New phosphine-imine and phosphine-amine ligands derived from D-gluco-, D-galacto- and D-allosamine in Pd-catalysed asymmetric allylic alkylation

Article abstract of DOI:10.1016/j.tet.2018.02.009

New phosphine-imine and phosphine-amine chiral ligands which were easily prepared from D-gluco-, D-galacto- and D-allosamine furnished a high level of enantiomeric excess (up to 99%) in the Pd(0)-catalysed asymmetric allylic alkylation of racemic 1,3-diphenyl-2-propenyl acetate with malonates.

Full text of DOI:10.1016/j.tet.2018.02.009

Tetrahedron xxx (2018) 1e10
Contents lists available at ScienceDirect
Tetrahedron
journal homepage: www.elsevier.com/locate/tet
New phosphine-imine and phosphine-amine ligands derived from
D-gluco-,
D
-galacto- and -allosamine in Pd-catalysed asymmetric
D
allylic alkylation
Izabela Szulc, Robert Kołodziuk, Anna Zawisza*
ꢀ ꢀ
ꢀ ꢀ
Department of Organic and Applied Chemistry, University of Łodz, Tamka 12, 91-403 Łodz, Poland
a r t i c l e i n f o
a b s t r a c t
Article history:
New phosphine-imine and phosphine-amine chiral ligands which were easily prepared from D-gluco-, D-
Received 30 November 2017
Received in revised form
31 January 2018
Accepted 2 February 2018
Available online xxx
galacto- and
D-allosamine furnished a high level of enantiomeric excess (up to 99%) in the Pd(0)-
catalysed asymmetric allylic alkylation of racemic 1,3-diphenyl-2-propenyl acetate with malonates.
© 2018 Elsevier Ltd. All rights reserved.
Keywords:
D
D
D
-glucosamine
-galactosamine
-allosamine
Iminophosphine
Aminophosphine
Homogeneous catalysis
Asymmetric alkylation
Palladium
1. Introduction
asymmetric allylic substitution reaction which is a fundamental
transformation in organic synthesis and one of the most powerful
tools for the formation of carbon-carbon and carbon-heteroatom
bonds. The best results in Pd-catalysed asymmetric allylic alkyl-
ation of 1,3-symmetrically disubstituted acetates (ee up to 98%)
provided phosphine-oxazoline,9 phosphinite-oxazoline,10 phos-
phite-oxazoline,11 phosphite-phosphoramidite12 and phosphine-
Catalytic asymmetric synthesis has been one of the most active
research areas in modern organic chemistry. To achieve the highest
levels of reactivity and selectivity in enantioselective reactions the
design of efficient synthetic chiral catalysts is at the center of
contemporary studies.
In recent years impressive results have been obtained using
carbohydrate-based ligands.1 These chiral natural derivatives have
many advantages: they are readily available, can be easily func-
tionalized, have several stereogenic centers and successfully used
in a large number of asymmetric catalytic reactions, such as: hy-
drogenation,2 1,2-addition of nucleophiles to C¼O and C¼NR,3 1,4-
addition of nucleophiles to Michael acceptors,4 hydroformylation,5
Heck reaction,6 cyclopropanation7 and hydrovinylation.8 De-
amide13 derivatives of
D-glucosamine. Just a few phosphine-imine
ligands with a pyranoside backbone have been developed for Pd-
catalysed allylic substitution.13c,13d,14 The studies indicated that
the presence of the imine-phosphine residue at C2 provides better
enantioselectivities than when the residue is at C1 of the pyrano-
side backbone. Additionally the C2 imine group in ligands has been
replaced by an amine group and also provided good results.13d
Herein, we report a simple and efficient synthesis of novel
phosphine-imine and phosphine-amine chiral ligands derived from
rivatives of the most accessible NH2-containing sugar, D-glucos-
amine, have been mainly evaluated as chiral ligands in Pd-catalysed
D-gluco-, D-galacto- and D-allosamine hydrochloride (Fig. 1) and
their application in the Pd-catalysed allylic alkylation reaction with
various nucleophiles.
* Corresponding author.
E-mail address: azawisza@chemia.uni.lodz.pl (A. Zawisza).
https://doi.org/10.1016/j.tet.2018.02.009
0040-4020/© 2018 Elsevier Ltd. All rights reserved.
Please cite this article in press as: Szulc I, et al., New phosphine-imine and phosphine-amine ligands derived from D-gluco-, D-galacto- and D-
allosamine in Pd-catalysed asymmetric allylic alkylation, Tetrahedron (2018), https://doi.org/10.1016/j.tet.2018.02.009

2
I. Szulc et al. / Tetrahedron xxx (2018) 1e10
Fig. 1. New P,N-ligands used in this work.
2. Results and discussion
protected a
-derivatives 5,15 6,16 7 and 8 were obtained in 82%, 82%,
55% and 60% yields, respectively, by the reaction of 1e4 with tri-
methylsilyl chloride (TMSCl) and hexamethyl disilazane (HMDS) in
pyridine15,17. Under these conditions the amino functional group
remains unprotected.15 Condensation of 2-(diphenylphosphino)-
2.1. Synthesis of the starting materials
The new phosphine-imine ligands 9e12, derivatives of
D
-gluco-
and
D
-galactosamine were easily prepared according to Scheme 1.
benzaldehyde onto
D-glucopyranose 5, 7e8 and D-galactopyranose
Glucosamine hydrochloride 1 was first treated with TBDPSCl or
TBDMSCl in pyridine to give 6-O-silyl protected derivatives 3 and 4
as yellow oil in 63% and 72% yields, respectively. Per-O-silyl
6 derivatives in toluene furnished the corresponding phosphine-
imine derivatives 9,18 10,16 11 and 12 in 77%, 67%, 43% and 45%
yields, respectively.
Scheme 1. Synthesis of ligands L1, L2, L4 and L5; reagents and conditions: (a) TBDPSCl or TBDMSCl, Py, rt; (b) TMSCl, HMDS, Py, rt; (c) 1,2-Ph2P-C6H4-CHO, toluene, 60 ꢀC.
Please cite this article in press as: Szulc I, et al., New phosphine-imine and phosphine-amine ligands derived from D-gluco-, D-galacto- and D-
allosamine in Pd-catalysed asymmetric allylic alkylation, Tetrahedron (2018), https://doi.org/10.1016/j.tet.2018.02.009

I. Szulc et al. / Tetrahedron xxx (2018) 1e10
3
The synthesis of phosphine-imine ligand derivative of
amine 21 we started from the inexpensive -glucosamine hy-
drochloride which was N-acetylated to give -N-acetyl-
D
-allos-
entries 1e4). Based on these results, we decided under the same
conditions, to carry out the palladium-catalysed allylic substitution
of 1,3-diphenyl-2-propenyl acetate with various nucleophiles using
L1-L7 chiral phosphine-imine ligands and amino-phosphine li-
gands L8-L9 (Table 1). The activity of some saccharide ligands (L4-
L9), containing other than TMS protective groups, was also inves-
tigated in tetrahydrofuran.
a-D
1
a-D
glucosamine 1319 (Scheme 2). In the two following steps, 1-O-
methyl and 4,6-O-benzylidene protecting groups were introduced
according to known procedures,20 leaving the 3-hydroxy group of
15 unprotected. The mesylation reaction of this group20b followed
by the substitution with OH group causes the inversion of config-
uration at C-3.20b Deprotection of 4 and 621 positions of the
Initially, we performed the palladium-catalysed allylic substi-
tution of 1,3-diphenyl-2-propenyl acetate 32 with dimethyl malo-
saccharide 17, as well as 1 and 222 in acidic conditions leads to
a-
D-
nate (Table 1, entries 1e22). Ligands L2 derived from
a-D-
allosamine hydrochloride 19. Per-O-silylation and condensation
galactosamine and L3 derived from -allosamine were the most
a-D
with 2-(diphenylphosphino)-benzaldehyde gave the correspond-
reactive in these conditions and gave compound 33 with the
highest enantiomeric excess e over 99% ee at 0 ꢀC (Table 1, entries
5e8). It should be noted that the configuration of the substituent at
ing phosphine-imine
The synthesis of ligands L6-L9 was started by protecting the
amino group in -glucosamine hydrochloride 1 with a 2,2,2-
D-allo-ligand 21 in 57% yield.
a
-D
the C4 and C3 position of the carbohydrate moiety of the
ligand L2 and -allo ligand L3 had an influence on the configuration
of the alkylation product 33. The (R) configuration of the obtained
product was opposite to that observed for the reaction using
gluco ligand L2 (Table 1, entries 1e4). The phosphine-imine ligands
L4 and L5 of the -gluco configuration with the large substituents
D-galacto
trichloroethoxycarbonyl group23 (Scheme 3). Selective depro-
tection of the hydroxyl group located on the anomeric carbon with
benzylamine leads to 23,23 which is easily converted into 1-O-silyl
protected derivatives 24 and 25. In the next step, these derivatives
reacted with activated Zn dust in glacial acetic acid gave 26 and 27
with free amino groups in 80% and 83% yields, respectively.
Condensation with 2-(diphenylphosphino)-benzaldehyde afforded
the corresponding phosphine-imine ligands 28 and 29 (75% and
85% yields, respectively). The imino functionality was then reduced
with NaBH3CN to provide phosphine-amines 30 and 31 with
quantitative yields.
D
D
-
a-D
at the C6 position of a saccharide were less reactive and gave 33
with practically quantitative yield but ee's of 40e56% in favor of the
(R)-enantiomer (Table 1, entries 9e12). The reactions with
b-D-
gluco ligands L6 and L7 were characterised by excellent yields and
high enantioselectivity e up to 93% ee (Table 1, entries 13e18). The
obtained results also confirmed that dichloromethane is a better
solvent for this type of reaction than tetrahydrofuran. Comparing
the results obtained with ligands L4-L7, we can also conclude that
only bulky protecting groups at the C1 position of the sugar have
the influence on the course of the reaction and the mode
complexation of ligands with palladium whereas such groups in the
C6 position show only minimal effect.
Finally, we performed the allylic alkylation reaction using
phosphine-amine ligands L8 and L9 (Table 1, entries 19e22). The
reaction gave 33 in excellent yield but an ee of 10% in favor of the
(S)-enantiomer in CH2Cl2.
