Asymmetric allylic amination catalyzed by Pd-BINAP complexes

Article abstract of DOI:10.1055/s-2001-11414

The asymmetric allylic amination of rac-1,3-diphenyl-2-propenyl acetate (1) with potassium phthalimide (2b) has been carried out in the presence of 2.5 mol% Pd₂(dba)₃·CHCl₃ and 5.0 mol% (S)-Tol-BINAP to give the allylic pr

Full text of DOI:10.1055/s-2001-11414

LETTER
385
Asymmetric Allylic Amination Catalyzed by Pd-BINAP Complexes
Hidehiko Kodama, Toshiji Taiji, Tetsuo Ohta,* Isao Furukawa
Department of Molecular Science and Technology, Faculty of Engineering, Doshisha University, Kyotanabe, Kyoto 610-0394, Japan
Fax+81-774-65-6789; E-mail: tota@mail.doshisha.ac.jp
Received 4 December 2000
ligands with 1,1’-binaphthyl skeleton. A popular chiral bi-
dentate diphosphine ligand, BINAP, has been utilized in
Abstract: The asymmetric allylic amination of rac-1,3-diphenyl-2-
propenyl acetate (1) with potassium phthalimide (2b) has been car-
ried out in the presence of 2.5 mol% Pd (dba) CHCl and 5.0
3
the Rh(I)- or Ru(I)-catalyzed asymmetric hydrogenation,
2
3
3
4
5
mol% (S)-Tol-BINAP to give the allylic product (3b) in 75% yield double bond isomerization, and Heck addition. Despite
with 99% ee.
the great success that the BINAP ligand has enjoyed over
the years, less satisfactory or even poor results have been
reported for their application in the palladium(0)-cata-
Key words: asymmetric catalysis, aminations, palladium, phospho-
rus, allyl complexes
6
lyzed allylic substitution. In 1999, Tanaka et al. found
that zinc malonates free from other metals can give high
ees in allylic alkylations catalyzed by a palladium(0)-BI-
The palladium-catalyzed asymmetric allylic amination is
a useful synthetic transformation as the resulting amines
can be converted into various kinds of chiral compounds
7
NAP complex. Therefore, we have examined the allylic
amination catalyzed by the Pd(0)-BINAP complex.8
1
The palladium-catalyzed allylic amination was carried out
in tetrahydrofuran using a catalyst prepared in situ by
mixing 2.5 mol% Pd (dba) CHCl and 5.0 mol% (S)-BI-
including α-amino acid derivatives. Recently, Hayashi
1
b
and Ito’s ferrocenyl phosphine ligands, Togni’s phos-
1
d
phine-pyrazole ligands, and Helmchen and Pfaltz’s
2
3
3
1
g
NAP or (S)-Tol-BINAP (Scheme, Table 1). As nitrogen
nucleophiles, 2.4 equiv benzylamine, potassium phthal-
imide, and sodium p-toluenesulfonamide were used.
phosphino-oxazoline ligand, have also been reported to
be applicable to the palladium-catalyzed allylic amina-
tion. As far as we know, there have been a few reports on
2
the allylic alkylation, but there have been no reports on The palladium-catalyzed allylic amination of rac-1,3-
the palladium-catalyzed allylic amination using the chiral diphenyl-2-propenyl acetate (1) with benzylamine (2a)
and potassium phthalimide (2b) using the (S)-BINAP
ligand gave the corresponding aminated products (S)-3a
OAc
and (S)-3b in 79% and 41% yield with 39% ee and 90%
Nu-M
Ph
Ph
ee, respectively (Entries 1 and 2, Table 1). Using (S)-Tol-
BINAP as the ligand for this reaction leads to an increase
in the enantioselectivities (Entries 4-6, Table 1). Howev-
er, by using sodium p-toluenesulfonamide (2c) as the nu-
cleophile, this reaction did not occur (Entries 3 and 7,
Table 1). Moreover, in spite of using 5.0 mol%
Pd (dba) CHCl and 10 mol% (S)-Tol-BINAP, this reac-
2
2
2
a: Nu = BnNH, M = H
b: Nu = PhthN, M = K
c: Nu = TsNH, M = Na
1
Nu
Pd2(dba)3, Ligand
THF
Ph
Ph
Ligand : (S)-BINAP
3a: Nu = BnNH
b: Nu = PhthN
c: Nu = TsNH
3
3
2
3
3
(
S)-Tol-BINAP
tion did not occur (Entry 8, Table 1).
cheme Asymmetric Allylic Amination Catalyzed by Pd-BINAP
omplexes
Next, the effect of an additive was examined for the reac-
tion using the (S)-Tol-BINAP ligand (Table 2). The allylic
Table 1 Palladium-BINAP Catalyzed Asymmetric Allylic Amination
a
b
c
Isolated yield. Determined by HPLC analysis using a DAICEL CHIRALCEL OD-H column. The 5.0 mol%
.
Pd (dba) CHCl catalyst and the 10 mol% (S)-Tol-BINAP ligand were used.
2
3
3
Synlett 2001 No. 3, 385–387 ISSN 0936-5214 © Thieme Stuttgart · New York

