Asymmetric allylic substitution catalyzed by palladium-Yliphos complex

Article abstract of DOI:10.1016/S0957-4166(03)00046-6

Allylic substitution reactions catalyzed by Pd- or Pt-Yliphos complexes are examined. The reaction of 1,3-diphenyl-2-propenyl acetate with benzylamine proceeded in the presence of Pd(dba)₂-Yliphos to give N-benzyl-1,3-diphenyl-2-propenylamine i

Full text of DOI:10.1016/S0957-4166(03)00046-6

TETRAHEDRON:
ASYMMETRY
Pergamon
Tetrahedron: Asymmetry 14 (2003) 537–542
Asymmetric allylic substitution catalyzed by palladium–Yliphos
complex
Tetsuo Ohta,* Hiroyuki Sasayama, Osakazu Nakajima, Nobukazu Kurahashi, Takeshi Fujii and
Isao Furukawa
Department of Molecular Science and Technology, Faculty of Engineering, Doshisha University, Kyotanabe,
Kyoto 610-0394, Japan
Received 17 September 2002; revised 26 December 2002; accepted 27 December 2002
Abstract—Allylic substitution reactions catalyzed by Pd– or Pt–Yliphos complexes are examined. The reaction of 1,3-diphenyl-2-
propenyl acetate with benzylamine proceeded in the presence of Pd(dba)2–Yliphos to give N-benzyl-1,3-diphenyl-2-propenylamine
in high yields with high enantioselectivities (up to 90% ee). Furthermore, the allylic alkylation of 1,3-diphenyl-2-propenyl acetate
with dimethyl malonate catalyzed by Pd–Yliphos complex resulted in high enantioselectivity (95% ee) in the presence of LiH as
base. © 2003 Elsevier Science Ltd. All rights reserved.
1. Introduction
2. Results and discussion
2.1. Amination reaction
The asymmetric allylic substitution reaction by chiral
metal complexes has attracted much attention in view
of the high asymmetric induction and usefulness of the
products.1 Although many important results have been
reported so far, recent approaches have been directed
toward substrate-tailored catalyst systems. Recently,
chiral bidentate ligands having different kinds of coor-
dination sites have opened a new era in asymmetric
reactions.2,3
The reaction of 1,3-diphenyl-2-propenyl acetate 3a with
benzylamine 4a (2.5 equiv. to 3a) proceeded slowly in
THF in low yield with good enantioselectivity (78% ee)
using (S)-2a–Pd(0) complex as the catalyst (Scheme 1,
Table 1, entry 6). The reaction conditions were then
optimized (Table 1). In cyclohexane, acetonitrile, or
dichloromethane, the enantiomeric excesses were some-
what low, while no reaction occurred in DMF or
DMSO. Consequently, the reaction occurs either in
toluene, THF, or dioxane. Using 2.5 equiv. of amine
resulted in a low yield of the product, while increasing
the amount of amine made the reaction proceed faster.
With 20 equiv. of amine relative to 3a, the yield of 5a
became 98% without any loss of enantiomeric excess
(Table 1, entry 8). The reaction temperature did not
strongly affect the yields and enantiomeric excesses
(Table 1, entries 8–10). The combination of (S)-2a and
Pt(dba)2 showed no catalytic activity at all.
We have already reported the preparation of chiral
mono ylide–mono phosphine ligands (Yliphos, 2) from
diphosphine (TolBINAP, 1) and also the preparation of
their metal complexes.4,5 These Yliphos–Pd(0) com-
plexes were successfully applied to asymmetric allylic
substitution reactions. Herein we wish to describe the
details of this reaction.
Next, the effect of a substituent on the ylide carbon was
investigated. Three Yliphos ligands (S)-2a–c were used
for this reaction, and cyano-substituted Yliphos 2a
(CN-TolYliphos) showed good results, while using
* Corresponding author. Fax: 81-774-65-6789.
Scheme 1.