2.2. Application of ligands L1eL9 in the Pd(0)-catalysed
asymmetric allylic alkylation
In a previous paper,16 we examined the influence of base, sol-
vent, Pd/ligand ratio and substrate/nucleophile ratio on the
outcome of the asymmetric allylic alkylation using [(h
3-C3H5)
PdCl]2 as the palladium source and 9 (L1) as the ligand. The best
results were obtained with a Pd/ligand ratio of 1:2 and substrate/
nucleophile ratio of 1:2 in CH2Cl2 in the presence of a mixture of
N,O-bis(trimethylsilyl)acetamide (BSA) and KOAc as base (Table 1,
In the next step, the effectiveness of the ligands L1-L9 has been
Scheme 2. Synthesis of ligand L3; reagents and conditions: (a) (CH3CO)2O, CH3ONa, CH3OH, 40 ꢀC, 24 h; (b) Amberlite IR-120, CH3OH, reflux, 24 h; (c) PhCH(OCH3)2, p-TsOH, DMF,
40 ꢀC, 48 h; (d) MsCl, Py, 0 ꢀC, 16 h; (e) CH3OCH2CH2OH, CH3COONa, reflux / rt, 12 h; (f) 60% CH3COOH, 40 ꢀC, 3 h; (g) 2N HCl, 80 ꢀC, 2 h; (h) TMSCl, HMDS, Py, rt, 10 h; (i) 1,2-Ph2P-
C6H4-CHO, toluene, 60 ꢀC, 24 h.
Please cite this article in press as: Szulc I, et al., New phosphine-imine and phosphine-amine ligands derived from D-gluco-, D-galacto- and D-
allosamine in Pd-catalysed asymmetric allylic alkylation, Tetrahedron (2018), https://doi.org/10.1016/j.tet.2018.02.009

4
I. Szulc et al. / Tetrahedron xxx (2018) 1e10
Scheme 3. Synthesis of ligands L6 e L9; reagents and conditions: (a) 1. CCl3CH2OCOCl, NaHCO3, H2O, rt, 2 h; 2. (CH3CO)2O, Py, rt, 24 h; (b) BnNH2, THF, rt, 24 h; (c) TBDPSCl or
TBDMSCl, CH3CN, rt, 24 h; (d) Zn, CH3COOH, rt, 24 h; (e) 1,2-Ph2P-C6H4-CHO, toluene, 60 ꢀC, 24 h; (f) NaBH3CN, CH3COOH, CH3OH, rt, 0.5 h.
tested in the reaction with other nucleophiles.
in improving the enantioselectivity of the reaction. The b-D-gluco-
The reaction with ligand L1 and diethyl malonate at 25 ꢀC
required longer reaction times and was characterised by low yields
(35% conversion) and an ee of 71% (Table 1, entry 23). Increasing the
temperature to 36 ꢀC afforded the product in 100% conversion after
24 h but did not improve the selectivity of the reaction (Table 1,
entries 23e24). Ligand L2 was more reactive with the same
nucleophile and gave 33 with an improved yield and enantiose-
lectivity; 83% ee at 25 ꢀC and 99% ee at 0 ꢀC in favor of the (R)-
ligands L6 and L7 in the reaction with dimethyl methylmalonate
produced the highest enantiomeric excess: 89% and 75% in THF and
92% and 89% in CH2Cl2, respectively (Table 1, entries 51e54).
Phosphine-amine ligands L8 and L9 were again ineffective in allyl
substitution reactions.
The reactions carried out in their presence provided a 60%
conversion and an enantiomeric excess not exceeding 20% in favor
of the (S)-enantiomer.
enantiomer (Table 1, entries 25e26). The
a
-
D
-allo-ligand L3 gave
As reported previously, to determine the mode of complexation
of phosphine-imine ligands with palladium, an NMR and IR study
of the palladium complex was made using ligand L2 before and
after complexation with palladium.16 Both 1H NMR and IR spectra
excluded the coordination of the imine nitrogen to the palladium
metal center. The 1H NMR spectra of free ligand L2 displayed the
imine proton at 9.00 ppm, which was not shifted after chelatation
with the metal. The IR spectroscopic data of complex L2 with
palladium did not reveal a batochromic shift with respect to the
slightly weaker results: 80% ee at 25 ꢀC (Table 1, entry 27). Ligands
L4 and L5 generate moderate results under the same conditions:
69% ee and 39% ee, respectively. Lowering the temperature to 0 ꢀC
did not improve the selectivity of the reaction (Table 1, entries
29e31). However, it should be noted that the ligand L4 with a larger
substituent (TBDPS) in the C6 position of
generated significantly higher enantiomeric excesses than ligand
L5 with TBDMS substituent. The -gluco-ligands L6 and L7 in the
a-D-glucopyranose
b-D
reaction with diethyl malonate produced results comparable to
those obtained for dimethyl malonate (83% and 82% ee's, respec-
tively at 25 ꢀC in CH2Cl2), although these reactions required elon-
gation of reaction time to 48 h (Table 1, entries 33e37). Phosphine-
amine ligands L8 and L9 showed slightly higher efficiency in the
reaction with diethyl malonate (Table 1, entries 38e41). In this case,
enantioselectivity of 40% for L8 and 71% for L9 with a conversion of
100% was observed after a reaction time of 24 h at 25 ꢀC in CH2Cl2.
The reaction in THF gave comparable results.
free ligand,24 with a vC¼N stretching vibration band at 1636 cmꢁ1
.
However, a significant downfield shift of the single 31P resonances
of ligand L2 to 15.86 ppm after complexation compared
to ꢁ16.57 ppm for the free ligand confirmed coordination of the
phosphine moiety to the palladium center.
3. Conclusion
Finally, a series of Pd-catalysed asymmetric allylation reactions
were performed with 1,3-diphenyl-2-propenyl acetate 32 and
dimethyl methylmalonate (Table 1, entries 42e58). The use of tri-
In conclusion, a series of saccharides phosphine-imine and
phosphine-amine chiral ligands which were easily prepared from
D-gluco-, D-galacto- and D-allosamine have been examined in
methylsilyl a-D-glucoside derivative L1 as the ligand, gave 35% and
85% conversion at 25 ꢀC after 24 and 48 h, respectively (Table 1,
entries 42 and 43). The obtained enantioselectivity was 74% and
asymmetric allylic alkylation. We have shown the influence of
factors such as sugar configuration, type of solvent or nucleophile
on the course of the reaction. The phosphine-imine ligands L2
72% ee in favor of the (R)-enantiomer. a-D-Galactoside derivative L2
derived from
a-D-galactosamine and L3 derived from a-D-allos-
gave a more active catalyst, a 98% conversion end 75% ee being
obtained at 25 ꢀC and a 87% conversion end 96% ee at 0 ꢀC after 48 h
amine were the most reactive in dichloromethane and gave the
substitution product with the highest enantiomeric excess (over
99% ee at 0 ꢀC) while phosphine-amine ligands L8 and L9 did not
show activity under these conditions. In addition, we have shown
that synthesized ligands utilize the chirality of the sugar moiety
and induce chirality to the coordination sphere solely by phos-
phorus atom coordination.
(Table 1, entries 44e45). The
sults in these conditions e 77% conversion and 52% ee (R) (Table 1,
entry 46). The phosphine-imine ligands L4 and L5 of the -gluco
a-D-allo ligand L3 gave moderate re-
a-D
configuration gave quite similar results (Table 1, entries 47e50).
However, a total conversion occurred at 25 ꢀC after 24 h, the
enantioselectivity was only 56% and 46% ee, respectively in favor of
the (S)-enantiomer. Lowering the temperature to 0 ꢀC did not result
Further work is underway to utilize the obtained P,N-ligands in
other asymmetric reactions.
Please cite this article in press as: Szulc I, et al., New phosphine-imine and phosphine-amine ligands derived from D-gluco-, D-galacto- and D-
allosamine in Pd-catalysed asymmetric allylic alkylation, Tetrahedron (2018), https://doi.org/10.1016/j.tet.2018.02.009

I. Szulc et al. / Tetrahedron xxx (2018) 1e10
5
Table 1
Effect of nucleophiles and ligands on Pd0-catalysed asymmetric allylic alkylationa.
Entry
Ligand
Nu-H
Solvent
Temp. [ºC]
Time [h]
Conv. [%]b
ee [%]c (config.)d
1
2
3
4
5
6
7
8
L1
L1
L1
L1
L2
L2
L3
L3
L4
L4
L5
L5
L6
L6
L6
L7
L7
L7
L8
L8
L9
L9
L1
L1
L2
L2
L3
L4
L4
L5
L5
L6
L6
L6
L7
L7
L7
L8
L8
L9
L9
L1
L1
L2
L2
L3
L4
L4
L5
L5
L6
L6
L7
L7
L8
L8
L9
L9
CH2(CO2Me)2
CH2(CO2Me)2
CH2(CO2Me)2
CH2(CO2Me)2
CH2(CO2Me)2
CH2(CO2Me)2
CH2(CO2Me)2
CH2(CO2Me)2
CH2(CO2Me)2
CH2(CO2Me)2
CH2(CO2Me)2
CH2(CO2Me)2
CH2(CO2Me)2
CH2(CO2Me)2
CH2(CO2Me)2
CH2(CO2Me)2
CH2(CO2Me)2
CH2(CO2Me)2
CH2(CO2Me)2
CH2(CO2Me)2
CH2(CO2Me)2
CH2(CO2Me)2
CH2(CO2Et)2
CH2(CO2Et)2
CH2(CO2Et)2
CH2(CO2Et)2
CH2(CO2Et)2
CH2(CO2Et)2
CH2(CO2Et)2
CH2(CO2Et)2
CH2(CO2Et)2
CH2(CO2Et)2
CH2(CO2Et)2
CH2(CO2Et)2
CH2(CO2Et)2
CH2(CO2Et)2
CH2(CO2Et)2
CH2(CO2Et)2
CH2(CO2Et)2
THF
25
25
0
e20
25
0
25
0
25
0
25
0
25
25
0
25
25
0
25
25
25
25
25
36
25
0
25
25
0
25
0
25
25
0
25
25
0
25
25
25
25
25
25
25
0
24
24
24
24
24
24
15 min
24
24
24
24
24
24
24
24
24
24
24
24
24
24
24
78
24
24
24
24
24
48
24
24
48
48
48
48
48
48
24
24
24
24
24
48
48
48
24
24
48
24
24
72
72
72
72
96
96
96
96
100
100
98
100
100
98
55 (S)
73 (S)
81 (S)
80 (S)
85 (R)
>99 (R)
93(R)
>99 (R)
56 (R)
50 (R)
44 (R)
40 (R)
83 (S)
89 (S)
93 (S)
69 (S)
83 (S)
86 (S)
10 (S)
10 (S)
8 (S)
10 (S)
71 (S)
67 (S)
83 (R)
>99 (R)
80 (R)
69 (R)
69 (R)
39 (R)
35 (R)
81 (S)
83 (S)
88 (S)
60 (S)
82 (S)
e
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
THF
CH2Cl2
CH2Cl2
THF
CH2Cl2
CH2Cl2
THF
100
100
100
100
100
97
100
100
100
100
100
100
100
100
100
100
35
100
100
100
100
100
100
100
100
100
100
36
100
100
traces
100
100
100
100
35
78
98
87
77
100
76
100
67
57
54
55
70
62
61
58
60
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
CH2Cl2
THF
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
THF
CH2Cl2
CH2Cl2
THF
CH2Cl2
CH2Cl2
THF
40 (R)
38 (R)
71 (R)
71 (R)
74 (R)
73 (R)
75 (R)
96 (R)
52 (R)
56 (S)
60 (S)
46 (S)
45 (S)
89 (S)
92 (S)
75 (S)
89 (S)
20 (S)
3 (S)
CH2Cl2
THF
CH2(CO2Et)2
CH2(CO2Et)2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
THF
CH2Cl2
THF
CH2Cl2
THF
CH2Cl2
THF
CH2Cl2
MeCH(CO2Me)2
MeCH(CO2Me)2
MeCH(CO2Me)2
MeCH(CO2Me)2
MeCH(CO2Me)2
MeCH(CO2Me)2
MeCH(CO2Me)2
MeCH(CO2Me)2
MeCH(CO2Me)2
MeCH(CO2Me)2
MeCH(CO2Me)2
MeCH(CO2Me)2
MeCH(CO2Me)2
MeCH(CO2Me)2
MeCH(CO2Me)2
MeCH(CO2Me)2
MeCH(CO2Me)2
25
25
0
25
0
25
25
25
25
25
25
25
25
17 (S)
13 (S)
a
Reaction conditions: [7]:[Nu-H]:[KOAc]:[BSA]:[Pd]:[L] ¼ 1:2:0.05:2:0.05:0.1.
b
c
Determined by 1H NMR analysis.
