Palladium-catalyzed asymmetric reduction of racemic allylic esters with formic acid: Effects of phosphine ligands on isomerization of π- allylpalladium intermediates and enantioselectivity

Article abstract of DOI:10.1016/S0040-4020(99)01107-2

A new MOP ligand (lb), (R)-(+)-2-(bis(3- trifluoromethylphenyl)phosphino)-2'-methoxy-1,1'-binaphthyl, was found to be more enantioselective than other MOP ligands for the palladium-catalyzed asymmetric reduction of α,α-disubstituted allylic esters with formic acid. The reduction of DL-2-(1-naphthyl)-3-buten-2-yl benzoate gave 3-(1-naphthyl)- 1-butene of 90% ee. The higher enantioselectivity of lb is ascribed to fast syn-anti isomerization of π-allylpalladium intermediates formed by oxidative addition of allylic ester to a palladium(0) species. The rate of syn-anti isomerization was measured by the magnetization saturation transfer in ¹H NMR. (C) 2000 Elsevier Science Ltd.

Full text of DOI:10.1016/S0040-4020(99)01107-2

TETRAHEDRON
Pergamon
Tetrahedron 56 (2000) 2247±2257
Palladium-Catalyzed Asymmetric Reduction of Racemic Allylic
Esters with Formic Acid: Effects of Phosphine Ligands on
Isomerization of p-Allylpalladium Intermediates
and Enantioselectivity
²
Motoi Kawatsura, Yasuhiro Uozumi, Masamichi Ogasawara and Tamio Hayashi
*
Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo, Kyoto 606-8502, Japan
Accepted 7 December 1999
AbstractÐA new MOP ligand (1b), (R)-(1)-2-(bis(3-tri¯uoromethylphenyl)phosphino)-20-methoxy-1,10-binaphthyl, was found to be more
enantioselective than other MOP ligands for the palladium-catalyzed asymmetric reduction of a,a-disubstituted allylic esters with formic
acid. The reduction of dl-2-(1-naphthyl)-3-buten-2-yl benzoate gave 3-(1-naphthyl)-1-butene of 90% ee. The higher enantioselectivity of 1b
is ascribed to fast syn±anti isomerization of p-allylpalladium intermediates formed by oxidative addition of allylic ester to a palladium(0)
species. The rate of syn±anti isomerization was measured by the magnetization saturation transfer in 1H NMR. q 2000 Elsevier Science Ltd.
All rights reserved.
Introduction
p-Allylpalladium complexes bearing a sterically bulky
monodentate phosphine ligand (L), an anionic ligand (X),
and p-allyl moiety that contains two alkyl substituents (R1
and R2) at 1-position take a trans geometry with respect to
the phosphine ligand and the disubstituted p-allyl carbon
due to a steric repulsion between them.3 In this type of
p-allylpalladium complexes where R1 and R2 are different
to each other, there are three patterns of isomerization. They
are (A) epimerization, (B) syn-anti isomerization and (C)
cis±trans isomerization (Scheme 2). (A) The epimerization
proceeds through a s-allylpalladium intermediate that
forms s-bond at the C-3 position (cis to phosphorous
atom). By the rotation around C2±C3 bond in this s-allyl-
palladium intermediate, the palladium metal moves to the
other face of p-allyl. During this isomerization, syn and anti
Asymmetric allylic substitutions catalyzed by palladium
complexes containing optically active phosphine ligands
have attracted signi®cant interest due to their synthetic
utility.1 The catalytic cycle of the reactions involves a
p-allylpalladium complex as a key intermediate. Enantio-
selectivity in the asymmetric allylic substitutions is strongly
dependent on the isomerization of p-allylpalladium inter-
mediates which proceeds via well-known s±p±s mecha-
nism. When a palladium atom shifts from one face to the
other face, a substituent at the terminal position of p-allyl
group coordinated to a palladium undergoes syn-anti inter-
conversion with respect to the hydrogen at the center
position by the s±p±s mechanism2 (Scheme 1).
Scheme 1.
Keywords: isomerization; p-allylpalladium; enantioselectivity.
* Corresponding author. Tel.: 181-75-753-3983; fax: 181-75-753-3988; e-mail: thayashi@kuchem.kyoto-u.ac.jp
Present address: Department of Organic Chemistry, Faculty of Pharmaceutical Sciences, Nagoya City University, Mizuho-ku, Nagoya 467-8603, Japan.
²
0040±4020/00/$ - see front matter q 2000 Elsevier Science Ltd. All rights reserved.
PII: S0040-4020(99)01107-2

2248
M. Kawatsura et al. / Tetrahedron 56 (2000) 2247±2257
Scheme 2.
substituents on C-1 carbon stay at the original positions, so
we call this one epimerization. (B) The syn±anti isomeri-
zation proceeds through a s-allylpalladium intermediate
that forms the s-bond at the C-1 position (trans to phos-
phorous atom). The syn±anti interconversion takes place
through rotation around C1±C2 bond in this s-allylpalladium
intermediate. The isomerization of the substituents from syn
to anti and vice versa leads to the shift of palladium atom
from one face to the other. (C) The cis±trans isomerization
is an exchange of phosphine ligand (L) and anionic ligand
(X) on the palladium atom. The cis±trans interconversion
takes place through rotation of palladium±carbon bond in
the s-allylpalladium intermediates. It should be noted that
the epimerization (A) and syn±anti isomerization (B) are
the same type of isomerization occurring through the
s±p±s mechanism, but the epimerization is generally
much faster than the syn±anti isomerization because of
the stability of the primary alkylpalladium intermediate
Scheme 3.

M. Kawatsura et al. / Tetrahedron 56 (2000) 2247±2257
2249
Scheme 4.
compared with the tertiary alkylpalladium. To obtain high
stereoselectivity in palladium-catalyzed reaction that
proceeds through monophosphine p-allylpalladium inter-
mediates, it is important to control these three isomeri-
zations. Palladium-catalyzed reduction of allylic esters
with formic acid proceeds through this type of mono-
phosphine p-allylpalladium intermediate.
alkyl groups at the a-position is a sterically bulky group.9
For example, racemic methyl 1-vinyl-1,2,3,4-tetrahydro-
naphthyl benzoate, obtained from tetralone, gave reduction
product with 93% enantiomeric purity. The high enantio-
selectivity can be accounted for by the selective formation
of a p-allylpalladium intermediate that contains the more
bulky group at the syn position (Scheme 4). However, for
the asymmetric reduction of a,a-disubstituted allylic esters
where the selectivity in forming syn or anti p-allyl-
palladium intermediates is not high, the enantioselectivity
was lower. Here we wish to report that high enantio-
selectivity is also attained for such allylic esters by use of
new MOP ligand 1b containing 3-CF3C6H4 group on the
phosphorous. The ligand 1b accelerates the syn±anti
isomerization to result in the reductive elimination from
thermodynamically more stable syn isomer.