0957-4166/03/$ - see front matter © 2003 Elsevier Science Ltd. All rights reserved.
doi:10.1016/S0957-4166(03)00046-6

538
T. Ohta et al. / Tetrahedron: Asymmetry 14 (2003) 537–542
a
Table 1. Effects of reaction conditions on the reaction of 3a and benzylamine 4a catalyzed by (S)-2a/Pd(dba)2
Entry
Ligand
Solvent
Amount of 4a (equiv. to 3a)
Product 5a
Yield (%)b
% eec
1
2
3
4
5
6
7
8
(S)-2a
(S)-2a
(S)-2a
(S)-2a
(S)-2a
(S)-2a
(S)-2a
(S)-2a
(S)-2a
(S)-2a
(S)-2b
(S)-2c
Cyclohexane
Toluene
1,4-Dioxane
CH2Cl2
CH3CN
THF
THF
THF
THF
THF
2.5
2.5
2.5
2.5
2.5
2.5
10
20
20
20
20
48
69
46
75
56
30
75
98
99
72
32
28
68
90
87
62
46
78
82
79
84
85
54
25
9d
10e
11
12
THF
THF
20
a A mixture of 3a (0.25 mmol), 4a, and catalyst (5 mol%, (S)-2/Pd(dba)2) in solvent (1 mL) was stirred at 50°C for 48 h.
b Isolated yield based on 3a.
c Determined by HPLC analysis using a Daicel Chiralcel OD-H column.
d At room temperature.
e At 0°C.
alkoxycarbonyl-substituted Yliphos 2b or 2c resulted in
low yields with low selectivities (Table 1, entries 8, 11,
and 12).
Furthermore, almost no reaction occurred on employing
3d as a substrate.
Various nitrogen nucleophiles were employed under
standard reaction conditions in the presence of the
(S)-2a–Pd(0) complex (Scheme 2 and Table 2). When
primary amines 4a–c were used, the bulkiness of the
nucleophiles 4 substantially influenced the yields of the
products. That is, the reactions of benzylamine and
butylamine proceeded smoothly to give the product in
almost quantitative yield with about 80% ee, while no
reaction occurred with the use of t-butylamine as a
substrate.
From our previous study, Yliphos ligands (S)-2a–c
coordinatetothemetalcenterstronglyviathephosphorus
atom of the phosphine moiety and weakly via the anionic
carbon atom of the ylide.4 That is, Yliphos can act as a
monodentate and/or a bidentate ligand. To obtain infor-
mation on the coordination modes of Yliphos,
monophosphine–monophosphonium compounds (S)-
2a–c·HBr, Yliphos·HBr, precursors to Yliphos, were used
forthisreactionasligands(Table3), becauseYliphos·HBr
may coordinate only as a monodentate ligand. Interest-
ingly, the enantiomeric excesses of the product 5a from
the reaction of 3a with benzylamine 4a were nearly similar
using (S)-2a–c·HBr as a ligand, although substituted
derivatives were different (Table 3). In the case of the
reactionsusing(S)-2a–casaligand, enantiomericexcesses
of the products were different (Table 1, entries 8, 10, and
11). These results indicate that Yliphos may not coordi-
nate to the palladium center in monodentate fashion
unlike Yliphos·HBr.
Scheme 2.
Several allylic substrates were tried for this amination:
1,3-diphenyl-2-propenyl acetate 3a was converted to all
corresponding allylamine derivatives in good yield with
high enantiomeric excess. Less hindered substrate 3b was
converted to 5f in good yield with low ee (95% yield, 5%
ee), while 5g was obtained from the reaction of 3-propen-
2-yl acetate 3c in 43% yield with no stereoselectivity.

T. Ohta et al. / Tetrahedron: Asymmetry 14 (2003) 537–542
Table 2. Several nucleophiles in catalytic allylic amination reactiona
539
Entry
Nucleophiles
Product
Yield (%)b
% eec
Config.d
1
4a
4a
4b
4b
4c
4d
4e
5a
5a
5b
5b
5c
5d
5e
98
99
Quant.
Quant.
