3
896
C. Rabeyrin, D. Sinou / Tetrahedron: Asymmetry 14 (2003) 3891–3897
4. Experimental
PrOH 97:3, tR 16 min (+)-isomer and 17 min (−)-iso-
mer; 2-[(E)-1,3-diphenylprop-2-en-1-yl]-1H-isoindole-
1
,3-(2H)-dione 3d, Daicel Chiralpak AD, hexane/2-
4.1. General
PrOH 97:3, t 36 min (S)-isomer and 42 min (R)-iso-
mer; dimethyl [(E)-1-n-propylhex-2-en-1-yl]malonate
R
All reactions were conducted in Schlenk tubes under
nitrogen. NMR spectra were recorded on a Brucker 300
6b, Daicel Chiralpak AD, hexane/2-PrOH 150:1, t 36
R
min (S)-isomer and 42 min (R)-isomer; ethyl 2-allyl-1-
MHz instrument and referenced to Me Si as internal
oxo-1,2,3,4-tetrahydronaphtalene-2-carboxylate
10,
4
20
standard. Conversion was determined by GC using a
[h] =−2.5 (c 0.8, CHCl ) (ee=10%), Daicel Chiralpak
D 3
Quadrex OV1 column (30 m×0.25 mm), enantiomeric
AD, hexane/2-PrOH 200:1, t 44 min (+)-isomer and 46
R
AD
excess was determined by HPLC with Chiralpak
min (−)-isomer.
column (25 cm×4.6 mm) using hexane/2-PrOH as the
eluent, the flow rate being 0.5 mL/min, the detection
being done by UV at 225 nm.
The separation of the racemic mixture of dimethyl
37
[(E)-1-methylbut-2-en-1-yl]malonate 6a and dimethyl
3
8
1
cyclohex-2-en-1-ylmalonate 8 was performed by H
All detergents and most of the ligands were purchased
from commercial sources and used as obtained.
C H NMe HSO (CTAHSO or cetyltrimethylammo-
NMR using Eu(hfc) in C D .
3
6
6
3
9
40
39
41
42
The absolute configuration of 2a, 2b, 2c, 2d, 3a,
16
33
3
4
4
43
39
nium hydrogen sulfate), C H OSO Na (SDS or
3d, and 6b were determined by correlation with their
specific rotations.
1
2
25
3
sodium dodecyl sulfate), Tween 40 (polyoxyethylene
sorbitan monopalmitate), DeDAPS (N-decyl-N,N-
dimethyl-3-ammonio-1-propanesulfonate),
were
3
4.3. [(E)-1,3-diphenylprop-2-en-1-yl](1-naphthylmethyl)-
obtained from Aldrich, [PdCl(h -C H )] and (R)-
3
5 2
3
3
34
amine, 3c
Binap from Strem. Unsaturated acetates 1, 5a–b,
3
5
36
7
,
and ketoester 9 were prepared in accordance with
2
0
R =0.5 (petroleum ether-ethyl acetate 20:3); [h] =
f
D
the literature.
−
11.2 (c 2.5, CHCl ) (ee=91%); HPLC, Daicel Chiral-
3
pak AD, 0.5 mL/min, hexane/2-PrOH 95:5, 225 nm, t
R
4.2. Standard alkylation reaction
1
1
8 min (−)-isomer and 20 min (+)-isomer; H NMR
3
(300 MHz, CDCl ): l 1.76 (bs, 1H, NH), 4.20 (d,
3
A mixture of [PdCl(h -C H )] (5.5 mg, 15 mmol), the
3
5 2
J=5.1 Hz, 2H, CH ), 4.49 (d, J=7.5 Hz, 1H, CHNH),
2
appropriate ligand (60 mmol), and then the surfactant
0.2 mmol) in water (4 mL) was stirred in a Schlenk
6
.36 (dd, J=15.8, 7.5 Hz, 1H, =CH-), 6.61 (d, J=15.8
(
13
Hz, 1H, =CH-), 7.16–8.10 (m, 17H, Harom); C NMR
75 MHz, CDCl ): l 49.7, 65.9, 124.3, 125.8, 126.1,
tube for 15 min. This solution was added to a Schlenk
tube containing the allylic acetate (0.6 mmol) and
diphenyl ether (102.1 mg, 0.6 mmol), as the internal
standard. After 10 min, this solution was transferred to
another Schlenk tube containing K CO (249 mg, 1.8
(
3
1
1
26.5, 126.6, 126.9, 127.8, 127.9, 128.2, 128.9, 129.1,
30.9, 133.1, 136.4, 137.4, 143.4. Anal. calcd for
C H N (349.48): C, 89.36; H, 6.63; found: C, 89.57;
26
23
2
3
H, 6.77.
mmol), the nucleophile (1.8 mmol), and eventually the
surfactant (0.2 mmol) in water (4 mL). After being
stirred for the indicated time, THF (2 mL) was added
to the mixture and the solution was filtered. Evapora-
tion of the solvents gave a residue that was subjected to
column chromatography on silica gel. The conversion
was determined by GC and the enantioselectivity by
HPLC.
Acknowledgements
C.R. acknowledges the M.E.N.R.T. for a fellowship.
The separation of the racemic mixture under HPLC
conditions is as follows: dimethyl [(E)-1,3-diphenyl-
prop-2-en-1-yl]malonate 2a, Daicel Chiralpak AD, hex-
ane/2-PrOH 6:4, tR 16 min (R)-isomer and 20 min
References
1. Cornils, B.; Herrmann, W. A. Applied Homogeneous
Catalysis with Organometallic Compounds; VCH: Wein-
heim, 1996.
2. Beller, M.; Bolm, C. Transition Metals for Organic Syn-
thesis; VCH: Weinheim, 1998.
(
S)-isomer; dimethyl [(E)-1,3-diphenylprop-2-en-1-
yl](methyl)malonate 2b, Daicel Chiralpak AD, hexane/
-PrOH 98:2, tR 37 min (R)-isomer and 40 min
S)-isomer; 3-[(E)-1,3-diphenylprop-2-en-1-yl]pentane-
2
(
2
7
,4-dione 2c, Daicel Chiralpak AD, hexane/2-PrOH
:3, tR 15 min (R)-isomer and 16 min (S)-isomer;
3. Cornils, B.; Herrmann, W. A. Aqueous-Phase
Organometallic Chemistry: Concepts and Applications;
VCH: Weinheim, 1998.
4. Oehme, G.; Paetzold, E.; Selke, R. J. Mol. Catal. 1992,
71, L1–L5.
diethyl
yl]malonate 2d, Daicel Chiralpak AD, hexane/2-PrOH
7:3, tR 21 min (R)-isomer and 27 min (S)-isomer;
(acetylamino)[(E)-1,3-diphenylprop-2-en-1-
9
(
E)-N-benzyl-1,3-diphenylprop-2-en-1-amine 3a, Daicel
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49, 6605–6612.
Chiralpak AD, hexane/2-PrOH 98:2, t 47 min (R)-iso-
R
mer and 54 min (S)-isomer; 4-[(E)-1,3-diphenylprop-2-
en-1-yl]morpholine 3b, Daicel Chiralpak AD, hexane/2-
6. Grassert, I.; Vill, V.; Oehme, G. J. Mol. Catal. A: Chem.
1997, 116, 231–236.