Enantioselectivity (ee) was measured by chiral stationary phase HPLC on a KROMASIL AD column (25 cm ꢂ 4.6 mm);
l
¼ 254 nm, hexane/i-propanol (85:15), flow
¼ 254 nm, hexane/i-
m Amylose-1 column (25 cm ꢂ 4.6 mm);
rate ¼ 0.5 mL minꢁ1, tR ¼ 17.2 min and tS ¼ 23.8 min for dimethyl malonate; on a Phenomenex - Lux®
5
m
m Amylose-1 column (25 cm ꢂ 4.6 mm);
l
propanol (95:5), flow rate ¼ 0.4 mL minꢁ1, tR ¼ 32.4 min and tS ¼ 38.5 min for diethyl malonate and on a Phenomenex - Lux®
5 m
l
¼ 254 nm, hexane/i-propanol (99:1), flow rate ¼ 0.4 mL minꢁ1, tR ¼ 22.6 min and tS ¼ 26.6 min for dimethyl methylmalonate.
d
Determined by comparison with an authentic sample.
Please cite this article in press as: Szulc I, et al., New phosphine-imine and phosphine-amine ligands derived from D-gluco-, D-galacto- and D-
allosamine in Pd-catalysed asymmetric allylic alkylation, Tetrahedron (2018), https://doi.org/10.1016/j.tet.2018.02.009

6
I. Szulc et al. / Tetrahedron xxx (2018) 1e10
4. Experimental
10 eq.) was added followed by TMSCl (14.7 mL, 115.9 mmol, 10 eq.).
The resulting mixture was stirred at rt and the reaction monitored
via TLC (petroleum ether/ethyl acetate, 5:1). During the reaction a
lot of salt byproduct precipitated. After completion of the reaction
(approx. 3 h), the mixture was evaporated in vacuo with a cooling
trap between rotary evaporator and pump stand. The residue was
twice co-evaporated with toluene to remove the residual pyridine.
The raw material was then submitted to short column filtration
over silica gel (petroleum ether/ethyl acetate) to remove the pyr-
idinium salts.
4.1. General
All solvents and reagents were purchased from Sigma-Aldrich
and were used as supplied, without additional purification. NMR
spectra were recorded in CDCl3 on Varian Gemini 2000 (200 MHz
for 1H NMR, 50 MHz for 13C NMR) or Bruker Avance III (600 MHz for
1H NMR, 150 MHz for 13C NMR), coupling constants are reported in
Hz. Chromatographic purification of compounds was achieved with
230e400 mesh size silica gel. The progress of reactions was
monitored by silica gel thin layer chromatography plates (Merck
TLC Silicagel 60 F254). Optical rotations were measured on a Perkin-
Elmer 241 polarimeter. The enantiomeric ratio was determined by
HPLC (ProStar Varian) employing a KROMASIL AD or Phenomenex -
4.3.1. 2-Amino-2-deoxy-1,3,4,6-tetra-O-trimethylsilyl-a-D-
glucopyranose 5
The analytically pure, colourless solid 2-amino-2- deoxy-1,3,4,6-
tetra-O-trimethylsilyl-a-D-glucopyranose (5) was prepared ac-
Lux®
5
mm Amylose-1 column (25 cm ꢂ 4.6 mm).
cording to literature15 in 82%. The spectroscopic data are in accor-
dance to ref.15
4.2. Typical procedure for the synthesis of silyl derivatives 3 and 4
25
25
Mp. 50e52 ꢀC; [
a]
¼ þ90.5 (c 0.4, CHCl3); Lit.15
[
a]
¼ þ87.0 (c
D
D
3.4, CHCl3); Rf (petroleum ether/ethyl acetate, 5:1) 0.82.
To a suspension of gluco- or galactosamine hydrochloride
(23.2 mmol, 1eq.) in pyridine (80 mL) was added tert-butyldiphe-
nylsilylchloride (TBDPSCl) or tert-butyldimethylsilylchloride
(TBDMSCl) (30.2 mmol,1.3 eq.). The resulting mixture was stirred at
room temp. and monitored via TLC (CH2Cl2/CH3OH, 10: 3). After
completion of the reaction (approx. 48 h), the mixture was evap-
orated under reduced pressure. The crude product was purified by
flash column chromatography on silica gel.
4.3.2. 2-Amino-2-deoxy-1,3,4,6-tetra-O-trimethylsilyl-a-D-
galactopyranose 6
Synthesis and spectral data for 2-amino-2-deoxy-1,3,4,6-tetra-
O-trimethylsilyl- -galactopyranose 6 see: Szulc, I.; Kołodziuk, R.;
a-D
Kryczka, B.; Zawisza, A. Tetrahedron Lett. 2015, 56, 4740e4743.
4.3.3. 2-Amino-2-deoxy-1,3,4-tri-O-trimethylsilyl-6-O-tert-
4.2.1. 2-Amino-2-deoxy-6-O-tert-butyldiphenylsilyl-D-
butyldiphenylsilyl-
a-D-glucopyranose 7
25
glucopyranose hydrochloride 3
Yellow oil, 4.0 g, 55% yield; [
a
]
D
¼ þ15.0 (c 0.5, CHCl3); Rf (pe-
25
Yellow oil, 6.1 g, 63% yield; [
a
]
¼ þ27.0 (c 0.5, CHCl3); Rf
D
troleum ether/ethyl acetate, 5:1) 0.76; dH (600 MHz, CDCl3) 0.08 (s,
9H, OSi(CH3)2), 0.11 (s, 9H, OSi(CH3)2), 0.20 (s, 9H, OSi(CH3)2), 1.06
(s, 9H, OSiC(CH3)3), 1.52 (s, 2H, NH2), 2.55 (dd, 1H, J 9.0, 3.2, H-2),
3.53e3.57 (m, 2H, H-3, H-4), 3.63e3.70 (m, 1H, H-5), 3.78 (dd, 1H, J
11.4, 2.4, H-6), 3.85 (dd, 1H, J 11.4, 3.9, H-60), 5.10 (d, 1H, J 3.2, H-1),
7.30e7.45 (m, 6H, C6H5), 7.64e7.79 (m, 4H, C6H5); dC (150 MHz,
CDCl3) 0.1 (OSi(CH3)3), 0.4 (OSi(CH3)3), 1.0 (OSi(CH3)3),19.5
(OSiC(CH3)3), 27.2 (OSiC(CH3)3), 59.8 (C-2), 60.6 (C-6), 72.7 (C-4),
63.5 (C-5), 78.3 (C-3), 98.8 (C-1), 127.6, 127.7, 127.8, 129.7, 129.8,
135.9, 136.0, 136.1, 136.4 (C6H5); MS-EI (m/z): 634.1 [(MþH)þ, 100].
(CH2Cl2/CH3OH, 10: 3) 0.78; dH (600 MHz, CDCl3) 1.00 (s, 9H,
OSiC(CH3)3), 2.50e2.57 (m, 0.33H, H-2 ), 2.85 (dd, 0.66H, J 10.2, 3.2,
, H-4 and , H-5 and
, H-60
, 3 ꢂ OH), 5.31 (d, 0.66H, J 3.2, H-1 ), 5.34 (d,
), 5.69 (d, 0.66H, J 5.3, NH2a), 5.85 (d, 0.33H, J 5.3,
b
H-2
and
a
b
), 3.20e4.20 (m, 8H, H-3
, H-6 and
a
and
b
a
b
a
b
a
a
b
a
0.33H, J 5.4, H-1
b
NH2b), 7.35e7.50 (m, 6H, C6H5), 7.60e7.77 (m, 4H, C6H5); dC
(150 MHz, CDCl3) 18.9 (OSiC(CH3)3), 26.6 (OSiC(CH3)3), 54.5, 57.3
(C-2
C-5
a
and
b
), 63.2, 63.4 (C-6
a
and
b
), 69.9, 72.0, 72.5 (C-4
a and b,
a
and
b
), 76.6 (C-3 and
a
b
), 89.0, 93.0 (C-1
a
and ), 123.8, 127.7,
b
129.7, 133.2, 133.3, 135.1, 136.1 (C6H5); MS-EI (m/z): 476.2
[(MþNa)þ, 100].
4.3.4. 2-Amino-2-deoxy-1,3,4-tri-O-trimethylsilyl-6-O-tert-
butyldimethylsilyl-
a-D-glucopyranose 8
4.2.2. 2-Amino-2-deoxy-6-O-tert-butyldimethylsilyl-D-
25
Yellow oil, 3.5 g, 60% yield; [
a]
¼ þ59.0 (c 0.5, CHCl3); Rf (pe-
D
glucopyranose hydrochloride 4
troleum ether/ethyl acetate, 5:1) 0.77; dH (600 MHz, CDCl3) 0.15 (s,
9H, OSi(CH3)2), 0.16 (s, 3H, OSi(CH3)2), 0.17 (s, 3H, OSi(CH3)2), 0.18
(s, 9H, OSi(CH3)2), 0.20 (s, 9H, OSi(CH3)2), 0.88 (s, 9H, OSiC(CH3)3),
1.45 (s, 2H, NH2), 2.51 (dd, 1H, J 9.6, 3.2, H-2), 3.52 (dd, 1H, J 9.4, 8.6,
H-4), 3.55 (dd, 1H, J 9.6, 8.6, H-3), 3.57e3.61 (m, 1H, H-5), 3.79 (dd,
1H, J 11.5, 2.2, H-6), 3.79 (dd, 1H, J 11.5, 3.9, H-60), 5.10 (d, 1H, J 3.2,
H-1); dC (150 MHz, CDCl3) ꢁ5.4 (OSi(CH3)2), ꢁ0.1 (OSi(CH3)3), 0.8
(OSi(CH3)3), 1.33 (OSi(CH3)3), 18.4 (OSiC(CH3)3), 25.8 (OSiC(CH3)3),
57.5 (C-2), 62.3 (C-6), 71.5 (C-5), 73.1 (C-4), 77.6 (C-3), 94.6 (C-1);
found: C, 49.65; H, 10.21; N, 2.69. C21H51NO5Si requires C, 49.46; H,
10.08; N, 2.75%.