Trace
40
79
84
78
81
–
S
S
2e
3
(−)
(−)
–
(−)
S
4e
5
6
63
69
7
5
a A mixture of 3a (0.25 mmol), 4 (5.0 mmol), and catalyst (5 mol%, (S)-2a/Pd(dba)2) in THF (1 mL) was stirred at 50°C for 48 h.
b Isolated yield based on 3a.
c Determined by HPLC analysis using a Daicel Chiralcel OD-H column.
d Determined by the sign of the optical rotation value and/or the retention time in chiral HPLC analysis.
e At room temperature.
Table 3. Effect of ligand on the reaction of 3a with 4a by
Bases containing lithium were then tried for this cataly-
sis. Lithium hydride gave excellent results, while other
lithium compounds showed good but lower selectivities
than lithium hydride. Sodium hydride and potassium
hydride were not good bases for this reaction. Interest-
ingly, the addition of LiCl to the NaH promoted
reaction increased the enantiomeric excess of 70–81%.
The reaction of 3a with 6 in the presence of LiH
proceeded smoothly at room temperature to give the
alkylation product 7a in 91% yield with 95% enan-
tiomeric excess.
Pd complexa
Entry
Ligand
Yield (%)b
% eec
Config.d
1
2
3
(S)-2a·HBr
(S)-2b·HBr
(S)-2c·HBr
76
80
42
83
83
82
S
S
S
a A mixture of 3a (0.25 mmol), 4a (5.0 mmol), and catalyst (5 mol%,
ligand/Pd(dba)2) in THF (1 mL) was stirred at 50°C for 48 h.
b Isolated yield based on 3a.
c Determined by HPLC analysis using a Daicel Chiralcel OD-H
column.
Using LiH as the base, the reaction conditions (catalyst
ratio, ligand, amount of nucleophile, reaction tempera-
ture) were optimized. As shown in Table 4, the most
favorable reaction conditions are room temperature, 2
mol% catalyst, and 3 equiv. of 6 to 3a. CN–Yliphos
(S)-2a is the best among the Yliphos ligands tested,
while Yliphos ligands having an alkoxycarbonyl sub-
stituent showed moderate enantioselectivities.
d Determined by the sign of the optical rotation value and/or the
retention time in chiral HPLC analysis.
2.2. Alkylation reaction
Alkylation of 3a using the anion of dimethyl malonate
with NaH in THF resulted in poor selectivity using
platinum– or palladium–Yliphos catalyst. The reaction
solvent was optimized for the reaction of 3a with 6 in
the presence of potassium acetate and BSA with
Pd(dba)2–(S)-2a catalyst (Scheme 3 and Table 4). The
reaction proceeded smoothly in THF or DMF, while
higher selectivity was obtained in CH3CN or CH2Cl2.
When sterically less hindered allylic substrates 3b, 3b%,
3c were employed, the selectivity and reactivity were
lower as in the case of the amination reaction (7b from
3b: 88% yield, 7b from 3b%: 84, 7c from 3c: 57% yield.
Every product was racemic).
Scheme 3.
3. Conclusion
Next, the effect of the base was examined for the
reaction of 3a and 6 (Table 4). Using metal acetate
combined with BSA as a base system, lithium acetate
showed the best results among the metal acetates used.
Diethylzinc, which is effective for the allylic alkylation
using the BINAP–Pd complex,6 showed low selectivity.
The activity of the Yliphos–Pd complexes for allylic
substitution has been demonstrated. In the amination
reaction, a higher concentration of amine accelerates
the reaction, while LiH was the most effective base
additive for alkylation. Further investigations on the
utility of this unique Yliphos are in progress.