Palladium-catalyzed reduction of allylic esters with formic
acid developed by Tsuji and co-workers4 provides a con-
venient method for regioselective synthesis of less-substituted
ole®ns. Mechanistic studies5 on the catalytic reduction have
revealed that the ole®n is produced by reductive elimination
from the key intermediate, Pd(II)(p-allyl)(hydrido)(L),
which is generated by the decarboxylation of the palladium
formate complex, and that the use of monodentate phos-
phine ligand is essential for the high regioselectivity. We
have previously reported6,7 that the asymmetric reduction of
g,g-disubstituted allylic carbonates 2 with formic acid in the
presence of a palladium catalyst coordinated with axially
Results and Discussion
chiral
monodentate
phosphine
ligand,
(R)-2-di-
The results obtained for the asymmetric reduction of a,a-
disubstituted allylic esters dl-5 (Scheme 5) are summarized
in Table 1, which also contains the data for g,g-disubsti-
tuted esters (E)-2. The asymmetric reduction of allyl
carbonate dl-5b that contains sterically bulky 1-naphthyl
group at 1-position in the presence of 1 mol% of palladium
catalyst coordinated with (R)-MeO±MOP (1a) proceeded
regioselectively to give 94% yield of terminal ole®n
(R)-3-(1-naphthyl)-1-butene (4b) of 65% ee (entry 1).
Benzoate ester dl-5b0 also underwent the asymmetric
reduction to give (R)-4b in 72% ee (entries 2 and 3). The
enantioselectivity was lower in the reaction of sterically less
bulky esters, dl-5d, dl-5e and dl-5f, the enantioselectivities
being 40% ee, 29% ee and 55% ee, respectively (entries 7, 9
and 11). On the other hand, (E)-3,3-disubstituted-2-propenyl
phenylphosphino-20-methoxy-1,10-binaphthyl ((R)-MeO±
MOP)8 (1a), or its biphenanthryl analog, (R)-MOP-phen7
(1e) gives optically active ole®ns 4 of up to 91% ee (Scheme
3). The reduction of geometrically pure E- or Z- allylic
esters of 3,3-disubstituted-2-propenols proceeds by way of
Pd(II)X(p-allyl)L intermediates 3 where the epimerization
is fast but the syn±anti isomerization is slow compared with
the reductive elimination forming ole®n 4 and the stereo-
chemical outcome is mainly determined by the thermo-
dynamic stability of the epimeric p-allylpalladium
intermediates.
Recently, we found that some racemic tertiary allylic esters
can also be used for the asymmetric reduction if one of the
Scheme 5.

2250
M. Kawatsura et al. / Tetrahedron 56 (2000) 2247±2257
Table 1. Asymmetric reduction of racemic allylic esters (dl-5b±f) and (E)-3,3-disubstituted-2-propenyl esters ((E)-2b,d±f) catalyzed by palladium/(R)-MeO±
MOP complex (the reaction was carried out with 2.2 equiv. of formic acid in dioxane (0.5 M) in the presence of 1.2 equiv. of base and 1.0 mol% of catalyst
prepared in situ by mixing Pd2(dba)3´CHCl3 and (R)-MeO-MOP (P/Pdˆ2/1) at 208C)
Entry
Allyl ester
X in 5
Base
Conditions time (h)
Yield (%)a of 4
% ee of 4 (con®g)b
1
2
dl-5b
dl-5b0
dl-5b0
dl-5b
(E)-2b
dl-5c
dl-5d
(E)-2d
dl-5e
(E)-2e
dl-5f
OCO2Me
OCOPh
OCOPh
P. S.
P. S.
Et3N
P. S.
P. S.
P. S.
P. S.
P. S.
P. S.
P. S.
P. S.
P. S.
12
10
36
36
144
36
2
19
2
15
5
94
75
73
92
84
96
80
88
99
99
82
95
65b (R)
72b (R)
72b (R)
71b (R)
88b (R)
75d
3
4c
5
OCO2Me
OCO2Me
OCO2Me
OCOMe
OCO2Me
OCOMe
OCO2Me
OCO2Me
OCO2Me
6
7
8
9
10
11
12
40e (R)
60e (R)
29e (R)
71e (R)
55d (S)
76d (S)
(E)-2f
14
a Isolated yield by silica gel column chromatography.
b Determined by GLC analysis with chiral stationary phase column, CP Cyclodex b236M.
c Reaction with (R)-MOP-phen.
d Determined by HPLC analysis of dianilide of carboxylic acid, obtained by the oxidation (NaIO4-KMnO4) of 4f with Sumichiral OA-4100 (hexane/
dichloroethane/ethanolˆ50/15/1).
e Determined by HPLC analysis of anilide of carboxylic acid, obtained by the oxidation (NaIO4-KMnO4) of 4c, 4d and 4e with Sumichiral OA-2000 (hexane/
dichloroethane/ethanolˆ250/20/1).
esters (E)-2b, (E)-2d, (E)-2e and (E)-2f, which are regio-
isomeric esters of dl-5 gave the ole®ns 4 of 88% ee, 60% ee,
71% ee and 76% ee, respectively (entries 5, 8, 10 and 12).
Thus, the enantioselectivity is higher for (E) esters 2 than for
the corresponding dl esters 5. These results are as expected,
because (E)-2 should form only syn isomer of the p-allyl-
palladium intermediate at the oxidative addition while dl-5
will form both syn and anti isomers. The reductive elimi-
nation from the anti isomer will produce an ole®n of
opposite absolute con®guration to that from syn isomer.
isomers where 1-naphthyl is syn to the hydrogen on the
C-2 carbon are thermodynamically much more stable than
anti isomers. (E)-Allylic ester (E)-2b, which should form
only syn-p-allylpalladium intermediate, gave optically
active alkene 4b of 88% ee. In this reaction, the enantio-
selectivity is determined by the epimerization of syn-p-
allylpalladium intermediates. On the other hand, the
reaction of racemic allyl ester dl-5b mainly forms the
syn-p-allylpalladium intermediates but a minor amount of
anti-p-allylpalladium intermediates are also formed. This
anti-p-allylpalladium intermediate gives an opposite
enantiomer after the epimerization and, as a result, the
enantioselectivity in the catalytic reduction was reduced.
In order to attain the higher enantioselectivity in the
asymmetric reduction of a,a-disubstituted esters 5, it is
necessary to accelerate the syn±anti isomerization in the
p-allylpalladium intermediates to reach the equilibrium
where syn isomers are predominant.
p-Allylpalladium complex, PdCl[1-(1-naphthyl)-1-methyl-
p-allyl](MeO-MOP) (8), was prepared by mixing [PdCl{1-
(1-naphthyl)-1-methyl-p-allyl}]2 (7) with 1 equiv. (to Pd) of
(R)-MeO±MOP and it was characterized by 1H, 13C and 31
P
NMR spectra. In CDCl3 at 2508C the complex exists as a
mixture of isomers in a ratio of 3:2. These two isomers have
substituted carbon (C-1) of the p-allyl trans to the phos-
phorus atom of MeO±MOP and the unsubstituted carbon
(C-3) cis to phosphorous, which is determined by a large
coupling constant (Jˆ9.8 Hz) between methyl group and
phosphorous and no coupling between C-3 protons and
phosphorous. Both isomers contain 1-naphthyl and methyl
groups syn and anti positions, respectively, which was
determined by NOE's between the hydrogen on the C-2
position of p-allyl moiety and one of the hydrogens on
the 1-naphthyl group, probably C-80 hydrogen. Thus, the
structures of the isomers are assigned to be 8a and 8b
shown in Scheme 6. These results reveal that the syn
Several reaction conditions were examined for the
asymmetric reduction of dl-2-(1-naphthyl)-3-buten-2-yl
benzoate (dl-5b0). The results are summarized in Table 2.