25
Yellow oil, 4.9 g, 72% yield; [
a
]
¼ þ34.0 (c 0.5, CHCl3); Rf
D
(CH2Cl2/CH3OH, 10: 3) 0.78; dH (600 MHz, CDCl3) 0.00 (s, 6H,
OSiC(CH3)3), 0.83 (s, 9H, OSi(CH3)2), 2.40 (dd, 0.33H, J 10.4, 5.5, H-
2
b
b
), 2.75 (dd, 0.67H, J 10.4, 3.3, H-2
), 3.53e3.60 (m, 5H, H-4 and , H-5
), 3.68 (dd, 0.67H, J 11.1, 4.9, H-60
), 3.82 (d, 0.33H, J 11.1, H-6 ), 5.16 (d, 0.67H, J 3.3,
), 5.21 (d, 0.33H, J 5.5, H-1 ), 5.57 (d, 0.67H, J 5.2, NH2a), 5.70
(d, 0.33H, J 5.2, NH2b); dC (150 MHz, CDCl3) ꢁ5.2 (OSi(CH3)2), 18.1
(OSiC(CH3)3), 25.9 (OSiC(CH3)3), 54.5, 57.3 (C-2 and ), 62.6, 62.7
, C-5
a
), 3.00e3.12 (m, 1H, H-3
and
, 3 ꢂ OH), 3.63 (dd,
), 3.75 (d,
a and
a
b
a
b
0.33H, J 11.1, 5.3, H-60
b
a
0.67H, J 11.1, H-6
H-1
a
b
a
b
a
b
(C-6
and
100].
a
and
b
), 69.8, 69.9, 72.2, 72.7 (C-4
a
and
b
a i b), 76.8 (C-3
a
b
), 89.0, 93.2 (C-1
a
and
b
); MS-EI (m/z): 352.2 [(MþNa)þ,
4.4. Typical procedure for the synthesis of phosphine-imine ligands
9e12
4.3. Typical procedure for the synthesis of trimethylsilyl derivatives
5e8
In a Schlenk tube under nitrogen, a-D-pyranose 5e8 (2.1 mmol)
and 2-(diphenylphosphino)benzaldehyde (621 mg, 2.1 mmol) were
stirred in toluene (40 mL) at 60 ꢀC for 12 h. After concentration, the
residue was purified by flash column chromatography on silica gel.
To a suspension of gluco- or galactosamine hydrochloride 1e4
(11.59 mmol,1eq.) in pyridine (50 mL), HMDS (24.2 mL,115.9 mmol,
Please cite this article in press as: Szulc I, et al., New phosphine-imine and phosphine-amine ligands derived from D-gluco-, D-galacto- and D-
allosamine in Pd-catalysed asymmetric allylic alkylation, Tetrahedron (2018), https://doi.org/10.1016/j.tet.2018.02.009

I. Szulc et al. / Tetrahedron xxx (2018) 1e10
7
25
25
4.4.1. 1,3,4,6-Tetra-O-trimethylsilyl-2-deoxy-2-{[2-
(diphenylphosphino)benzoyl]imino}- -glucopyranose 9 (L1)
Synthesis and spectral data for 1,3,4,6-tetra-O-trimethylsilyl-2-
184.0e185.0 ꢀC; [
a
]
D
¼ þ128.0 (c 0.5, H2O); Lit.30
[
a
]
¼ þ127.0
D
a-
D
(c 1.0, H2O); Rf (CH2Cl2/CH3OH, 10: 3) 0.75.
deoxy-2-{[2-(diphenylphosphino)benzoyl]imino}-
9 see: Olszewska, B.; Szulc, I.; Kryczka, B.; Kubiak, A.; Porwanski, S.;
Zawisza, A. Tetrahedron: Asymmetry 2013, 24, 212e216.
a
-
D
-glucopyranose
4.5.3. Methyl 2-acetamido-4,6-O-benzylidene-2-deoxy-a-D-
glucopyranoside 15
ꢀ
The synthesis and spectroscopic data for methyl 2-acetamido-
4,6-O-benzylidene-2-deoxy-a-D-glucopyranoside 15 are in accor-
dance to ref.31
4.4.2. 1,3,4,6-Tetra-O-trimethylsilyl-2-deoxy-2-{[2-
Colorless solid, 50% yield; m.p. 200.0e202.0 ꢀC; Lit.32 m.p.
(diphenylphosphino)benzoyl]imino}-
Synthesis and spectral data for 1,3,4,6-tetra-O-trimethylsilyl-2-
deoxy-2-{[2-(diphenylphosphino)benzoyl]imino}- -galactopyr-
a-D-galactopyranose 10 (L2)
199.0e200.0 ꢀC; [
a
]
¼ þ15.6 (c 0.5, CHCl3); Lit.33
[
a]
¼ þ32.0 (c
25
25
D
D
1.0, CH2Cl2); Rf (CH2Cl2/CH3OH, 8: 1) 0.82.
a-D
anose 10 see: Szulc, I.; Kołodziuk, R.; Kryczka, B.; Zawisza, A. Tet-
rahedron Lett. 2015, 56, 4740e4743.
4.5.4. Methyl 2-acetamido-4,6-O-benzylidene-3-O-mesyl-2-deoxy-
a-D
-glucopyranoside 16
The synthesis and spectroscopic data for methyl 2-acetamido-
4.4.3. 1,3,4,-Tri-O-trimethylsilyl-6-O-tert-butyldiphenylsilyl-2-
deoxy-2-{[2-(diphenyl-phosphino)benzoyl]imino}-a-D-
4,6-O-benzylidene-3-O-mesyl-2-deoxy-
a
-
D
-glucopyranoside
16
are in accordance to ref.31
glucopyranose 11 (L4)
Colorless solid, 75% yield; m.p. 187.0e190.0 ꢀC; Lit.31 m.p. 196 ꢀC,
25
Yellow oil, 0.8 g, 43% yield; [
a]
¼ þ8.0 (c 0.5, CHCl3); Rf (hex-
D
25
25
[a
]
¼ þ42.6 (c 0.5, CHCl3); Lit.34 [
a]
¼ þ42.0 (c 1.0, CHCl3); Rf
ane/ethyl acetate, 24:1) 0.72; dH (600 MHz, CDCl3) ꢁ0.07 (s, 9H,
OSi(CH3)3), 0.00 (s, 9H, OSi(CH3)3), 0.01 (s, 9H, OSi(CH3)3), 1.06 (s,
9H, OSiC(CH3)3), 3.03 (dd, 1H, J 8.7, 7.3, H-2), 3.42 (d, 1H, J 8.5, H-4),
3.50 (ddd, 1H, J 8.5, 7.3, 1.7, H-5), 3.68 (dd, 1H, J 10.8, 7.3, H-60), 3.89
(dd, 1H, J 10.8, 1.7, H-6), 3.93 (dd, 1H, J 8.7, 8.5, H-3), 4.76 (d, 1H, J 7.3,
H-1), 7.26e7.38 (m, 24H, C6H5), 9.05 (d, 1H, J 5.8, NCH); dC
(150 MHz, CDCl3) 0.1 (OSi(CH3)3), 0.8 (OSi(CH3)3), 1.4 (OSi(CH3)3),
19.2 (OSiC(CH3)3), 26.9 (OSiC(CH3)3), 64.4 (C-2), 72.4 (C-6), 77.6,
77.9 (C-4, C-5), 79.4 (C-3), 95.8 (C-1), 128.5128.6, 128.7, 128.8, 128.9,
129.1, 129.5, 130.4, 133.8, 133.9, 134.0, 134.1, 135.8, 135.9, 136.7
(C6H5), 162.3 (d, J ¼ 25.5, NCH); found: C, 66.34; H, 7.70; N, 1.47.
D
D
(CH2Cl2/CH3OH, 8: 1) 0.90.
4.5.5. Methyl 2-acetamido-4,6-O-benzylidene-2-deoxy-a-D-
allopyranoside 17
The synthesis and spectroscopic data for methyl 2-acetamido-
4,6-O-benzylidene-2-deoxy-a-D-allopyranoside 17 are in accor-
dance to ref.31
Colorless solid, 84% yield; m.p. 194.0e195.5 ꢀC; Lit.31b m.p.
25
25
196 ꢀC, [
a
]
D
¼ þ66.4 (c 1.0, CHCl3); Lit.34
[
a
]
¼ þ64.0 (c 0.5,
D
CHCl3); Rf (ethyl acetate/CH3OH, 40: 1) 0.39.
C
50H68NO5PSi4 requires C, 66.26; H, 7.56; N, 1.55%.
4.5.6. Methyl 2-acetamido-2-deoxy-a-D-allopyranoside 18
The synthesis and spectroscopic data for methyl 2-acetamido-2-
4.4.4. 1,3,4,-Tri-O-trimethylsilyl-6-O-tert-butyldimethylsilyl-2-
deoxy-2-{[2-(diphenyl-phosphino)benzoyl]imino}-a-D-
deoxy-
a
-D
-allopyranoside 18 are in accordance to ref.35
25
Colorless oil, 93% yield; [
a
]
¼ þ76.6 (c 0.5, H2O); Lit.35
glucopyranose 12 (L5)
D
25
25
[a
]
¼ þ77.9 (c 0.7, H2O); Rf (ethyl acetate/CH3OH, 8: 1) 0.19.
Yellow oil, 0.7 g, 45% yield; [
a
]
¼ þ15.6 (c 0.5, CHCl3); Rf
D
D
(CH2Cl2/CH3OH, 12: 1) 0.89; dH (600 MHz, CDCl3) ꢁ0.04 (s, 9H,
OSi(CH3)3), 0.00 (s, 9H, OSi(CH3)3), 0.19 (s, 9H, OSi(CH3)3), 0.09 (s,
3H, OSi(CH3)2), 0.10 (s, 3H, OSi(CH3)2), 0.92 (s, 9H, OSiC(CH3)3), 3.00
(dd, 1H, J 9.0, 7.3, H-2), 3.32 (ddd, 1H, J 9.2, 5.0, 1.9, H-5), 3.61 (t,1H, J
9.2, H-4), 3.77 (dd, 1H, J 11.2, 5.0, H-60), 3.86 (dd, 1H, J 11.2, 1.9, H-6),
3.94 (dd,1H, J 9.2, 9.0, H-3), 4.70 (d,1H, J 7.3, H-1), 6.97e6.99 (m,1H,
C6H5), 7.23e7.39 (m, 13H, C6H5), 9.05 (d, 1H, J 5.6, NCH); dC
(150 MHz, CDCl3) ꢁ5.3 (OSi(CH3)2), 0.1 (OSiC(CH3)3), 0.9
(OSiC(CH3)3), 1.4 (OSiC(CH3)3), 18.4 (OSiC(CH3)3), 26.0 (OSiC(CH3)3),
62.8 (C-6), 71.7 (C-4), 77.1 (C-5), 77.9 (C-3), 79.4 (C-2), 95.9 (C-1),
127.3, 128.1, 128.2, 128.4, 128.5, 128.6, 128.7, 128.8, 128.9, 130.3,
133.7, 133.8, 133.9, 134.2, 136.8, 137.6 (C6H5), 162.3 (d, J ¼ 26.4,
NCH); found: C, 61.25; H, 7.94; N, 2.05. C40H64NO5PSi4 requires C,
61.41; H, 8.25; N, 1.79%.