540
T. Ohta et al. / Tetrahedron: Asymmetry 14 (2003) 537–542
Table 4. Allylic alkylation reaction catalyzed by Pd complexa
Entry
Ligand
Solvent
Base
Yieldd
%
eeb,c
1
2
3
4
5
6
7
8
(S)-2a
(S)-2a
(S)-2a
(S)-2a
(S)-2a
(S)-2a
(S)-2a
(S)-2a
(S)-2a
(S)-2a
(S)-2a
(S)-2a
(S)-2a
(S)-2a
(S)-2a
(S)-2a
(S)-2a
(S)-2b
(S)-2c
(S)-2a
(S)-2a
THF
CH3CN
DMF
CH2Cl2
THF
THF
THF
THF
THF
THF
THF
THF
THF
THF
THF
THF
THF
THF
THF
THF
THF
KOAc+BSA
KOAc+BSA
KOAc+BSA
KOAc+BSA
LiOAc+BSA
NaOAc+BSA
RbOAc+BSA
CsOAc+BSA
ZnEt2
LiH
n-BuLi
LDA
CH3Li
NaH
KH
NaH+LiCl
LiH
LiH
LiH
LiH
LiH
99
83
92
57
47
44
90
69
65
91
92
65
85
97
94
98
33
81
43
93
87
32
43
12
38
84
59
22
39
15
95
73
73
87
70
14
81
87
61
64
80
91
9
10
11
12
13
14
15
16
17d
18
19
20e
21f
a A mixture of 3a (0.50 mmol), 6 (1.50 mmol), base (1.50 mmol), and catalyst (2 mol%, Pd2(dba)3·CHCl3+(S)-2a) in THF (2 mL) was stirred at
room temperature for 24 h.
b Isolated yield based on 3a. Absolute configuration of the product of each entry was (R).
c Determined by HPLC analysis using a Daicel Chiralcel OD-H column. Absolute configuration of the product of each entry was (R).
d At 0°C.
e 1 mol% of catalyst was used.
f 1.0 mmol of 6 was used.
4. Experimental
4.1. Asymmetric allylic amination reaction: general
procedure
1H NMR spectra were measured on a JEOL JNM-
A400 (400 MHz) spectrometer using tetramethylsilane
as the internal standard. IR spectra were measured on
a Shimadzu IR-408. Optical rotations were recorded on
a Horiba SEPA-200 spectrophotometer. Gas chromato-
graphic analyses were conducted on a Shimadzu GC-
8A (5% Silicone SE-30 on Chromosorb W (AW-DMCS
80–100 mesh), 2 m, 80–220°C). Liquid chromato-
graphic analyses were conducted using Hitachi L-7100
(Daicel CHIRALCEL OD-H, 0.25 m). GC–MS spectra
were measured on a Shimadzu QP-2000. HRMS (FAB)
was measured on JEOL M-700 using m-nitrobenzyl
alcohol as a matrix and PEG-200 as a calibration
standard.
Under Ar, ligand ((S)-2a–c, (S)-2a–c·HBr, 0.025
mmol), Pd(dba)2 (214 mg, 0.025 mmol), THF (1.0 mL)
were mixed and stirred for 30 min in a 20 mL Schlenk
tube. To this were added 1,3-diphenyl-2-propenyl ace-
tate 3a (126 mg, 0.50 mmol) and benzylamine 4a (1.09
mL, 10.0 mmol), and the mixture was stirred at 50°C
for 48 h. The reaction mixture was divided into satu-
rated aqueous ammonium chloride and diethyl ether.
Organic layer was dried over anhydrous magnesium
sulfate, concentrated, and purified by column chro-
matography (silica gel, ethyl acetate:hexane=1:4) to
give 5a as a colorless oil.
4.1.1. (E)-N-Benzyl-1,3-diphenyl-2-propenylamine 5a.
Yield 99%; 84% ee (S) (Daicel Chiralcel OD-H, 1:99
2-propanol:hexane, 0.5 mL/min, UV 254 nm, 15.4 (R),
16.2 (S)); [h]D25=+21.0 (c 1.4, CHCl3) (lit.10 [h]2D5=+25
All reactions were carried out under an argon atmo-
sphere. The solvents were distilled prior to use: diethyl
ether, THF, dioxane, 1,2-dimethoxyethane, benzene
and toluene were distilled over Na/benzophenone; ace-
tonitrile and dichloromethane were distilled over P2O5;
methanol and ethanol were distilled over Mg; chloro-
form, DMF, and DMSO were distilled over CaH2.