Under the standard conditions so far used, where 2.2 equiv.
(to allyl ester) of formic acid was added in one portion, the
enantioselectivity was 73% ee (entry 1). A little higher
enantioselectivity (76% ee) was observed in the reduction
with 1.1 equiv. of formic acid (entry 2). The enantioselec-
tivity was further increased by slow addition of formic acid
over a period of 10 h, which gave (R)-4b of 80% ee (entry
Scheme 6.

M. Kawatsura et al. / Tetrahedron 56 (2000) 2247±2257
2251
Table 2. Asymmetric reduction of dl-2-(1-naphthyl)-3-buten-2-yl benzoate (dl-5b0) and methyl (E)-3-(1-naphthyl)-2-buten-2-butenyl carbonate (E)-2b with
formic acid catalyzed by palladium-MOP complexes (the reaction was carried out with 2.2 or 1.1 equiv. of formic acid in THF-dioxane (1:1) in the presence of
1.2 equiv. of Et3N and 1.0 mol% of catalyst prepared in situ by mixing Pd2(dba)3´CHCl3 and MOP ligand (P/Pdˆ2/1) at 08C)
Entry
Allyl ester
MOP ligand
HCOOH (equiv.)
Methoda
Time (days)
Yield (%)b of 4b
% ee of 4bc (con®g)d
1
2
3
4
5
6
7
8
dl-5b0
dl-5b0
dl-5b0
dl-5b0
dl-5b0
dl-5b0
dl-5b0
dl-5b0
dl-5b0
dl-5b0
(E)-2b
1a
1a
1a
1e
1e
1d
1c
1b
1b
1b
1b
2.2
1.1
1.1
2.2
1.1
2.2
2.2
2.2
1.1
1.1
2.2
A
A
B
A
B
A
A
A
A
B
A
1.5
2.0
3.0
1.5
2.0
4.5
0.7
3.5
3.0
3.0
6.0
81
85
77
91
92
83
76
92
77
86
86
73 (R)
76 (R)
80 (R)
77 (R)
82 (R)
69 (R)
76 (R)
84 (R)
86 (R)
90 (R)
88 (R)
9
10
11e
a Method A; formic acid was added in one portion. Method B; formic acid was added slowly over 10 h.
b Isolated yield by silica gel column chromatography.
c Determined by GLC analysis with chiral stationary phase column, CP Cyclodex b236M.
d Speci®c rotation of 4b in entry 10 is [a]2D0ˆ116.3 (cˆ0.35, chloroform)
e The reaction was carried out at 208C.
3). These results suggest that the slow addition extends the
lifetime of p-allylpalladium intermediates to provide a
chance for the syn±anti isomerization. However, the
enantioselectivity observed here (80% ee) is still lower
than that in the reduction of (E)-5b which gave 4b of 88%
ee (entry 5 in Table 1). It follows that the equilibration to
syn-p-allylpalladium intermediates is not reached in the
reaction of dl-5b0 and a certain amount of anti inter-
mediates are still involved even in the reaction under the
slow addition conditions. The asymmetric reduction of
dl-5b0 was also examined with some other axially chiral
monophosphine ligands, (R)-MOP-phen (1e) and MeO-
MOP analogues containing substituents on the diphenyl-
phosphino group, 1b (Arˆ3-CF3C6H4), 1c (Arˆ4-
CF3C6H4), and 1d (Arˆ4-MeOC6H4). Under the standard
conditions, 1e, 1d, 1c, and 1b gave (R)-4b of 77, 69, 76,
and 84% ee, respectively (entries 4, 6, 7 and 8). Thus, the
order of enantioselectivity in the reaction with MeO±MOP
analogues
is
1b
(Arˆ3-CF3C6H4).1c
(Arˆ4-
CF3C6H4).1a (ArˆPh).1d (Arˆ4-MeOC6H4). The high-
est enantioselectivity (90% ee) was obtained in the reaction
with 1b by the slow addition of formic acid, the enantio-
selectivity being essentially the same as that obtained in the
reduction of (E)-2b catalyzed by palladium/1b (entry 11). It
is expected that the syn-anti isomerization is accelerated by
the introduction of tri¯uoromethyl group on the MeO±MOP
Scheme 7.

2252
M. Kawatsura et al. / Tetrahedron 56 (2000) 2247±2257
ligand and that the reaction of dl-5b0 produces ole®n
4b from syn-p-allylpalladium intermediates after the
equilibration.
remarkable difference in the enantioselectivity for reduction
of dl-5b0. It would be better to use p-allylpalladium-MOP
complexes bearing 1,1-disubstituted p-allyl groups, but the
syn±anti isomerization is too slow to measure the rate by the
saturation transfer.
The stereochemical results in the reduction of dl-5b0 and
(E)-2b with MOP are illustrated in Scheme 7. The p-allyl-
palladium intermediate resulting from (E)-2b should be syn-
8, which contains 1-naphthyl group at the syn position. After
the epimerization between syn-(2R)-8 and syn-(2S)-8, the
product (R)-4b is formed from thermodynamically more
stable syn-(2S)-8. On the other hand, dl-5b0 forms both
syn-p-allylpalladium intermediate (syn-8) and anti-p-allyl-
palladium intermediate (anti-8) in a certain ratio, syn-8
being predominant. To attain the high enantioselectivity in
the reduction of dl-5b, the isomerization of anti-8 to syn-8
is necessary. The experimental results indicate that the slow
addition of formic acid extends the lifetime of p-allyl-
palladium intermediates to reach the equilibration and that
MOP ligand 1b accelerates the syn±anti isomerization.
In complex 9a, syn and anti protons on the C-1 position of
the p-allyl group which is trans to phosphorus, are named
Ha and Hb, respectively, and syn and anti protons on the C-3
position are named Hc and Hd, respectively. The isomeri-
zation which corresponds to the syn±anti isomerization of
p-(1,1-disubstituted allyl)palladium, (B) in Scheme 2, is
that proceeds through route A. By this conversion of 9a to
9b±i, protons Ha and Hb on the C-1 position exchange their
syn and anti positions while Hc and Hd on the C-3 position
stay at the original positions. By the isomerization which
corresponds to the epimerization, (A) in Scheme 2, 9a is
converted into 9b-ii through route B, where Ha and Hb stay
at the original positions while Hc and Hd are exchanged. In
the cis±trans isomerization, (C) in Scheme 2, all protons
remain on the original positions, but palladium moves from
one p-allyl face to the other. As a result, it appears that
protons Ha and Hc exchange their positions. It is possible
to measure the rate constants of the three isomerizations by
the magnetization saturation transfer technique in 1H NMR
because the Ha proton on 9a shifts to the different positions
on 9b depending on the type of isomerization. The rate
Rate constants for the isomerization of p-allylpalladium
complexes coordinated with MOP ligands were measured
1
by the magnetization saturation transfer technique in H
NMR.10 As a model of the p-allylpalladium intermediates,
we chose nonsubstituted p-allylpalladium complexes
PdCl(p-C3H5)(MOP) (9) where MOP ligands are 1a, 1b,
and 1d (Scheme 8). These MOP ligands showed a
Scheme 8.