4.5.7. 2-Amino-2-deoxy allosamine hydrochloride 19
Procedure for the synthesis of 2-amino-2-deoxy allosamine
hydrochloride 19 see ref.34
Yellow solid, 100% yield; m.p. 145.0e147.5 ꢀC; Lit.36 m.p.
25
25
145e148 ꢀC, [
a]
¼ þ15.4 (c 1.0, H2O); Lit.36
[
a]
¼ þ16.0 (c 1.4,
D
D
H2O); Rf (CH2Cl2/CH3OH, 8: 3) 0.26; dH (600 MHz, CDCl3) 2.89 (m,
1H, H-2), 3.30e3.80 (m, 4H, H-4, H-5, H-6, H-60), 4.07 (s, 1H, H-3),
4.88 (d, 1H, J 8.3, H-1), 8.00 (s, 2H, NH2); dC (150 MHz, CDCl3) 54.3
(C-2), 61.0 (C-6), 66.8 (C-5), 67.9 (C-3), 74.4 (C-4), 90.9 (C-1).
4.5.8. 2-Amino-2-deoxy-1,3,4,6-tetra-O-trimethylsilyl-a-D-
allopyranose 20
Procedure for the synthesis of 2-amino-2-deoxy-1,3,4,6-tetra-O-
trimethylsilyl- -allopyranose 20 see 4.3.
Colorless oil, 2.3 g, 40% yield; [
a-D
25
4.5. Synthesis of 1,3,4,6-tetra-O-trimethylsilyl-2-deoxy-2-{[2-
a]
¼ þ38.6 (c 0.5, CHCl3); Rf
D
(diphenylphosphino) benzoyl]imino}-a-D-allopyranose 21 (L3)
(petroleum ether/ethyl acetate, 5: 1) 0.62; dH (600 MHz, CDCl3) 0.11
(s, 9H, OSi(CH3)3), 0.13 (s, 9H, OSi(CH3)3), 0.14 (s, 9H, OSi(CH3)3),
0.18 (s, 9H, OSi(CH3)3), 1.48 (s, 2H, NH2), 2.38 (dd, 1H, J 7.6, 2.3, H-2),
3.52 (dd, 1H, J 9.1, 2.2, H-4), 3.58 (dd, 1H, J 10.9, 5.8, H-60), 3.70e3.75
(m, 2H,H-5, H-6), 4.01 (s, 1H, H-3), 4.64 (d, 1H, J 7.6, H-1); dC
(150 MHz, CDCl3) ꢁ0.2 (OSi(CH3)3), 0.5 (OSi(CH3)3), 0.6 (OSi(CH3)3),
0.9 (OSi(CH3)3), 57.7 (C-2), 62.7 (C-6), 70.4 (C-4), 74.4 (C-5), 75.3 (C-
3), 97.7 (C-1); found: C, 46.20; H, 9.50; N, 3.19. C18H45NO5PSi4 re-
quires C, 46.21; H, 9.69; N, 2.99%.
4.5.1. 2-Acetamido-2-deoxy- -glucopyranose 13
a-D
The synthesis and spectroscopic data for 2-acetamido-2-deoxy-
a
-
D
-glucopyranose 13 are in accordance to ref.25
Colorless solid, 78% yield; m.p. 202.0e204.0 ꢀC; Lit.26 m.p.
25
25
203.0e205.0 ꢀC; [
0.5, H2O); Rf (CH2Cl2/CH3OH, 10: 3) 0.57.
a
]
¼ þ66.0 (c 0.5, H2O); Lit.27
[a
]
¼ þ70.0 (c
D
D
4.5.2. Methyl 2-acetamido-2-deoxy-
The synthesis and spectroscopic data for methyl 2-acetamido-2-
deoxy-
-glucopyranoside 14 are in accordance to ref.28
Yellow solid, 70% yield; m.p. 190.0e192.0 ꢀC; Lit. m.p.29
a-D-glucopyranoside 14
4.5.9. 1,3,4,6-Tetra-O-trimethylsilyl-2-deoxy-2-{[2-
a
-D
(diphenylphosphino)benzoyl] imino}-a-D-allopyranose 21 (L3)
Procedure for the synthesis of 1,3,4,6-tetra-O-trimethylsilyl-2-
Please cite this article in press as: Szulc I, et al., New phosphine-imine and phosphine-amine ligands derived from D-gluco-, D-galacto- and D-
allosamine in Pd-catalysed asymmetric allylic alkylation, Tetrahedron (2018), https://doi.org/10.1016/j.tet.2018.02.009

8
I. Szulc et al. / Tetrahedron xxx (2018) 1e10
deoxy-2-{[2-(diphenylphosphino)benzoyl] imino}-
a
-
D
-allopyranose
5), 95.2 (CCl3CH2OCO), 96.3 (C-1), 154.2 (CCl3CH2OCO), 169.6, 170.7,
21 (L3) see 4.4.
170.8 (CH3CO); MS-EI (m/z): 616.3 [(MþNa)þ, 100]; found: C, 42.49;
H, 5.64; N, 2.23. C21H34Cl3NO10Si requires C, 42.39; H, 5.76; N,
2.35%.
25
Yellow oil, 0.9 g, 57% yield; [
a]
¼ þ16.8 (c 0.5, CHCl3); Rf
D
(hexane/ethyl acetate, 5: 1) 0.82; dH (600 MHz, CDCl3) 0.03 (s, 9H,
OSi(CH3)3), 0.08 (s, 9H, OSi(CH3)3), 0.12 (s, 9H, OSi(CH3)3), 0.14 (s,
9H, OSi(CH3)3), 2.97 (dd, 1H, J 7.4, 2.0, H-2), 3.57 (dd, 1H, J 9.4, 2.4,
H-4), 3.66 (dd, 1H, J 11.2, 5.9, H-60), 3.74e3.82 (m, 2H, H-5, H-6),
3.99 (dd, 1H, J 2.4, 2.0, H-3), 5.23 (d, 1H, J 7.4, H-1), 7.15e7.70 (m,
13H, C6H5), 8.15e8.19 (m, 1H, C6H5), 9.04 (d, 1H, J ¼ 5.6, NCH); dC
(150 MHz, CDCl3) ꢁ0.2, 0.3, 0.4, 0.8 (4OSi(CH3)3), 57.5 (C-2), 62.9 (C-
6), 69.3 (C-4), 74.5 (C-5), 76.5 (C-3), 93.8 (C-1), 127.0 (d, J 4.4, C6H5),
128.6, 128.7, 128.8,129.0,129.1, 130.4,130.6,132.1, 133.7, 133.9, 134.0
(C6H5), 134.1 (d, J 5.5, C6H5), 137.0 (d, J 9.8, C6H5), 137.9 (d, J 18.7,
C6H5), 160.8 (d, J ¼ 26.7, NCH); found: C, 60.14; H, 7.94; N, 1.78.
4.6.5. 1-O-tert-Butyldiphenylsilyl-3,4,6-tri-O-acetyl-2-deoxy-2-
amino-b-D-glucopyranoside 26
The synthesis and spectroscopic data for 1-O-tert-butyldiphe-
nylsilyl-3,4,6-tri-O-acetyl-2-deoxy-2-amino-b-D-glucopyranoside
26 are in accordance to ref.37
25
Colorless oil, 80% yield; [
a
]
¼ þ4.7 (c 0.5, CHCl3); Rf (hexane/
D
ethyl acetate, 1: 2) 0.65.
4.6.6. 1-O-tert-Butyldimethylsilyl-3,4,6-tri-O-acetyl-2-deoxy-2-
amino- -glucopyranoside 27
b-D
C
37H58NO5PSi4 requires C, 60.04; H, 7.90; N, 1.89%.
To a solution of compound 25 (2,0 g, 3.4 mmol) in glacial acetic
acid (100 mL), activated Zn dust (4.6 g, 70.0 mmol) [washed with aq
2 M HCl, water, acetone, diethyl ether, and then dried under vac-
uum] was added in one portion and the mixture was vigorously
stirred for 24 h (TLC monitoring) at room temperature. The solid
was then filtered off and most of acetic acid was evaporated under
reduced pressure. The residue was diluted with AcOEt and the
resulting solution was shaken with saturated aq NaHCO3, washed
with brine until neutral, dried (Na2SO4). The solvents were evap-
orated under reduced pressure and the crude residue was purified
4.6. Synthesis of ligands L6-L9
4.6.1. 1,3,4,6-Tetra-O-acetyl-2-deoxy-2-(2,2,2-
trichloroethoxycarbonylamino)-
a,b-D-glucopyranoside 22
The synthesis and spectroscopic data for 1,3,4,6-tetra-O-acetyl-
2-deoxy-2-(2,2,2-trichloroethoxycarbonylamino)-D-glucopyrano-
side 22 are in accordance to ref.37
Colorless oil, 74% yield; Rf (petroleum ether/ethyl acetate, 1: 1)
0.73.
by flash column chromatography on silica gel.
25
Colorless solid, 1.3 g, 83% yield; m.p. 61.0e63.0 ꢀC; [
a
]
¼ þ21.8
D
4.6.2. 3,4,6-Tri-O-acetyl-2-deoxy-2-(2,2,2-
trichloroethoxycarbonylamino)- -glucopyranose 23
The synthesis and spectroscopic data for 3,4,6-tri-O-acetyl-2-
(c 0.5, CHCl3); Rf (hexane/ethyl acetate, 1: 2) 0.50; dH (600 MHz,
CDCl3) 0.14, 0.15 (s, 6H, 2 ꢂ Si-CH3), 0.95 (s, 9H, C(CH3)3), 1.54 (s, 2H,
NH2), 2.03, 2.08, 2.08 (s, 9H, 3 ꢂ CH3), 2.81e2.88 (m, 1H, H-2),
3.66e3.72 (m, 1H, H-5), 4.13 (dd, 1H, J 12.0, 2.5, H-6a), 4.21 (dd, 1H, J
12.0, 6.1, H-6b), 4.52 (d, 1H, J 7.5, H-1), 4.91e4.98 (m, 2H, H-3, H-4);
dC (150 MHz, CDCl3) ꢁ5.2, ꢁ4.3 (Si-CH3), 18.2 ((CH3)3C), 20.7, 20.8,
20.9 (CH3CO), 25.6 ((CH3)3C), 57.7 (C-2), 62.8 (C-6), 69.3 (C-4), 72.2
(C-3), 75.3 (C-5), 99.2 (C-1), 169.9, 170.7, 170.7 (CH3CO); MS-EI (m/
z): 420.2 [(MþH)þ, 100]; found: C, 51.48; H, 7.96; N, 3.42.
a,b-D
deoxy-2-(2,2,2-trichloroethoxycarbonylamino)-a,b-D-glucopyr-
anose 23 are in accordance to ref.37
Yellow solid, 84% yield; m.p. 172.0e175.0 ꢀC; Rf (petroleum
ether/ethyl acetate, 1: 1) 0.60.