3
86
H. Kodama et al.
Table 2 Effect of Additive on Palladium-catalyzed Asymmetric Allylic Amination
LETTER
a
c
b
Isolated yield. Determined by HPLC analysis using a DAICEL CHIRALCEL OD-H column.
BSA = N,O-bis(trimethylsilyl)acetamide
(
(
4) a) Tani, K.; Yamagata, T.; Otsuka, S.; Akutagawa, S.;
amination catalyzed by Pd(0)-Tol-BINAP using 1.5 equiv
BSA (N,O-bis(trimethylsilyl)acetamide) as an additive
proceeded more smoothly to give the aminated products
Kumobayashi, H.; Taketomi, T.; Takaya, H.; Miyashita, A.;
Noyori, R. J. Chem. Soc., Chem. Commun. 1982, 600. b) Tani,
K.; Yamagata, T.; Akutadawa, S.; Kumobayashi, H.;
Taketomi, T.; Takaya, H.; Miyashita, A.; Noyori, R.; Otsuka,
S. J. Am. Chem. Soc. 1984, 106, 5208.
(
(S)-3a and (-)-3c) than no additive (Entries 1 and 3, Ta-
ble 2).
5) a) Ozawa, F.; Kubo, A.; Hayashi, T. J. Am. Chem. Soc. 1991,
In conclusion, the asymmetric allylic amination of rac-
113, 1417. b) Ozawa, F.; Kubo, A.; Hayashi, T. Tetrahedron
1
,3-diphenyl-2-propenyl acetate (1) with potassium
phthalimide (2a) smoothly proceeded in the presence of
.5 mol% Pd (dba) CHCl and 5.0 mol% (S)-Tol-BINAP
Lett. 1992, 33, 1485. c) Hayashi, T.; Uozumi, Y. Pure Appl.
Chem. 1992, 64, 1911. d) Sato, Y.; Watanabe, S.; Shibasaki,
M. Tetrahedron Lett. 1992, 33, 2589.
2
2
3
3
(
(
(
6) Yamaguchi, M.; Shima, T.; Yamagishi, T.; Hida, M.
to give the allylic product (3a) in 75% yield with 99% ee.
Furthermore, the asymmetric allylic amination of rac-1,3-
diphenyl-2-propenyl acetate (1) with sodium p-toluene-
sulfonamide (2c) using BSA proceeded to give 3c in 40%
yield with 91% ee.
Tetrahedron Lett. 1990, 31, 5049.
7) Fuji, K.; Kinoshita, N.; Tanaka, K. Chem. Commun. 1999,
1895.
8) A typical procedure for the palladium-catalyzed asymmetric
allylic alkylation of rac-1,3-diphenyl-2-propenyl acetate (1)
with benzylamine (2a).
A solution of (S)-Tol-BINAP (0.017 g, 0.025 mmol) and
Pd (dba) ·CHCl (0.013 g, 0.013 mmol) in tetrahydrofuran (2
Acknowledgement
2
3
3
mL) was stirred at room temperature for 30 min. This solution
was successively treated with a solution of rac-1,3-diphenyl-
We thank Dr. Takayuki Yamashita for helpful discussions during
the course of this work. This work was partially supported by Do-
shisha University’s Research Promotion Fund and a grant to
RCAST at Doshisha University from the Ministry of Education, Ja-
pan.
2-propenyl acetate (1) (0.13 g, 0.50 mmol) in tetrahydrofuran
(1 mL) and benzylamine (2a) (0.13 g, 1.2 mmol). The reaction
mixture was then stirred for 48 h at 50 °C. The reaction
mixture was quenched with saturated aqueous ammonium
chloride, and then extracted with diethyl ether. The organic
layer was dried over anhydrous sodium sulfate and evaporated
to dryness, and the residue was chromatographed on silica gel
References and Notes
(
1) a) Hayashi, T.; Yamamoto, A; Ito, Y.; Nishikawa, E.; Miura,
H.; Yanagi, K. J. Am. Chem. Soc. 1989, 111, 6301. b) Hayashi,
T.; Kishi, K.; Yamamoto, A.; Ito, Y. Tetrahedron Lett. 1990,
(
ethyl acetate:hexane = 1:4) to give N-((E)-1,3-diphenyl-2-
25
propenyl)benzylamine ((S)-3a). [α]D = +10.9 (c = 1.7,
CHCl ) (Entry 4, Table 1) (lit. [α] = +25 (c = 1.76,
CHCl ) ). The enantiomeric excess was determined by an
25
3
D
31, 1743. c) Yamazaki, A.; Achiwa, K. Tetrahedron:
9
3