M. Kawatsura et al. / Tetrahedron 56 (2000) 2247±2257
2253
Table 3. Rate constants (k) for exchange of p-allylpalladium complexes [PdCl(p-C3H5)L] (9a and 9b); syn±anti isomerization (k1), epimerization (k2) and cis±
trans isomerization (k3) (the rate constants were measured by saturation of Ha proton in 9a at 08C in CDCl3)
Entry
MOP ligand
(L)
k1 (s21
syn±anti isomerization
)
k2 (s21
epimerization
)
k3 (s21
)
cis±trans isomerization
1
2
3
1b (Arˆ3-CF3C6H4)
1.7
0.4
0.08
3.1
8.0
17
3.3
2.0
1.3
1a (ArˆPh) (MeO-MOP)
1d (Arˆ4-MeOC6H4)
constants of the isomerization of p-allylpalladium
complexes 9 are summarized in Table 3. In the complex
coordinated with (R)-MeO±MOP (1a), the rate constants
for syn±anti isomerization, epimerization, and cis±trans
isomerization were 0.4 s21, 8.0 s21, and 2.0 s21, respec-
tively. The rate of syn±anti isomerization (k1) was strongly
dependent on the MOP ligands coordinated to palladium.
Thus, the rate constants (k1) for the palladium complex of 1b
(Arˆ3-CF3C6H4) and 1d (Arˆ4-MeOC6H4) are 1.7 s21 and
0.08 s21, respectively. The isomerization with 1b is fastest,
four times faster than that with 1a and twenty times faster
than that with 1d. The order of the rate constants (k2) for the
epimerization was reverse, slowest with 1b and fastest with
1d, though the difference was not so large as the rate
constants for the syn-anti isomerization.
stationary phase column, CP Cyclodex b-236M (50 m).
Optical rotation were measured on a JASCO DIP-370
polarimeter.
Materials
THF was dried over sodium benzophenone ketyl and
distilled prior to use. [PdCl(p-C3H5)]2,11 Pd2(dba)3´CHCl3,12
(R)-MeO-MOP,8 1d (Arˆ4-MeOC6H4),8b (R)-MOP-phen,7
(E)-3-cyclohexyl-2-butenol,13 (E)-3-phenyl-2-butenol14 and
ethyl 3-(1-naphthyl) crotonate15 were prepared according
to the reported procedures. New MOP analogues 1b
(Arˆ3-CF3C6H4) and 1c (Arˆ4-CF3C6H4) were prepared
by the modi®ed procedure of MOP synthesis (see below).
Preparation of new MOP analogues 1b (Arˆ3-CF3C6H4)
and 1c (Arˆ4-CF3C6H4)
New MOP analogues were prepared from (R)-2-hydroxy-20-
methoxybinaphthyl by the sequence of (1) sulfonylation, (2)
palladium-catalyzed phosphinylation, and (3) reduction.
The fast rate of the syn±anti isomerization observed for the
p-allylpalladium complex 9 coordinated with 1b (Arˆ
3-CF3C6H4) is in good agreement with the high enantio-
selectivity in the catalytic asymmetric reduction of
a,a-disubstituted allylic ester dl-5b0. The syn and anti
p-allylpalladium intermediates 8 formed by the oxidative
addition of dl-5 to palladium(0) coordinated with 1b
undergo the syn±anti isomerization, faster than those of
other MOP ligands, to reach the equilibration where syn
intermediates are predominant. The syn intermediates will
produce the reduction product 4b of high enantiomeric
excess. The slow addition of formic acid will also increase
the enantioselectivity by providing a chance for the isomeri-
zation to syn-intermediates.
(R)-(2)-2-Methoxy-20-((tri¯uoromethanesulfonyl)oxy)-
1,10-binaphthyl
To a solution of (R)-2-hydroxy-20-methoxybinaphthyl16
(10.6 g, 35.3 mmol) and pyridine (3.6 g, 45.5 mmol) in
CHCl3 (100 mL) at 08C was added dropwise tri¯uoro-
methanesulfonic anhydride (14.3 g, 50.7 mmol). The
mixture was stirred at 08C for 2 h. The reaction mixture
was evaporated. The residue was diluted with EtOAc and
washed with 5% hydrochloric acid, saturated sodium bicar-
bonate and brine, dried over anhydrous sodium sulfate and
evaporated. The residue was chromatographed on silica gel
(hexane/EtOAcˆ1/1) to give 13.5 g (89%) of (R)-(2)-2-
methoxy-20-((tri¯uoromethanesulfonyl)oxy)-1,10-binaphthyl:
[a]2D0ˆ292.5 (cˆ1.7, CHCl3); 1H NMR (CDCl3, 500 MHz)
d 3.82 (s, 3H), 7.00±8.20 (m, 12H). Anal. Calcd for
C22H15F3SO4: C, 61.11; H, 3.50. Found: C,60.88; H, 3.51.
Experimental
General
All manipulations were carried out under a nitrogen atmos-
phere. Nitrogen gas was dried by passage through P2O5
(Merck, SICAPENT). NMR spectra were recorded on a
JEOL JNM-EX270 spectrometer (270 MHz for 1H and
109 MHz for 31P), JEOL JNM-AL400 spectrometer
(R)-(1)-2-(Bis(3-tri¯uoromethylphenyl)phosphinyl)-20-
methoxy-1,10-binaphthyl
1
(400 MHz for H NMR), or JEOL JNM LA500 spectro-
1
meter (500 MHz for H, 125 MHz for 13C and 202 MHz
for 31P). Chemical shifts are reported in d ppm referenced
to an internal SiMe4 standard for 1H NMR, and to an exter-
nal 85% H3PO4 standard for 31P NMR. Residual chloroform
(d 77.0 for 13C) was used as internal reference for 13C NMR.
1H, 13C and 31P NMR spectra were recorded in CDCl3 at
258C unless otherwise noted. HPLC analysis was performed
on a Shimadzu LC-6A liquid chromatograph system and a
JASCO PU-980 liquid chromatograph system with chiral
stationary phase column Sumitomo Chemical Co. Ltd.,
Sumipax OA series. GLC analysis was performed on a
HEWLETT PACKARD HP 6890 series with a chiral
To a mixture of (R)-(2)-2-((tri¯uoromethanesulfonyl)oxy)-
20-methoxy-1,10-binaphthyl (1.03 g, 2.61 mmol), bis(3-
tri¯uoromethylphenyl)phosphine oxide (1.35 g, 3.99
mmol), palladium diacetate (115 mg, 0.51 mmol) and 1,4-
bis(diphenylphosphino)butane (dppb) (228 mg, 0.54 mmol)
were added 40 mL of dimethyl sulfoxide and diisopropyl-
ethylamine (1.8 mL, 10.2 mmol) and the mixture was
heated with stirring at 1008C for 12 h. After cooling to
room temperature, the reaction mixture was concentrated
under reduced pressure to give a dark brown residue. The
residue was diluted with EtOAc, washed with water, dried

2254
M. Kawatsura et al. / Tetrahedron 56 (2000) 2247±2257
over anhydrous sodium sulfate and evaporated. The residue
was chromatographed on silica gel (hexane/EtOAcˆ1/1) to
give 1.36 g (80%) of (R)-(1)-2-(bis(3-tri¯uoromethyl-
stirred for 1.5 h. The reaction was quenched with brine
and extracted with ether. The organic layer was washed
with saturated sodium bicarbonate solution, dried over
anhydrous sodium sulfate and evaporated. The crude
product was puri®ed by silica gel column chromatography
(hexane/ EtOAcˆ10/1) to give 657 mg (94%) of methyl
phenyl)phosphinyl)-20-methoxy-1,10-binaphthyl:
[a]2D0ˆ
1
1116.1 (cˆ0.8, CHCl3); H NMR (CDCl3, 500 MHz) d
3.68 (s, 3H), 6.79±8.06(m, 20H). 31P{1H} NMR (CDCl3,
202 Hz, RT) d 26.9. Anal. Calcd for C35H23F6O2P: C,
67.75; H, 3.74. Found: C, 68.01; H, 3.77.