4.6.3. 1-O-tert-Butyldiphenylsilyl-3,4,6-tri-O-acetyl-2-deoxy-2-
(2,2,2-trichloroethoxycarbonylamino)-b-D-glucopyranoside 24
The synthesis and spectroscopic data for 1-O-tert-butyldiphe-
nylsilyl-3,4,6-tri-O-acetyl-2-deoxy-2-(2,2,2-
C18H33NO8Si requires C, 51.53; H, 7.93; N, 3.34%.
4.6.7. 1-O-tert-Butyldiphenylsilyl-3,4,6-tri-O-acetyl-2-deoxy-2-
trichloroethoxycarbonylamino)-
b
-D
-glucopyranoside 24 are in
amino-{[2-(diphenylphosphino)benzoyl] imino}-
b -D-
accordance to ref.37
glucopyranose 28 (L6)
Procedure for the synthesis of 1-O-tert-butyldiphenylsilyl-3,4,6-
tri-O-acetyl-2-deoxy-2-amino-{[2-(diphenylphosphino)benzoyl]
25
Colorless solid, 75% yield; m.p. 147.0e149.0 ꢀC; [
a]
¼ þ9.6 (c
D
0.5, CHCl3); Rf (hexane/ethyl acetate, 3: 1) 0.44.
imino}-
b -D-glucopyranose 28 (L6) see 4.4.
25
4.6.4. 1-O-tert-Butyldimethylsilyl-3,4,6-tri-O-acetyl-2-deoxy-2-
(2,2,2-trichloroethoxycarbonylamino)- -glucopyranoside 25
Yellow solid, 1.1 g, 75% yield; m.p. 58.0e67.0 ꢀC; [
a
]
¼ þ17.1 (c
D
b-
D
0.5, CHCl3); Rf (hexane/ethyl acetate, 2: 1) 0.54; dH (600 MHz,
CDCl3) 0.98 (s, 9H, C(CH3)3), 1.65,1.97, 2.01 (s, 9H, 3 ꢂ CH3), 3.41 (dd,
1H, J 9.8, 7.5, H-2), 3.48 (ddd, 1H, J 9.8, 5.4, 2.3, H-5), 3.99 (dd, 1H, J
12.0, 2.3, H-6a), 4.13 (dd, 1H, J 12.0, 5.6, H-6b), 4.88 (d, 1H, J 7.5, H-1),
5.03 (dd, 1H, J 9.8, 9.8, H-4), 5.21 (dd, 1H, J 9.8, 9.8, H-3), 6.91e6.95
(m, 1H, C6H5), 7.19e7.22 (m, 6H, C6H5), 7.24e7.40 (m, 12H, C6H5),
7.55e7.60 (m, 2H, C6H5), 7.67 7.69 (m, 2H, C6H5), 8.03e8.07 (m, 1H,
C6H5), 9.10 (d, 1H, J 5.6, N¼CH); dC (150 MHz, CDCl3) 19.3 ((CH3)3C),
20.4, 20.8, 20.8 (CH3CO), 26.9 ((CH3)3C), 62.3 (C-6), 69.2 (C-4), 71.6
(C-5), 73.4 (C-3), 76.3 (C-2), 96.9 (C-1), 127.2e139.4 (C6H5), 162.9 (d,
J 30.6 N¼CH), 169.9, 169.9, 170.7 (CH3CO); MS-EI (m/z): 816.4
[(MþH)þ, 100]; found: C, 69.03; H, 6.18; N, 1.52. C47H50NO8PSi re-
quires C, 69.03; H, 6.18; N, 1.72%.
To a magnetically stirred solution of 23 (2.5 g, 5.0 mmol) in
anhydrous CH3CN (30 mL) at room temperature, solid imidazole
(0.78 g, 11.5 mmol) was added in one portion, followed by tert-
butyldimethylchlorosilane (TBDPSCl) (1.7 mL, 11.5 mmol), added
dropwise. After 24 h the solvent was removed under reduced
pressure. The crude residue was dissolved in CHCl3 and the solution
was washed with brine until neutral, dried (Na2SO4), and the sol-
vents evaporated under vacuum. The final product was isolated by
flash column chromatography on silica gel.
Colorless solid, 2.6 g, 84% yield; m.p. 160.0e162.0 ꢀC;
25
[
a]
¼ þ4.4 (c 0.5, CHCl3); Rf (hexane/ethyl acetate, 3: 1) 0.42; dH
D
(600 MHz, CDCl3) 0.10, 0.12 (s, 6H, 2 ꢂ Si-CH3), 0.89 (s, 9H, C(CH3)3),
2.01, 2.03, 2.06 (s, 9H, 3 ꢂ CH3), 3.57e3.63 (m, 1H, H-2), 3.68e3.74
(m,1H, H-5), 4.14 (dd,1H, J 11.7, 2.2, H-6a), 4.21 (dd,1H, J 11.7, 5.8, H-
6b), 4.62 (d, 1H, J 11.8, Ha-Troc), 4.75 (d, 1H, J 11.8, Hb-Troc), 4.83 (d,
1H, J 7.8, H-1), 5.05 (dd, 1H, J 9.6, 9.6, H-3), 5.15 (d, 1H, J 8.3, NH),
5.27 (dd, 1H, J 9.6, 9.6, H-4); dC (150 MHz, CDCl3) ꢁ5.2, ꢁ4.4 (Si-
CH3), 17.8 ((CH3)3C), 20.7, 20.7, 20.8 (CH3CO), 25.7 ((CH3)3C), 58.4
(C-2), 62.6 (C-6), 69.2 (C-4), 71.8 (C-3), 72.3 (CCl3CH2OCO), 74.5 (C-
4.6.8. 1-O-tert-Butyldimethylsilyl-3,4,6-tri-O-acetyl-2-deoxy-2-
amino-{[2-(diphenylphosphino)benzoyl] imino}-
glucopyranose 29 (L7)
b -D-
Procedure for the synthesis of 1-O-tert-butyldimethylsilyl-3,4,6-
tri-O-acetyl-2-deoxy-2-amino-{[2-(diphenylphosphino)benzoyl]
imino}-
b -D-glucopyranose 29 (L7) see 4.4.
Please cite this article in press as: Szulc I, et al., New phosphine-imine and phosphine-amine ligands derived from D-gluco-, D-galacto- and D-
allosamine in Pd-catalysed asymmetric allylic alkylation, Tetrahedron (2018), https://doi.org/10.1016/j.tet.2018.02.009

I. Szulc et al. / Tetrahedron xxx (2018) 1e10
9
25
Yellow solid, 1.4 g, 85% yield; m.p. 49.0e57.0 ꢀC; [
a]
¼ ꢁ7.5 (c
(3xCH3CO), 26.0 ((CH3)3C), 51.1 (d, J 22,2, CH2), 62.9 (C-6), 63.8 (C-
2), 69.8 (C-4), 71.8 (C-5), 74.7 (C-3), 99.4 (C-1), 127.4 (Car), 128.7 (d, J
6.4, C6H5), 128,8 (d, J 5.9, C6H5), 128,9 (d, J 5.5, C6H5), 129.2 (C6H5),
133.9 (d, J 2.9, C6H5), 134.0 (d, J 2.2, C6H5), 135.3 (d, J 14.1, C6H5),
136.8 (d, J 9.8, C6H5), 136.9 (d, J 9.8, C6H5), 145.0 (d, J 18.7, C6H5),
169.9, 170.7, 171.0 (3xCH3CO); MS-EI (m/z): 694.3 [(MþH)þ, 100];
found: C, 63.81; H, 6.95; N, 1.99. C37H48NO8PSi requires C, 64.05; H,
6.97; N, 2.02%.
D
0.5, CHCl3); Rf (hexane/ethyl acetate, 2: 1) 0.54; dH (600 MHz,
CDCl3) ꢁ0.08, ꢁ0.02, (s, 6H, 2 ꢂ Si-CH3), 0.74 (s, 9H, C(CH3)3), 1.63,
1.96, 2.03 (s, 9H, 3 ꢂ CH3), 3.18 (dd, 1H, J 9.7, 7.6, H-2), 3.71 (ddd, 1H,
J 9.8, 5.2, 2.2, H-5), 4.03 (dd, 1H, J 11.9, 2.2, H-6a), 4.20 (dd, 1H, J 11.9,
5.2, H-6b), 4.81 (d, 1H, J 7.5, H-1), 4.92 (dd, 1H, J 9.8, 9.8, H-4), 5.28
(dd, 1H, J 9.8, 9.8, H-3), 6.77e6.85 (m, 1H, C6H5), 7.13e7.35 (m, 12H,
C6H5), 7.92e7.99 (m, 1H, C6H5), 8.99 (d, 1H, J 5.5, N¼CH); dC
(150 MHz, CDCl3) ꢁ5.3, ꢁ4.4 (Si-CH3), 18.0 ((CH3)3C), 20.4, 20.7,
20.8 (CH3CO), 25.5 ((CH3)3C), 62.7 (C-6), 69.1 (C-4), 71.8 (C-5), 73.2
(C-3), 76.2 (C-2), 96.6 (C-1), 127.7e139.4 (C6H5), 162.9 (d, J 25.4,
N¼CH), 169.9, 170.0, 170.7 (CH3CO); MS-EI (m/z): 692.3 [(MþH)þ,
100]; found: C, 64.25; H, 6.91; N, 1.91. C37H46NO8PSi requires C,
64.24; H, 6.70; N, 2.02%.
4.8. Typical procedure for the Pd0-catalysed reaction
The catalytic system was prepared by stirring [Pd(C3H5)Cl]2
(3.6 mg, 9.9 mmmol) and the ligand (19.8 mmmol) in an appropriate
anhydrous solvent (3 mL) for 0.5 h in a Schlenk tube under argon.
This solution was added, under argon, to a Schlenk tube containing
the 1,3-diphenyl-2-propenyl acetate 32 (50 mg, 0.198 mmol), KOAc
4.7. Typical procedure for the synthesis of phosphine-amine ligands
30e31
(0.97 mg, 9.9 mmmol), and BSA (0.1 mL, 0.4 mmol) and NuH
(0.4 mmol) in an appropriate anhydrous solvent (3 mL). The solu-
tion was stirred at 25 ꢀC (0 ꢀC or e 20 ꢀC). After an appropriate
period of time, removal of the solvent followed by column chro-
matography gave the corresponding product.