1,3-Diphenyl-2-propenyl acetate 3a,7 1-phenyl-2-
butenyl acetate 3b,7 2-acetoxy-3-pentene 3c,7 2-cyclo-
1
(c 1.76, CHCl3) for 96% ee (S)); H NMR (CDCl3) l
1.70 (s, 1H), 3.77 (d, J=13.2 Hz, 1H), 3.79 (d, J=13.2
Hz, 1H), 4.40 (d, J=7.6 Hz, 1H), 6.32 (dd, J=7.6 and
15.8 Hz, 1H), 6.58 (d, J=15.8 Hz, 1H), 7.13–7.52 (m,
15H).
hexenyl
acetate
3d,2a
phosphonium
salts
4.1.2. (E)-N-Butyl-1,3-diphenyl-2-propenylamine 5b.
Yield 100%; 81% ee (Daicel Chiralcel OD-H, 1:99
2-propanol:hexane, 0.5 mL/min, UV 254 nm, 9.4 (+),
10.2 (−)); [h]D25=−15.3 (c 1.5, CHCl3); 1H NMR
(CDCl3) l 0.90 (t, J=7.4 Hz, 3H), 1.27–1.39 (m, 2H),
TolYliphos·HBr, (S)-2a–c·HBr,4 TolYliphos (S)-2a–c,4
Pd(dba)2,8 and Pt(dba)2 were prepared according to
9
literature methods. Other materials were purchased and
used without further purification.

T. Ohta et al. / Tetrahedron: Asymmetry 14 (2003) 537–542
541
1.49 (q, J=7.4 Hz, 2H), 1.74 (s, 1H), 2.54 (dt, J=7.4
and 11.4 Hz, 1H), 2.65 (dt, J=7.4 and 11.4 Hz, 1H),
4.35 (d, J=7.4 Hz, 1H), 6.30 (dd, J=7.4 and 15.8 Hz,
1H), 6.56 (d, J=15.8 Hz, 1H), 7.18–7.41 (m, 10H); 13C
NMR (CDCl3) l 13.99, 20.43, 32.11, 47.37, 65.69,
126.34, 127.18, 127.22, 127.35, 128.42, 128.53, 130.10,
132.53, 136.83, 142.81; HRMS (FAB, in 3-nitrobenzyl
alcohol) calcd. for C19H23N: 264.1752, found 264.1762.
(c 1.1, EtOH) (lit.14 [h]2D3=+18.4 (c 1.1, EtOH)); 1H
NMR (CDCl3) l 3.52 (s, 3H), 3.70 (s, 3H), 3.96 (d,
J=11.2 Hz, 1H), 4.27 (dd, J=8.2 and 11.2 Hz, 1H),
6.33 (dd, J=8.2 and 16.0 Hz, 1H), 6.48 (d, J=16.0 Hz,
1H), 7.18–7.33 (m, 10H).
4.2.2. (E)-Dimethyl (1-styrylethyl)propanedioate 7b15.
Yield 88%; [h]2D5=+0.0 (c 1.8, CHCl3); 1H NMR
(CDCl3) l 1.19 (d, J=6.8 Hz, 3H), 3.09–3.16 (m, 1H),
3.40 (d, J=8.8 Hz, 1H), 3.66 (s, 3H), 3.73 (s, 3H), 6.12
(dd, J=8.0 and 16.0 Hz, 1H), 6.45 (d, J=16.0 Hz, 1H),
6.90–7.30 (m, 5H).
4.1.3. (E)-N-(1,3-Diphenyl-2-propenyl)-4-methylbenzene-
sulfonamide 5d11. Yield 40%; 63% ee (Daicel Chiralcel
OD-H, 20:80 2-propanol:hexane, 0.5 mL/min, UV 254
1
nm, 14.9 (−), 20.0 (+)); [h]2D5=−7.0 (c 1.5, CHCl3); H
NMR (CDCl3) l 2.32 (s, 3H), 4.99 (d, J=7.2 Hz, 1H),
5.11 (t, J=7.2 Hz, 1H), 6.07 (dd, J=6.8 and 15.6 Hz,
1H), 6.35 (d, J=15.6 Hz, 1H), 7.13–7.28 (m, 12H),
7.65–7.67 (m, 2H).