1
(E)-3-cyclohexyl-2-butenyl carbonate ((E)-2e): H NMR
(CDCl3) d 1.15±1.92 (m, 11H), 1.70 (s, 3H), 3.79 (s, 3H),
4.66 (d, Jˆ7.0 Hz, 2H), 5.36 (t, Jˆ7.0 Hz, 1H). Anal. Calcd
for C12H20O3: C, 67.89; H, 9.49. Found: C, 67.78; H, 9.47.
(R)-(1)-2-(Bis(3-tri¯uoromethylphenyl)phosphino)-20-
methoxy-1,10-binaphthyl (1b)
Methyl (E)-3-(1-naphthyl)-2-butenyl carbonate ((E)-2b).
1H NMR (CDCl3) d 2.16 (s, 3H), 3.78 (s, 3H), 4.91 (d,
Jˆ6.7 Hz, 2H), 5.71 (t, Jˆ6.7 Hz, 1H), 7.23±7.91 (m,
7H). 13C{1H} NMR (CDCl3, 202 Hz, RT) d 19.2, 54.6,
64.5, 123.6, 124.6, 125.2, 125.3, 125.6, 125.8, 127.3,
128.2, 130.5, 133.6, 141.6, 142.2, 155.7. Anal. Calcd for
C16H16O3: C, 74.98; H, 6.29. Found: C, 74.99; H, 6.18.
To a mixture of (R)-(1)-2-(bis(3-tri¯uoromethylphenyl)-
phosphinyl)-20-methoxy-1,10-binaphthyl (700 mg, 1.13
mmol) and Et3N (1.14 g, 11.3 mmol) in toluene (10 mL)
was added Cl3SiH (765 mg, 5.65 mmol) at 08C. The reac-
tion mixture was stirred at 1208C for 30 h. After being
cooled to room temperature, the mixture was diluted with
ether and quenched with a small amount of saturated sodium
bicarbonate. The resulting suspension was ®ltered through
Celite, and the solid was washed with ether. The combined
organic layer was dried over anhydrous magnesium sulfate
and evaporated. The crude product was chromatographed on
silica gel (hexane/EtOAcˆ9/1) to give 624 mg (92%) of
(R)-(1)-2-(bis(3-tri¯uoromethylphenyl)phosphino)-20-meth-
oxy-1,10-binaphthyl (1b): [a]D20ˆ147.7 (cˆ0.3, CHCl3); 1H
NMR (CDCl3, 500 MHz) d 3.48 (s, 3H), 6.85±8.03 (m,
20H). 31P{1H} NMR (CDCl3, 202 Hz, RT) d 212.0. Anal.
Calcd for C35H23F6OP: C, 69.54; H, 3.84. Found: C,69.38;
H, 3.89.
Methyl (E)-3-cyclohexyl-2-butenyl carbonate ((E)-2d).
1H NMR (CDCl3) d 2.13 (s, 3H), 3.80 (s, 3H), 4.85 (d,
Jˆ6.9 Hz, 2H), 5.91 (t, Jˆ6.9 Hz, 1H), 7.24±7.42 (m,
5H). Anal. Calcd for C12H14O3: C, 69.88; H, 6.84. Found:
C, 69.73; H, 6.82.
Geranyl methyl carbonate ((E)-2f).17 1H NMR (CDCl3) d
1.60 (s, 3H), 1.68 (s, 3H), 1.71 (s, 3H), 2.02±2.18 (m, 4H),
3.77 (s, 3H), 4.63 (d, Jˆ7.0 Hz, 2H), 5.07 (m, 1H), 5.38 (t,
Jˆ7.0 Hz, 1H).
(R)-(1)-2-(Bis(4-tri¯uoromethylphenyl)phosphinyl)-20-
methoxy-1,10-binaphthyl
Preparation of racemic 1,1-disubstituted propenyl esters
(dl-5b±f)
[a]2D0ˆ196.3 (cˆ2.0, CHCl3); 1H NMR (CDCl3, 500 MHz)
d 3.68 (s, 3H), 6.78±8.06 (m, 20H). 31P{1H} NMR (CDCl3,
202 Hz, RT) d 27.1. Anal. Calcd for C35H23F6O2P: C, 67.75;
H, 3.74. Found: C, 68.01; H, 3.41.
A typical procedure is given for dl-2-(1-naphthyl)-3-
butene-2-yl benzoate (dl-5b0). To a solution of vinylmag-
nesium bromide (7.2 mL of 0.9 M, 6.5 mmol) in diethyl
ether at 08C was added dropwise a solution of 10-aceto-
naphthone (1.0 g, 5.9 mmol) in THF (30 mL). The mixture
was stirred at room temperature for 12 h. It was quenched
with 0.5% sulfuric acid solution and extracted with ether.
The ether extracts were dried over anhydrous sodium
sulfate. Evaporation of the solvent gave a crude product.
To a solution of this crude allyl alcohol and 1,10-phenan-
throline (ca. 5 mg) in THF (10 mL) was added 1.5 M
n-butyllithium in hexane (4.7 mL, 7.1 mmol) at 2788C
and stirred for 0.5 h. To this reaction mixture was added
benzoyl chloride (993 mg, 7.1 mmol). The mixture was
allowed to warm to room temperature and stirred for 1 h.
The reaction was quenched with saturated sodium bicarbo-
nate solution and extracted with ether. The organic layer
was washed with saturated sodium bicarbonate solution
and brine, dried over anhydrous sodium sulfate and evapo-
rated. The crude product was puri®ed by alumina column
chromatography (hexane/Et3Nˆ10/1) to give 1.3 g (73%) of
dl-2-(1-naphthyl)-3-butene-2-yl benzoate (dl-5b0): 1H
NMR (CDCl3) d 2.26 (s, 3H) 5.27 (d, Jˆ17.6 Hz, 1H),
5.33 (d, Jˆ17.6 Hz, 1H), 6.56 (dd, Jˆ10.7 and 17.6 Hz,
1H), 7.28±8.41 (m, 12H). 13C{1H} NMR (CDCl3, 202 Hz,
RT) d 25.1, 114.5, 123.9, 124.2, 124.6, 125.4, 126.0, 127.1,
127.7, 128.5, 128.9, 129.8, 130. 2, 131.0, 132. 1, 133.3,
134.6, 138.2, 142.0, 143.1, 164.4. Anal. Calcd for
C21H18O2: C, 83.42; H, 6.00. Found: C, 83.50; H, 5.97.
