2(cod)] (0.054 mmol) in
CH2Cl2 (0.2 mL) at room temperature under inert atmosphere. The
reaction mixture was stirred for 2 h, after which the CH2Cl2 solvent
was evaporated off until the mixture had one fourth of its original
volume. Hexane (15.0 mL) was added, leading to the formation of a

precipitate, which was filtered off and then washed with a small
quantity of hexane (1 x 5.0 mL) to give the desired Pd(II) complexes
[PdCl2(1)] as yellowish powders.
Compound 8a. Palladium complex 8a was prepared following the
general procedure, starting from ligand 1a (117 mg, 0.142 mmol) and
[PdCl2(cod)] (37 mg, 0.129 mmol). It was obtained as a yellowish
powder (27 mg, 20% yield). mp 187.0190.0 °C. []D25 40.4 (c 0.10
in CH2Cl2). 1H NMR (500 MHz, C4D8O)  3.653.85 (12H, m),
4.234.26 (2H, m), 4.654.70 (2H, m), 6.75 (2H, d, 3JH,H  8.8 Hz),
7.257.35 (8H, m), 7.447.47 (2H, m), 7.527.55 (2H, m), 7.63 (2H,
d, 3JH,H  8.8 Hz), 7.77 (2H, d, 3JH,H  8.9 Hz), 7.97 (2H, d, 3JH,H  8.2
Hz), 8.068.08 (4H, m). 13C{1H} NMR (125 MHz, C4D8O)  70.8,
71.5, 71.7, 72.0, 121.8, 122.0, 122.6, 123.6, 126.6, 126.8, 127.6,
127.7, 127.9, 129.4, 129.6, 131.9, 132.1, 132.8, 133.1, 133.2, 133.4,
147.1. 31P{1H} NMR (202 MHz, C4D8O)  109.8 (s). HRMS
(MALDI) m/z calcd for C48H40O9P2ClPd [M  Cl] 963.0865, found
963.0839. Anal. Calcd. for C48H40O9P2Cl2Pd: C, 57.65; H, 4.03.
Found: C, 57.33; H, 4.44.
Compound 8c. Palladium complex 8c was prepared following the
general procedure, starting from ligand 1c (70 mg, 0.059 mmol) and
[PdCl2(cod)] (15 mg, 0.053 mmol). It was obtained as a yellowish
powder (47 mg, 65% yield). mp 210.2214.9 °C. []D27 160.6 (c
0.04 in CH2Cl2). 1H NMR (500 MHz, C4D8O)  0.41 (6H, s), 1.25
(6H, s), 2.762.80 (2H, m), 2.862.91 (2H, m), 3.203.25 (2H, m),
3.353.39 (6H, m), 3.543.60 (2H, m), 3.753.81 (2H, m), 5.07 (2H,
d, 3JH,H  8.4 Hz), 5.74 (2H, d, 3JH,H  8.4 Hz), 7.247.40 (24H, m),
7.517.52 (4H, m), 7.727.74 (4H, m), 7.837.85 (8H, m). 13C{1H}
NMR (125 MHz, C4D8O)  23.1, 24.8, 66.7, 68.6, 68.9, 77.6, 80.1,
86.6, 86.67, 86.71, 86.87, 86.92, 87.0, 111.1, 125.1, 125.3, 125.4,
125.6, 125.7, 125.9, 126.5, 127.5, 138.4, 139.2, 142.7, 143.5. 31P{1H}
NMR (202 MHz, C4D8O)  90.2 (s). HRMS (ESI) m/z calcd for
C70H73O14P2ClPd [M  OH Cl] 1340.3213, found 1340.3233. Anal.
Calcd. for C70H72O13P2Cl2Pd·0.5CH2Cl2: C, 60.35; H, 5.24. Found: C,
60.78; H, 5.68.
General procedure for Pd-mediated allylic alkylation of
rac-1,3-diphenylallyl acetate (2). A solution of [Pd(μ-Cl)(η3C3H5)]2 (2.50 mol) or [PdCl2(cod)] (5.00 mol) and enantiopure
bisphosphite 1 (5.50 mol) in CH2Cl2 (0.30 mL) was stirred for 15
min. Subsequently a solution of 1,3-diphenylallyl acetate 2 (0.1
mmol) in CH2Cl2 (0.10 mL), dimethyl malonate (0.3 mmol), N,Obis(trimethylsilyl)-acetamide (0.3 mmol) and regulation agent (RA,
5.50 mol; if appropriate) were added. The reaction mixture was
stirred at room temperature for the appropriate reaction time. The
reaction mixture was then diluted with Et2O (4.0 mL) and washed
with water (2 x 2.0 mL). The organic phase was dried over MgSO 4,
filtered and concentrated in vacuo. The conversion was determined by
1
H NMR spectroscopy and the enantiomeric excess was determined
by HPLC on chiral stationary phases (Daicel Chiralcel® ODH, 99:1
n-hexane/2-propanol, 0.5 mL/min, 216 nm).14
General procedure for Pd-mediated allylic amination of
rac-1,3-diphenylallyl acetate (2). A solution of [Pd(μ-Cl)(η3C3H5)]2 (2.50 mol) and enantiopure bisphosphite 1 (5.50 mol) in
CH2Cl2 (0.30 mL) was stirred for 15 min. Subsequently a solution of
1,3-diphenylallyl acetate 2 (0.1 mmol) in CH2Cl2 (0.10 mL), benzylamine (0.3 mmol), N,O-bis(trimethylsilyl)-acetamide (0.3 mmol) and
regulation agent (RA, 5.50 mol; if appropriate) were added. The
reaction mixture was stirred at rt for the appropriate reaction time.
The reaction mixture was then diluted with Et2O (4.0 mL) and washed
with water (2 x 2.0 mL). The organic phase was dried over MgSO 4,
filtered and concentrated in vacuo. The conversion was determined by
1
H NMR spectroscopy and the enantiomeric excess was determined
by HPLC on chiral stationary phases (Daicel Chiralcel® ODH, 99:1
n-hexane/2-propanol, 0.6 mL/min, 254 nm).15
General procedure for Pd-mediated allylic alkylation of
cinnamyl acetate (5). A solution of [Pd(μ-Cl)(η3-C3H5)]2 (2.50
mol) and enantiopure bisphosphite 1 (5.50 mol) in CH2Cl2 (0.30
mL) was stirred for 15 min. Subsequently a solution of cinnamyl
acetate 5 (0.1 mmol) in CH2Cl2 (0.10 mL), dimethyl malonate (0.3
mmol), N,O-bis(trimethylsilyl)-acetamide (0.3 mmol) and regulation