The phosphine-imine derivative 28 or 29 (0.26 mmol) was dis-
solved in a mixture of methanol (7.5 mL) and acetic acid (0.75 mL).
NaBH3CN (0.123 g, 1.95 mmol) was added to the previous solution,
and the mixture was stirred at room temperature for 15 min before
adding water (30 mL) in order to stop the reaction. The aqueous
phase was extracted with CH2Cl2 (3 ꢂ 30 mL), and the combined
organic phase was washed with a saturated solution of NaHCO3 and
then of brine, dried with Na2SO4, and concentrated. The phosphine-
amine compounds 30 and 31 were obtained in quantitative yield
without further purification.
Acknowledgements
This work was partly financed by the European Union within the
European Regional Development Fund (POIG.01.01.02-14-102/09).
Appendix A. Supplementary data
4.7.1. 1-O-tert-butyldiphenylsilyl-3,4,6-tri-O-acetyl-2-deoxy-2-{[2-
Supplementary data related to this article can be found at
https://doi.org/10.1016/j.tet.2018.02.009.
(diphenylphosphino) benzyl]amino}-b-D- glucopyranose 30 (L8)
Colorless, 0.2 g, quantitative yield; m.p. 56.0e67.0 ꢀC;
25
[
a]
¼ þ8.6 (c 0.5, CHCl3); Rf (petroleum ether/ethyl acetate, 5: 1)
D
References
0.33; dH (600 MHz, CDCl3) 1.00 (s, 9H, C(CH3)3), 1.50 (s, 1H, NH), 1.80
(s, 3H, CH3CO), 1.86 (s, 6H, 2xCH3CO), 2.83 (dd, 1H, J 9.7, 7.7, H-2),
3.17 (ddd, 1H, J 8.8, 5.2, 2.4, H-5), 3.72 (dd, 1H, J 12.0, 2.4, H-6a), 3.87
(dd, 1H, J 12.0, 5.2, H-6b), 4.02e4.04 (m, 2H, CH2NH), 4.43 (d, 1H,
J ¼ .7, H-1), 4.82, (dd, 1H, J 9.2, 9.7, H-3), 4.85 (dd, 1H, J 9.2, 8.8, H-4),
6,76 (ddd, 1H, J 7.6, 4.3, 0.8, C6H5), 7.06 (dt, 1H, J 7.6, 1.0, C6H5),
7.10e7.15 (m, 4H, C6H5), 7.19e7.26 (m, 11H, C6H5), 7.29e7.36 (m, 3H,
C6H5), 7.60e7.64 (m, 4H, C6H5); dC (150 MHz, CDCl3) 19.3 ((CH3)3C),
20.8, 21.1, 21.2 (3xCH3CO), 27.2 ((CH3)3C), 51.3 (d, J 23.2, CH2), 62.4
(C-6), 63.9 (C-2), 69.6 (C-4), 71.4 (C-5), 75.0 (C-3), 98.9 (C-1), 127.7
(C6H5), 128.6 (d, J 6.7, C6H5), 128,8 (C6H5), 128,9 (d, J 5.7, C6H5), 129.2
(C6H5), 129.9 (d, J 18.5, C6H5), 133.2 (C6H5), 135.5 (d, J 5.9, C6H5),
133.9 (d, J 10.7, C6H5), 134.0 (d, J 10.2, C6H5), 136.0, 136.2 (C6H5),
136.8 (d, J 10.4, C6H5), 136.9 (d, J 10.5, C6H5), 145.0 (d, J 23.9, C6H5),
169.9, 170.7, 171.0 (3xCH3CO); MS-EI (m/z): 818.4 [(MþH)þ, 100];
found: C, 68.82; H, 6.25; N, 1.78. C47H52NO8PSi requires C, 69.01; H,
6.41; N, 1.71%.
ꢀ
ꢁ
1. (a) Dieguez M, Pamies O, Ruiz A, Diaz Y, Castillon S, Claver C. Coord Chem Rev.
2004;248:2165e2192;
ꢀ
ꢁ
(b) Dieguez M, Pamies O, Claver C. Chem Rev. 2004;104:3189e3215;
ꢀ
ꢁ
(c) Dieguez M, Claver C, Pamies O. Eur J Org Chem. 2007:4621e4634;
(d) Boysen MMK. Chem Eur J. 2007;13:8648e8659;
ꢀ
ꢁ
(e) Woodward S, Dieguez M, Pamies O. Coord Chem Rev. 2010;254:2007e2030;
(f) van Leeuwen PWNM, Kamer PCJ, Claver C, Pamies O, Dieguez M. Chem Rev.
2011;111:2077e2118;
ꢁ
ꢀ
ꢁ
ꢀ
(g) Coll M, Pamies O, Dieguez M. Org Lett. 2014;16:1892e1895;
(h) Xing A, Pang Z, Li H, Wang L. Tetrahedron. 2014;70:8822e8828;
(i) Boysen MMK. Carbohydrates e Tools for Stereoselective Synthesis. Viley-VCH;
2013;
(j) Henderson AS, Bower JF, Galan MC. Org Biomol Chem. 2016;14:4008e4017.
2. See for example: (a) Nagel U, Rieger B. Organometallics. 1989;8:1534e1538;
(b) Gilbertson SR, Chang CWT. J Org Chem. 1995;60:6226e6228;
(c) Brunner H, Sievi R. J Organomet Chem. 1987;328:71e80;
(d) Dieguez M, Pamies O, Ruiz A, Castillon S, Claver C. Tetrahedron: Asymmetry.
2000;11:4701e4708;
(e) Wong YT, Yang C, Ying K-C, Jia G. Organometallics. 2002;21:1782e1787;
(f) Sinou D, Descotes G. React Kinet Catal Lett. 1980;14:463e466;
(g) Selke R. J Organomet Chem. 1989;370:249e256;
(h) RajanBabu TV, Ayers TA, Halliday GA, You KK, Calabrese JC. J Org Chem.
1997;62:6012e6028;
4.7.2. 1-O-tert-butyldimethylsilyl-3,4,6-tri-O-acetyl-2-deoxy-2-
(i) Yan YY, RajanBabu TV. J Org Chem. 2001;66:3277e3283;
(j) Yonehara K, Ohe K, Uemura S. J Org Chem. 1999;64:9381e9385;
(k) Naili S, Suisse I, Mortreux A, Agbossou F, Ali MA, Karim A. Tetrahedron Lett.
2000;41:2867e2870;
(l) Aghmiz M, Aghmiz A, Diaz Y, Masdeu-Bulto AM, Claver C, Castillon S. J Org
Chem. 2004;69:7502e7510;
{[2-(diphenylphosphino) benzyl]amino}-b-D- glucopyranose 31
(L9)
Colorless, 0.18 g, quantitative yield; m.p. 47.0e58.0 ꢀC;
25
[
a]
¼ þ11.1 (c 0.5, CHCl3); Rf (petroleum ether/ethyl acetate, 5: 1)
D
0.33; dH (600 MHz, CDCl3) 0.13 (s, 3H, Si(CH3)2), 0.14 (s, 3H,
Si(CH3)2), 0.90 (s, 9H, C(CH3)3), 1.70 (s, 1H, NH), 1.92, 2.00, 2.05 (3s,
9H, 3xCH3CO), 2.76 (dd, 1H, J 10.1, 7.7, H-2), 3.64 (ddd, 1H, J 9.7, 6,1,
2.5, H-5), 4.03 (dd, 1H, J 13.7, 2.5, H-6a), 4.06e4.12 (m, 2H, CH2NH),
4.15 (dd, 1H, J 12.0, 6.2, H-6b), 4.60 (d, 1H, J 7.7, H-1), 4.93 (dd, 1H, J
9.9, 9.7, H-4), 5.02 (dd, 1H, J 10.1, 9.9, H-3), 6.83 (ddd, 1H, J 7.6, 4.4,
0.7, C6H5), 7.13 (t, 1H, J 7.4, C6H5), 7.19e7.24 (m, 4H, C6H5), 7.28e7.35
(m, 7H, C6H5), 7.48 (dd, 1H, J 7.3, 4.6, C6H5); dC (150 MHz,
CDCl3) ꢁ4.7 (SiCH3), ꢁ4.1 (SiCH3), 18.2 ((CH3)3C), 20.8, 20.8, 21.1
(m) Guiu E, Muenoz B, Castillon S, Claver C. Adv Synth Catal. 2003;345:169e171;
(n) Dieguez M, Ruiz A, Claver C. J Org Chem. 2002;67:3796e3801;
(o) Axet MR, Benet-Buchholz J, Claver C, Castillon S. Adv Synth Catal. 2007;349:
1983e1998;
(p) Reetz MT, Mehler G. Angew Chem Int Ed. 2000;39:3889e3890;
(q) Huang H, Zheng Z, Luo H, Bai C, Hu X, Chen H. J Org Chem. 2004;69:
2355e2361;
(r) Guiu E, Aghmiz M, Diaz Y, et al. Eur J Org Chem. 2006:627e633;
(s) Dieguez M, Mazuela J, Pamies O, Verendel JJ, Andersson PG. J Am Chem Soc.
2008;130:7208e7209;
(t) Khiar N, Navas R, Suarez B, Alvarez E, Fernandez I. Org Lett. 2008;10:
Please cite this article in press as: Szulc I, et al., New phosphine-imine and phosphine-amine ligands derived from D-gluco-, D-galacto- and D-
allosamine in Pd-catalysed asymmetric allylic alkylation, Tetrahedron (2018), https://doi.org/10.1016/j.tet.2018.02.009

10
I. Szulc et al. / Tetrahedron xxx (2018) 1e10
3697e3700.
(c) Minuth T, Boysen MMK. Org Lett. 2009;11:4212e4215;
(d) Minuth T, Irmak M, Groschner A, Lehnert T, Boysen MMK. Eur J Org Chem.
2009:997e1008.
8. See for example: (a) Casalnuovo AL, RajanBabu TV, Ayers TA, Warren TH. J Am
Chem Soc. 1994;116:9869e9882;
3. See for example: (a) Hafner A, Duthaler RO, Marti R, Rihs G, Rothe-Streit P,
Schwarzenbach F. J Am Chem Soc. 1992;114:2321e2336;
(b) Li X-R, Loh T-P. Tetrahedron: Asymmetry. 1996;7:1535e1538;
(c) Pu L, Yu HB. Chem Rev. 2001;101:757e824;
(d) Emmerson DPG, Villard R, Mugnaini C, et al. Org Biomol Chem. 2003;1:
3826e3838;
(b) Park H, Kumareswaran R, RajanBabu TV. Tetrahedron. 2005;61:6352e6357.
9. (a) Glaser B, Kunz H. Synlett. 1998:53e55.