(R)-(1)-2-(Bis(4-tri¯uoromethylphenyl)phosphino)-20-
methoxy-1,10-binaphthyl (1c). [a]2D0ˆ161.1 (cˆ0.8,
CHCl3); 1H NMR (CDCl3, 500 MHz) d 3.43 (s, 3H),
6.83±8.02 (m, 20H). 31P{1H} NMR (CDCl3, 202 Hz, RT)
d 212.5. Anal. Calcd for C35H23F6OP: C, 69.54; H, 3.84.
Found: C,69.32; H, 4.04.
Preparation of 3,3-disubstituted propenyl esters ((E)-
2b,d,e and f)
Methyl (E)-3-(1-naphthyl)-2-butenyl carbonate ((E)-2b),
methyl (E)-3-phenyl-2-butenyl carbonate ((E)-2d), methyl
(E)-3-cyclohexyl-2-butenyl carbonate ((E)-2e) and geranyl
methyl carbonate ((E)-2f) were obtained by treatment of the
corresponding alcohols with methyl chloroformate and
pyridine.17 (E)-3-(1-Naphthyl)-2-butenol was prepared
from the corresponding alcohol which was readily prepared
by reduction of ethyl 3-(1-naphthyl) crotonate12 with
LiAlH4, and used without puri®cation. A typical procedure
is given for the preparation of methyl (E)-3-cyclohexyl-2-
butenyl carbonate ((E)-2e). Experimental procedures: To a
solution of (E)-3-cyclohexyl-2-butenol and pyridine
(522 mg, 6.6 mmol) in benzene (10 mL) was added methyl
chloroformate (467 mg, 4.9 mmol) dropwise at 08C and

M. Kawatsura et al. / Tetrahedron 56 (2000) 2247±2257
2255
dl-Methyl 2-(1-naphthyl)-3-butene-2-yl carbonate (dl-
5b). H NMR (CDCl3) d 2.14 (s, 3H), 3.54 (s, 3H), 5.18
Method B. (entry 10): To a solution of Pd2(dba)3´CDCl3
(5.1 mg, 0.0049 mmol) and ligand 1b (12.2 mg,
0.020 mmol) in THF/dioxane (0.25 mL/0.25 mL) was
added dl-2-(1-naphthyl)-3-butene-2-yl benzoate (dl-5b0)
(152.9 mg, 0.51 mmol) in THF/dioxane (0.25 mL/
0.25 mL) and Et3N (60.2 mg, 0.60 mmol). Formic acid
(24.3 mg, 0.53 mmol) was added slowly over 10 h at 08C
and the mixture was stirred at 08C. The reaction was
monitored by TLC and dilute with hexane. The catalyst
was removed by ®ltration through a short silica gel
(hexane). The ®ltrate was evaporated to give 79.3 mg
(86%) of (R)-3-(1-naphthyl)-1-butene ((R)-4b):18 1H NMR
(CDCl3, 400 MHz, RT) d 1.51 (d, Jˆ6.8 Hz, 1H), 4.31
(quintet, Jˆ6.8 Hz, 1H), 5.12 (dt, Jˆ11.7, 1.5 Hz, 1H),
5.13 (dt, Jˆ17.6, 1.5 Hz, 1H), 6.16 (ddd, Jˆ6.8, 11.7,
17.6 Hz, 1H), 7.04±8.54 (m, 7H). [a]2D0ˆ116.3 (cˆ0.35,
CDCl3); 90% ee. The enantiomeric purity was determined
by GLC analysis with CP Cyclodex b236M. The absolute
con®guration was assigned to be (R)-(1) by correlation with
1
(d, Jˆ17.4 Hz, 1H), 5.24 (d, Jˆ10.7 Hz, 1H), 6.44 (dd,
Jˆ10.7 and 17.4 Hz, 1H), 7.41±8.37 (m, 7H). 13C{1H}
NMR (CDCl3, 202 Hz, RT) d 26.1, 54.2, 85.8, 114.9,
124.6, 124.8, 125.2, 126.5, 129.0, 129.4, 130.3, 134.6,
137.4, 141.8, 153.3. Anal. Calcd for C16H16O3: C, 74.98;
H, 6.29. Found: C, 75.23; H, 5.96.
dl-Methyl 2-adamantyl-3-buten-2-yl carbonate (dl-5c).
1H NMR (CDCl3) d 1.59 (s, 3H), 1.60±1.80 (m, 15H), 1.95±
2.05 (m, 3H), 3.72 (s, 3H), 5.01 (d, Jˆ16.5 Hz, 1H), 5.26 (d,
Jˆ9.5 Hz, 1H), 5.92 (dd, Jˆ9.5, 16.5 Hz, 1H). 13C{1H}
NMR (CDCl3, 202 Hz, RT) d 28.4, 35.8, 36.9, 39.5, 53.9,
89.2, 115.0, 138.7, 154.2. Anal. Calcd for C16H24O3: C,
72.69; H, 9.15. Found: C,72.60; H, 9.30.
dl-2-Phenyl-3-buten-2-yl acetate (dl-5d). 1H NMR
(CDCl3) d 1.87 (s, 3H), 2.05 (s, 3H), 5.22 (d, Jˆ9.5 Hz,
1H), 5.25 (d, Jˆ16.0 Hz, 1H), 6.26 (dd, Jˆ9.5 and
16.0 Hz, 1H), 7.21±7.38 (m, 5H). 13C{1H} NMR (CDCl3,
202 Hz, RT) d 21.6, 24.2, 85.6, 117.1, 124.6, 126.6, 128.0,
128.2, 144.4, 169.9. Anal. Calcd for C12H14O2: C, 75.76; H,
7.42. Found: C, 68.00; H, 7.20.
1
known (S)-(1)-2-(1-naphthyl)propionic acid. H NMR and
analytical data for other reduction products 4c±f are shown
below.
3-Adamantyl-1-butene19 (4c) (75% ee). [a]2D0ˆ13.5
(cˆ1.0, chloroform) 1H NMR (CDCl3) d 0.90 (d,
Jˆ7.3 Hz, 3H), 1.20±2.00 (m, 16H), 1.95±2.05 (m, 3H),
4.87±4.96 (m, 2H), 5.26 (d, Jˆ10.5 Hz, 1H), 5.38 (d,
Jˆ17.5 Hz, 1H), 5.92 (dd, Jˆ10.5 and 17.5 Hz, 1H).
1
dl-2-Cyclohexyl-3-buten-2-yl acetate (dl-5e). H NMR
(CDCl3) d 0.82±1.86 (m, 11H), 1.57 (s, 3H), 2.02 (s, 3H),
5.10 (d, Jˆ16.5 Hz, 1H), 5.16 (d, Jˆ9.5 Hz,1H), 5.97 (dd,
Jˆ9.5, 16.5 Hz, 1H). 13C{1H} NMR (CDCl3, 202 Hz, RT) d
21.0, 24.9, 26.5, 27.0, 27.3, 47.9, 75.1, 111.8, 144.3, 170.0.
Anal. Calcd for C12H20O2: C, 73.43; H, 10.27. Found: C,
73.62; H, 9.96.
(R)-3-Phenyl-1-butene ((R)-4d) (60% ee). 1H NMR
(CDCl3)
d
1.39 (d, Jˆ6.8 Hz, 3H), 2.48 (quintet,
Jˆ6.8 Hz, 1H), 5.00±5.08 (m, 2H), 6.02 (ddd, Jˆ6.8, 10.5
and 16.0 Hz, 1H), 7.19±7.34 (m, 5H). [a]2D2ˆ22.2 (cˆ0.74,
chloroform). lit.20 (R)-(2): [a]2D2ˆ26.39 (neat).