Asymmetry 1995, 6, 51. d) Togni, A.; Burckhardt, U.;
Gramlich, V.; Pregosin, P. S.; Salzmann, R. J. Am. Chem. Soc.
HPLC analysis using a DAICEL CHIRALCEL OD-H column
(
eluent, 1:99 2-propanol−hexane; 0.5 mL/min flow rate;
detection, uv 254 nm; retention times, 15.4 min (R): 16.2 min
S)).
1996, 118, 1031. e) Trost, B. M.; Kruger, A. C.; Bunt, R. C.;
Zambrano, J. J. Am. Chem. Soc. 1996, 118, 6520. f) Trost, B.
M.; Vranken, D. L. V. Chem. Rev. 1996, 96, 395. g) von Matt,
P.; Loiseleur, O.; Koch, G.; Pfaltz, A.; Lefeber, C.; Feucht, T.;
Helmchen, G. Tetrahedron: Asymmetry 1994, 5, 573.
2) a) Vyskocil, S.; Smrcina, M.; Hanus, V.; Polasek, M.;
Kocovsky, P. J. Org. Chem. 1998, 63, 7738. b) Ogasawara,
M.; Yoshida, K.; Kamei, H.; Kato, K.; Uozumi, Y.; Hayashi,
T. Tetrahedron: Asymmetry 1998, 9, 1779.
(
In a similar method, N-((E)-1,3-diphenyl-2-
propenyl)phthalimide ((S)-3b) was prepared from rac-1,3-
diphenyl-2-propenyl acetate (1) and potassium phthalimide
(
(
(
2b) as a nitrogen nucleophile. The work-up, and
determination of the enantiomeric excesses and the absolute
configurations were performed using the same method
25
described above. [α] = +17.31 (c = 1.7, CHCl ) (Entry 6,
D
3
3) a) Ohta, T.; Takaya, H.; Kitamura, M.; Nagai, K.; Noyori, R.
J. Org. Chem. 1987, 52, 3174. b) Kawano, H.; Ikariya, T.;
Ishii, Y.; Saburi, M.; Yoshikawa, S.; Uchida, Y.;
26
9
Table 1) (lit. [α]D = -17 (c = 1.7, CHCl ) ). The enantiomeric
3
excess was determined by a DAICEL CHIRALCEL OD-H
column (eluent, 1:99 2-propanol−hexane; 0.5 mL/min flow
rate; detection, uv 254 nm; retention times, 22.3 min (S): 30.8
min (R)). Moreover, N-((E)-1,3-diphenyl-2-propenyl)-p-
toluenesulfonamide ((-)-3c) was prepared from rac-1,3-
diphenyl-2-propenyl acetate (1) and sodium p-toluene-
sulfonamide (2c) as a nitrogen nucleophile.
The work-up, and determination of the enantiomeric excesses
and the absolute configurations were performed using the
same method described above. The enantiomeric excess was
determined by a DAICEL CHIRALCEL OD-H column
Kumobayashi, H. J. Chem. Soc., Perkin Trans. 1989, 1571. c)
Noyori, R.; Ikeda, T.; Ohkuma, T.; Widhalm, M.; Kitamura,
M.; Takaya, H.; Akutagawa, S.; Sayo, N.; Saito, T.; Taketomi,
T.; Kumobayashi, H. J. Am. Chem. Soc. 1989, 111, 9134. d)
Noyori, R.; Ohkuma, T.; Kitamura, M.; Takaya, H.; Sayo, N.;
Kumobayashi, H.; Akutagawa, S. J. Am. Chem. Soc. 1987,
109, 5856. e) Kitamura, M.; Ohkuma, T.; Takaya, H.; Noyori,
R. Tetrahedron Lett. 1988, 29, 1555.
Synlett 2001, No. 3, 385–387 ISSN 0936-5214 © Thieme Stuttgart · New York

LETTER
Asymmetric Allylic Amination Catalyzed by Pd-BINAP Complexes
387
(
eluent, 20:80 2-propanol−hexane; 0.5 mL/min flow rate;
detection, uv 254 nm; retention times, 14.9 min (-): 20.0 min
+)).
products (3a-3c) were not obtained in high yields with
excellent enantioselectivities.
(10) Sudo, A.; Saigo, K. J. Org. Chem. 1997, 62, 5508.
(
(
9) Moreover, Saigo et al. reported that the amination products
were obtained with excellent enantioselectivitiy when acetic
1
0
acid was added to the reaction system. Therefore, the effect
of the addition of acetic acid was examined, but the amination
Article Identifier:
1437-2096,E;2001,0,03,0385,0387,ftx,en;Y20100ST.pdf
Synlett 2001, No. 3, 385–387 ISSN 0936-5214 © Thieme Stuttgart · New York