€
(e) Emmerson DPG, Hems WP, Davies BG. Org Lett. 2006;8:207e210;
(f) Irmak M, Boysen MMK. Adv Synth Catal. 2008;350:403e405;
10. (a) Yonehara K, Hashizume T, Mori K, Ohe K, Uemura S. Chem Commun. 1999:
415e416;
(g) Mata Y, Dieguez M, Pamies O, Woodward S.
8159e8165;
J
Org Chem. 2006;71:
(b) Yonehara K, Hashizume T, Mori K, Ohe K, Uemura S. J Org Chem. 1999;64:
9374e9380;
(h) Raluy E, Dieguez M, Pamies O. Tetrahedron: Asymmetry. 2009;20:
1575e1579;
(i) Raluy E, Dieguez M, Pamies O. Tetrahedron Lett. 2009;50:4495e4497;
(j) Shibasaki M, Kanai M. Org Biomol Chem. 2007;5:2027e2039;
(k) Shibasaki M, Kanai M, Matsunaga S, Kumagai N. Acc Chem Res. 2009;42:
1117e1127;
(e) Hashizume T, Yonehara K, Ohe K, Uemura S. J Org Chem. 2000;65:
5197e5201.
ꢀ ꢁ
11. Mata Y, Dieguez M, Pamies O, Claver C. Adv Synth Catal. 2005;347:1943e1947.
ꢁ
ꢀ
12. Mata Y, Pamies O, Dieguez M. Adv Synth Catal. 2009;351:3217e3234.
13. (a) Tollabi M, Framery E, Goux-Henry C, Sinou D. Tetrahedron: Asymmetry.
2003;14:3329e3333;
(l) Masumoto S, Usuda H, Suzuki M, Kanai M, Shibasaki M. J Am Chem Soc.
2003;125:5634e5635;
(b) Glegoła K, Framery E, Goux-Henry C, Pietrusiewicz KM, Sinou D. Tetrahe-
dron. 2007;63:7133e7141;
(m) Mita T, Sasaki K, Kanai M, Shibasaki M. J Am Chem Soc. 2005;127:514e515.
4. See for example: (a) Spescha M. Helv Chim Acta. 1993;76:1832e1847;
(b) Dieguez M, Ruiz A, Claver C. Tetrahedron: Asymmetry. 2001;12:2895e2900;
(c) Guimet E, Dieguez M, Ruiz A, Claver C. Tetrahedron: Asymmetry. 2005;16:
2161e2165;
(c) Johannesen SA, Glegoła K, Sinou D, Framery E, Skrydstrup T. Tetrahedron
Lett. 2007;48:3569e3573;
(d) Glegoła K, Johannesen SA, Thim L, Goux-Henry C, Skrydstrup T, Framery E.
Tetrahedron Lett. 2008;49:6635e6638.
14. (a) Borriello C, Cucialito ME, Panunzi A, Ruffo F. Inorg Chim Acta. 2003;353:
238e244;
(d) Mata Y, Dieguez M, Pamies O, Woodward S. J Organomet Chem. 2007;692:
4315e4320;
€
(b) Brunner H, Schonherr M, Zabel M. Tetrahedron: Asymmetry. 2003:
(e) Raluy E, Pamies O, Dieguez M, Rosset S, Alexakis A. Tetrahedron: Asymmetry.
2009;20:2167e2172;
(f) Mata Y, Dieguez M, Pamies O, Biswas K, Woodward S. Tetrahedron: Asym-
metry. 2007;18:1613e1617;
1115e1122.
15. Irmak M, Groschner A, Boysen MMK. Chem Commun. 2007:177e179.
16. Szulc I, Kołodziuk R, Kryczka B, Zawisza A. Tetrahedron Lett. 2015;56:
4740e4743.
(g) De Roma A, Ruffo F, Woodward S. Chem Commun. 2008:5384e5386;
(h) Pu X, Li P, Peng F, Li X, Zhang H, Shao Z. Eur J Org Chem. 2009:4622e4626;
(i) Bennett SMW, Brown SM, Cunningham A, et al. Tetrahedron. 2000;56:
2847e2855;
17. Wartchow CA, Wang P, Bednarski MD, Callstron MR. J Org Chem. 1995;60:
2216e2226.
18. Olszewska B, Szulc I, Kryczka B, Kubiak A, Porwanski S, Zawisza A. Tetrahedron:
ꢀ
Asymmetry. 2013;24:212e216.
(j) Jaszay Z, Pham TS, Nemeth G, Bako P, Petnehazy I, Toke L. Synlett. 2009:
1429e1432;
19. (a) Yamaguchi T, Hesek D, Lee M, Oliver AG, Mabashery S. J Org Chem. 2010;75:
3515e3517;
(k) Tewes F, Schlecker A, Harms K, Glorius F. J Organomet Chem. 2007;692:
4593e4602.
(b) Marchetti R, Lanzetta R, Michelow IC, Molinaro A, Silipo A. Eur J Org Chem.
2012;27:5275e5281.
5. See for example: (a) Dieguez M, Pamies O, Claver C. Tetrahedron: Asymmetry.
2004;15:2113e2122;
20. (a) Gao F, Yan X, Shakya T, et al. J Med Chem. 2006;49:5273e5281;
€
(b) Boge M, Fowelin Ch, Bednarski P, Heck J. Organometallics. 2015;34:
(b) Breit B. Top Curr Chem. 2007;279:139e172;
1507e1521.
(c)
.
In: van Leeuwen PWNM, Claver C, eds. Rhodium Catalysed Hydro-
21. Wong Ch-H, Ichikawa Y, Krach T, Narvor Ch, Dumas DP, Look GC. J Am Chem
Soc. 1991;113:8137e8145.
22. Jeanloz RW. J Am Chem Soc. 1957;79:2591e2592.
23. De Nisco M, Pedatella S, Bektas S, Nucci A, Caputo R. Carbohydr Res. 2012;356:
273e277.
formylation. Dordrecht: Kluwer Academic Press; 2000;
(d) Axtell AT, Cobley CJ, Klosin J, Whiteker GT, Zanotti-Gerosa A, Abboud KA.
Angew Chem Int Ed. 2005;44:5834e5838;
(e) Clark TP, Landis CR, Freed SL, Klosin J, Abboud KA. J Am Chem Soc. 2005;127:
5040e5042;
24. Mogorosi MM, Mahamo T, Moss JR, et al.
J Organomet Chem. 2011;696:
(f) Thomas PJ, Axtell AT, Klosin J, et al. Org Lett. 2007;9:2665e2668;
(g) Peng X, Wang Z, Xia C, Ding K. Tetrahedron Lett. 2008;49:4862e4864;
(h) Yan Y, Zhang X. J Am Chem Soc. 2006;128:7198e7202;
(i) RajanBabu TV, Ayers TA. Tetrahedron Lett. 1994;35:4295e4298;
(j) Dieguez M, Pamies O, Claver C. Chem Commun. 2005:1221e1223;
(k) Mazuela J, Coll M, Pamies O, Dieguez M. J Org Chem. 2009;74:5440e5445;
(l) Gual A, Godard C, Claver C, Castillon S. Eur J Org Chem. 2009:1191e1201.
6. See for example: (a) Yonehara K, Mori K, Hashizume T, Chung KG, Ohe K,
Uemura S. J Organomet Chem. 2000;603:40e49;
(b) Imbos R, Minnaard AJ, Feringa BL. J Am Chem Soc. 2002;124:184e185;
(c) Imbos R, Minnaard AJ, Feringa BL. Dalton Trans. 2003:2017e2023;
(d) Ozawa F, Kubo A, Hayashi T. J Am Chem Soc. 1991;113:1417e1419;
(e) Loiseleur O, Meier P, Pfaltz A. Angew Chem. 1996;108:218e220;
(f) Loiseleur O, Meier P, Pfaltz A. Angew Chem Int Ed Engl. 1996;35:200e202;
(g) Mata Y, Dieguez M, Pamies O, Claver C. Adv Synth Catal. 2005;347:
1943e1947;
3585e3592.
25. (a) Yamaguchi T, Hesek D, Lee M, Oliver AG, Mabashery S. J Org Chem. 2010;75:
3515e3517;
(b) Marchetti R, Lanzetta R, Michelow IC, Molinaro A, Silipo A. Eur J Org Chem.
2012;27:5275e5281.
26. Horton D, Wolfrom ML. J Org Chem. 1962;27:1794e1800.
27. Yoshihito S, Miwako K, Takuya K, et al. Phytochemistry. 2011;72:1400e1405.
28. Gao F, Yan X, Shakya T, et al. J Med Chem. 2006;49:5273e5281.
29. Tomic S, Ljevakovic D, Tomasic J. Carbohydr Res. 1989;188:222e227.
30. Kovac E. J Org Chem. 1992;57:2455e2467.
31. (a) Reckendorf WM. Chem Ber. 1969;102:4207e4208;
€
(b) Boge M, Fowelin Ch, Bednarski P, Heck J. Organometallics. 2015;34:
1507e1521.
32. (a) Roth W, Pigman W. J Am Chem Soc. 1960;82:4608e4611;
(b) Boutureira O, McGouran JF, Stafford RL, Emmerson DPG, Davis BG. Org
Biomol Chem. 2009;7:4285e4288;
(h) Mata Y, Dieguez M, Pamies O, Claver C. Org Lett. 2005;7:5597e5599;
(i) Mata Y, Pamies O, Dieguez M. Chem Eur J. 2007;13:3296e3304;
(j) Gilbertson SR, Xie D, Fu Z. J Org Chem. 2001;66:7240e7246;
(k) Henriksen ST, Norrby PO, Kaukoranta P, Andersson PG. J Am Chem Soc.
2008;130:10414e10421;
(l) Rubina M, Sherrill WM, Rubin M. Organometallics. 2008;27:6393e6395.
7. See for example: (a) Irmak M, Lehnert T, Boysen MMK. Tetrahedron Lett.
2007;48:7890e7893;
(c) Emmerson DPG, Villard R, Mugnaini C, et al. Org Biomol Chem. 2003;1:
3826e3838.
33. Schoeberl Ch, Jaeger V. Adv Synth Catal. 2012;354:790e796.
34. Jeanloz RW. J Am Chem Soc. 1957;79:2591e2592.
35. Wong Ch-H, Ichikawa Y, Krach T, Narvor Ch, Dumas DP, Look GC. J Am Chem
Soc. 1991;113:8137e8145.
36. Kuhn J. Justus Liebigs Ann Chem. 1961;641:143e150.
37. De Nisco M, Pedatella S, Bektas S, Nucci A, Caputo R. Carbohydr Res. 2012;356:
273e277.
(b) Irmak M, Groschner A, Boysen MMK. Chem Commun. 2007:177e179;
Please cite this article in press as: Szulc I, et al., New phosphine-imine and phosphine-amine ligands derived from D-gluco-, D-galacto- and D-
allosamine in Pd-catalysed asymmetric allylic alkylation, Tetrahedron (2018), https://doi.org/10.1016/j.tet.2018.02.009