1
dl-Methyl linalyl carbonate (dl-5f). H NMR (CDCl3) d
1.64 (s, 3H), 1.66 (s, 3H), 1.70 (s, 3H), 0.92 (t, Jˆ7.0 Hz,
3H), 1.90±2.00 (m, 2H), 2.10±2.20 (m, 3H), 3.80 (s, 3H),
5.17±5.22 (m, 1H), 5.24 (d, Jˆ9.5 Hz, 1H), 5.34 (d,
Jˆ16.2 Hz, 1H), 5.79 (dd, Jˆ9.5 and 16.2 Hz, 1H).
13C{1H} NMR (CDCl3, 202 Hz, RT) d 17.5, 22.0, 22.8,
25.2, 39.2, 53.5, 83.9, 113.6, 123.3, 131.4, 140.8, 153.5.
Anal. Calcd for C12H20O3: C, 67.89; H, 9.49. Found: C,
68.16; H, 9.78.
1
(R)-3-Cyclohexyl-1-butene ((R)-4e) (71% ee). H NMR
(CDCl3) d 0.98 (d, Jˆ6.9 Hz, 3H), 0.92±1.78 (m, 11H),
1.91±2.04 (m, 1H), 4.88±4.94 (m, 2H), 5.68 (m, 1H).
[a]D20ˆ13.6 (cˆ0.9, chloroform). lit.21 (R)-(1): [a]2D4ˆ
14.1 (cˆ0.67, chloroform).
(S)-3,7-Dimethyl-1,6-octadiene ((S)-4f) (76% ee). 1H
NMR (CDCl3) d 0.98 (d, Jˆ7.0 Hz, 3H), 1.27±1.36 (m,
2H), 1.60 (s, 3H), 1.67 (s, 3H), 1.96 (q, Jˆ7.0 Hz, 2H),
2.12 (septet, Jˆ7.0 Hz, 1H), 4.90 (d, Jˆ10.1 Hz, 1H),
4.92 (d, Jˆ17.1 Hz, 1H), 5.05±5.15 (m, 1H), 5.70 (ddd,
Jˆ17.1, 10.1 and 7.0 Hz, 1H). [a]2D3ˆ17.0 (cˆ1.10, chloro-
form). lit.22 (R)-(2): [a]Dˆ29.82 (cˆ6.18, chloroform).
Catalytic asymmetric reduction of racemic allylic esters
dl-5
Typical procedures are given for the reaction of dl-2-(1-
naphthyl)-3-buten-2-yl benzoate (dl-5b0) (entries 8 and 10
in Table 2).
Determination of the absolute con®guration of 3-(1-
naphthyl)-1-butene ((R)-4b)
Method A. (entry 8): To a solution of Pd2(dba)3´CDCl3
(3.4 mg, 0.0033 mmol) and ligand 1b (8.1 mg,
0.013 mmol) in THF/dioxane (0.15 mL/0.15 mL) was
added dl-2-(1-naphthyl)-3-buten-2-yl benzoate (dl-5b0)
(101.3 mg, 0.34 mmol) in THF/dioxane (0.15 mL/
0.15 mL) and Et3N (40.4 mg, 0.40 mmol). Formic acid
(16.1 mg, 0.35 mmol) was added and the mixture was
stirred at 08C. The reaction was monitored by TLC and
diluted with hexane. The catalyst was removed by ®ltration
through a short silica gel (hexane). The ®ltrate was evapo-
rated to give 47.0 mg (77%) of (R)-3-(1-naphthyl)-1-butene
((R)-4b).
To a solution of 3-(1-naphthyl)-1-butene ((R)-4b) (80 mg,
0.44 mmol; 61% ee) in t-BuOH (8 mL) and water (20 mL)
were added KMnO4 (175 mg, 1.11 mmol), NaIO4 (1.52 g,
7.11 mmol) and K2CO3 (396 mg, 2.87 mmol), and the
mixture was adjusted to pH 8 with 3 N aq NaOH. After
stirring at rt for 2 h, the mixture was acidi®ed with conc.
hydrochloric acid to pH 1 and sodium hydrogen sul®te was
added to reduce MnO2. The mixture was extracted with
ether, and the ether layer was extracted with 3 N aq.
NaOH. The aqueous solution was acidi®ed with conc.
hydrochloric acid and extracted with ether. The ether

2256
M. Kawatsura et al. / Tetrahedron 56 (2000) 2247±2257
extracts were dried (MgSO4) and evaporation of the solvent
gave 2-(1-naphthyl)propionic acid (17 mg). [a]2D0ˆ147.1
(cˆ0.65, ethanol). lit.23 (S)-(1)-2-(1-naphthyl)propionic
acid (96% ee): [a]2D0ˆ1120.0 (cˆ1.0, ethanol).
evaporated to give 940 mg (58%) of [PdCl[p-(1-naph-
thyl)-1-methylallyl]]2: H NMR (CDCl3) d 1.79 (brs, 3H),
1
2.60 (brs, 1H), 3.95 (brs, 1H), 5.91 (brs, 1H), 7.41±8.66 (m,
7H). 13C{1H} NMR (CDCl3, 202 Hz, RT) d 28.8, 58.6, 95.1,
108.5, 125.0, 125.6, 125.8, 126.2, 127.6, 127.8, 128.5,
131.9, 133.7, 137.7. Anal. Calcd for C28H26Cl2Pd2: C,
52.04; H, 4.06. Found: C, 51.84; H, 4.10.
Determination of absolute con®guration and enantio-
meric purities of 4c±f
Ole®ns 4d±f were converted into N-phenyl-2-adamantyl-
propanamide, N-phenyl-2-phenylpropanamide,24 N-phenyl-
2-cyclohexylpropanamide25 and N,N0-diphenyl-2-methyl-
pentane-1,5-dicarboxamide,26 respectively, by oxidation
with NaIO4/KMnO4 followed by treatment of the resulting
carboxylic acids with aniline and 1-ethyl-3-(3-dimethyl-
aminopropyl)carbodiimide (WSC). The conditions for the
determination of the enantiomeric purities of anilides with
chiral stationary phase columns were as follows. N-phenyl-
2-adamantylpropanamide: Sumichiral OA-2500I; hexane/
1,2-dichloroethane/EtOHˆ1000/20/1; (1) isomer eluted
faster than (2) isomer. N-Phenyl-2-cyclohexylpropanamide
and N-phenyl-2-phenylpropanamide: Sumichiral OA-2000;
NMR study of PdCl{1-(1-naphthyl)-1-methyl-p-
allyl}((R)-MeO-MOP) (8)
In an NMR sample tube were placed (R)-MeO-MOP (1a)
(13.8 mg, 0.030 mmol) and [PdCl{1-(1-naphthyl)-1-methyl-
p-allyl}]2 (7) (9.6 mg, 0.015 mmol). The tube was ®lled
1
with nitrogen and CDCl3 (0.5 mL) was added. H NMR,
31P NMR and 13C NMR spectra were measured. major
isomer: 1H NMR (CDCl3, 500 MHz, RT) d 1.74 (d,
Jˆ12.7 Hz, 1H, anti-H on C3), 2.11 (d, JH-Pˆ 9.8 Hz,
Me), 2.55 (d, Jˆ7.3 Hz, 1H, syn-H on C3), 3.14 (s, 3H,
OMe), 5.08 (dd, Jˆ7.3, 12.7 Hz, 1H, H on C2), 6.22±8.72
(m, 29H, aromatic). 13C{1H} NMR (CDCl3, 125 Hz, RT) d
27.5 (Me), 54.5 (C3), 54.9 (OMe), 112.3 (d, JC-Pˆ2.1 Hz,
C2), 112.3 (d, JC-Pˆ24.8 Hz, C1), 113.5±138.0 (aromatic).