agent (RA, 5.50 mol; if appropriate) were added. The reaction mixture was stirred at rt for the appropriate reaction time. The reaction
mixture was then diluted with Et2O (4.0 mL) and washed with water
(2 x 2.0 mL). The organic phase was dried over MgSO4, filtered and
concentrated in vacuo. The conversion was determined by 1H NMR
spectroscopy and the enantiomeric excess was determined by HPLC
on chiral stationary phases (Daicel Chiralcel® OJH, 97:3 nhexane/2-propanol, 0.7 mL/min, 220 nm).14

ASSOCIATED CONTENT
Supporting Information
The Supporting Information is available free of charge on the
ACS
Publications
website
at
DOI:
10.1021/acs.organomet.5b00962.
Text and figures giving characterization data, and NMR
spectra for new compounds (PDF)
Crystallographic data for 8a and 8c (CIF)

AUTHOR INFORMATION
Corresponding Author
* E-mail: avidal@iciq.cat
Notes
The authors declare no competing financial interest.

ACKNOWLEDGMENT
The authors would like to thank MINECO (CTQ2014-60256-P)
and the ICIQ Foundation for their financial support. L. R. is grateful to the ICIQ Foundation for her stipend. We would also like to
thank Dr. J. Benet-Buchholz for the X-ray crystallographic data.

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