4.2.3. (E)-Dimethyl (1-methyl-2-butenyl)propanedioate
1
7c16. Yield 57%; [h]D25=+0.0 (c 1.0, CHCl3); H NMR
(CDCl3) l 0.99 (d, J=6.8 Hz, 3H), 1.58 (d, J=6.8 Hz,
3H), 2.79–2.85 (m, 1H), 3.19 (d, J=8.8 Hz, 1H), 3.62
(d, J=14.8 Hz, 6H), 5.24–5.30 (m, 1H), 5.41–5.48 (m,
1H).
4.1.4. (E)-N-(1,3-Diphenyl-2-propenyl)phthalimide 5e11.
Yield 5%; 69% ee (S) (Daicel Chiralcel OD-H, 1:99
2-propanol:hexane, 0.5 mL/min, UV 254 nm, 22.3 (S),
1
30.8 (R)); H NMR (CDCl3) l 6.13 (d, J=8.6 Hz, 1H),
Acknowledgements
6.72 (d, J=15.6 Hz), 7.06 (dd, J=8.6 and 15.6 Hz, 1H),
7.23–7.49 (m, 10H), 7.70 (m, 2H), 7.83–7.85 (m, 2H).
We thank Dr. Takayuki Yamashita for the helpful
discussions during the course of this work. This work
was partially supported by Doshisha University’s
Research Promotion Fund and a grant to RCAST at
Doshisha University from the Ministry of Education,
Japan.
4.1.5. (E)-N-Benzyl-1-phenyl-2-buten-3-ylamine 5f12.
Yield 95%; 5% ee (Daicel Chiralcel OD-H, 1:99 2-
propanol:hexane, 0.5 mL/min, UV 254 nm, 13.9 (+),
1
15.4 (−)); [h]2D5=+1.3 (c 1.5, CHCl3); H NMR (CDCl3)
l 1.26 (d, J=6.4 Hz, 3H), 1.54 (s, 1H), 3.37–3.48 (m,
1H), 3.73 (d, J=13.2 Hz, 1H), 3.84 (d, J=13.2 Hz,
1H), 6.11 (dd, J=7.8 and 15.8 Hz, 1H), 6.48 (d, J=
15.8 Hz, 1H), 7.20–7.40 (m, 10H).
References
4.1.6. (E)-N-Benzyl-3-penten-2-ylamine 5g13. Yield 43%;
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1
[h]2D5=0.0 (c 2.0, CHCl3); H NMR (CDCl3) l 1.07 (d,
J=6.8 Hz, 3H), 1.62 (d, J=6.8 Hz, 3H), 1.93 (s, 1H),
3.10 (m, 1H), 3.59 (d, J=13 Hz, 1H), 3.71 (d, J=13
Hz, 1H), 5.26 (dd, J=8 and 15.2 Hz, 1H), 5.48 (dq,
J=6.8 and 15.2 Hz, 1H), 7.1–7.3 (m, 5H).
4.2. Asymmetric allylic alkylation reaction: general
procedure
Into a 20 mL Schlenk tube were added TolYliphos
(5.0×10−3 mmol), Pd(dba)2 (23 mg, 5.0×10−3 mmol) and
THF (1.0 mL) under an argon atmosphere. After the
mixture was stirred for 30 min, 1,3-diphenyl-2-propenyl
acetate 3a (63 mg, 0.25 mmol) was introduced. To this
was added a mixture of dimethyl malonate 6 (0.09 mL,
0.75 mmol) and lithium hydride (4 mg, 0.75 mmol) in
THF (1.0 mL). The resulting mixture was stirred for 24
h at room temperature. This reaction mixture was
divided into saturated aqueous ammonium chloride and
diethyl ether. The organic layer was dried over anhy-
drous magnesium sulfate, concentrated, and purified by
column chromatography (silica gel, ethyl acetate/hex-
ane=1:4) to give 7a as a colorless oil.
4.2.1. (E)-Dimethyl 1,3-diphenylprop-2-enylpropane-
dioate 7a. Yield 91%; 95% ee (R) (Daicel Chiralcel
OD-H column, 1:99 2-propanol:hexane, 0.3 mL/min,
UV 254 nm, 27.9 min (R), 29.2 min (S)); [h]2D5=+17.4

542
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