31P{1H} NMR (CDCl3, 202 MHz, RT) d 28.3 minor isomer:
1H NMR (CDCl3, 500 MHz, RT) d 2.21 (d, JH-Pˆ 9.8 Hz,
1H, Me), 2.26 (d, Jˆ12.7 Hz, anti-H on C3), 2.75 (d,
Jˆ7.3 Hz, 1H, syn-H on C3), 3.55 (s, 3H, OMe), 5.70 (dd,
Jˆ7.3, 12.7 Hz, 1H, H on C2), 6.22±8.72 (m, 29H,
aromatic). 13C{1H} NMR (CDCl3, 125 Hz, RT) d 27.8
(Me), 53.5 (C3), 55.1 (OMe), 111.7 (d, JC-Pˆ3.1 Hz, C2),
113.9 (d, JC-Pˆ23.8 Hz, C1), 111.9±137.6 (aromatic).
31P{1H} NMR (CDCl3, 202 MHz, RT) d 32.4.
hexane/1,2-dichloroethane/EtOHˆ250/20/1;
S
isomers
eluted faster than R isomers. N,N0-Diphenyl-2-methylpen-
tane-1,5-dicarboxamide: Sumichiral OA-4100; hexane/1,2-
dichloroethane/EtOHˆ50/15/1; R isomer eluted faster than
S isomer. A typical procedure for the conversion is given for
the reaction of 2f. To a solution of (S)-2f (61 mg,
0.44 mmol) in t-BuOH (10 mL) and water (20 mL), were
added KMnO4 (185 mg, 1.17 mmol), NaIO4 (1.46 g,
6.86 mmol) and K2CO3 (366 mg, 2.64 mmol), and the
mixture was adjusted to pH 8 with 3 N aq NaOH. After
stirring at room temperature for 2 h, the mixture was acidi-
®ed with conc. hydrochloric acid to pH 1 and sodium hydro-
gen sul®te was added to reduce MnO2. The mixture was
extracted with ether and the ether layer was extracted with
3N aq NaOH. The aqueous solution was acidi®ed with conc.
hydrochloric acid and extracted with ether. The ether
extracts were dried (MgSO4) and evaporation of the solvent
gave 2-methylpentanedioic acid (38 mg). To a solution of
the carboxylic acid (10 mg) obtained above in THF
(0.5 mL), were added aniline (15 mg, 0.16 mmol) and
WSC (30 mL), and the mixture was stirred at 408C for 1 h.
Conc. hydrochloric acid was added and the mixture was
extracted with EtOAc. Evaporation of the solvent followed
by silica gel column chromatography (hexane/EtOAcˆ1/1)
gave N,N0-diphenyl-2-methylpentane-1,5-dicarboxamide
(11 mg).
NMR study of [PdCl(p-C3H5)]L (9a and 9b)
A
typical procedure is given for the study of
[PdCl(p-C3H5)]((R)-MeO±MOP). In an NMR sample
tube were placed (R)-MeO±MOP (12.8 mg, 0.027 mmol)
and [PdCl(p-C3H5)]2 (5.0 mg, 0.014 mmol). The tube was
®lled with nitrogen and CDCl3 (0.5 mL) was added. H
NMR, 31P NMR and 13C NMR spectra were measured.
1
[PdCl(p-C3H5)]L (Lˆ1a (R)-MeO±MOP). major isomer:
1H NMR (CDCl3, 500 MHz, 2208C) d 0.82 (d, Jˆ11.7 Hz,
1H, anti-H on C3), 2.03 (dd, Jˆ10.7 Hz, JH±Pˆ13.2 Hz, 1H,
anti-H on C1), 2.10 (d, Jˆ6.4 Hz, 1H, syn-H on C3), 3.65 (s,
3H, OMe), 4.13 (dd, Jˆ4.9 Hz, JH±Pˆ7.3 Hz, 1H, syn-H on
C1), 4.99 (m, 1H, H on C2), 6.88±7.90 (m, 22H, aromatic).
13C{1H} NMR (CDCl3, 125 Hz, 2208C) d 55.4 (OMe), 64.7
(C3), 81.3 (d, JC±Hˆ31.0, C1), 117.9 (d, JC±Hˆ 4.1, C2),
113.9±155.7 (aromatic). 31P{1H} NMR (CDCl3, 202 MHz,
2208C) d 20.2. minor isomer: 1H NMR (CDCl3, 500 MHz,
2208C) d 1.48 (d, Jˆ12.2 Hz, 1H, anti-H on C3), 2.80 (d,
Jˆ6.4 Hz, 1H, syn-H on C3), 2.99 (dd, Jˆ8.8 Hz, JH±
Preparation of [PdCl{1-(1-naphthyl)-1-methyl-p-allyl}]2
(7)
Palladium chloride (900.4 mg, 5.0 mmol) and lithium
chloride (430.2 mg, 10.1 mmol) was dissolved in hot
water (1.5 mL) and to this solution were added ethanol
(3 mL), 2-(1-naphthyl)-3-buten-2-ol (1.0 g, 5.0 mmol) in
THF (15 mL) and aqueous hydrochloric acid (0.8 mL,
12 N). Carbon monoxide was passed through the solution
at room temperature and, after 1 h, a clear yellow orange
solution was obtained. The reaction mixture began to pre-
cipitate as orange±yellow crystals. After 4 h under carbon
monoxide, the solvent was removed under reduced pressure
and the residue was dissolved in CHCl3 which was washed
with water and dried over anhydrous sodium sulfate and
ˆ13.7 Hz, 1H, anti-H on C1), 3.24 (m, 1H, H on C2),
P
3.27 (s, 3H, OMe), 3.99 (dd, Jˆ6.8 Hz, JH±Pˆ 4.9 Hz, 1H,
syn-H on C1), 6.88±7.90 (m, 22H, aromatic). 13C{1H} NMR
(CDCl3, 125 Hz, 2208C) d 54.9 (OMe), 60.6 (C3), 80.0 (d,
JC±Hˆ30.0, C1), 117.8 (d, JC±Hˆ 4.1, C2), 113.9±155.7
(aromatic). 31P{1H} NMR (CDCl3, 202 MHz, 2208C) d
17.8.
[PdCl(p-C3H5)]L (Lˆ1d) (Arˆ4-MeOC6H4). major

M. Kawatsura et al. / Tetrahedron 56 (2000) 2247±2257
2257
1
2. Mackenzie, P. B.; Whelan, J.; Bosnich, B. J. Am. Chem. Soc.
1985, 107, 2046.
isomer: H NMR (CDCl3, 500 MHz, 2208C) d 1.18 (d,
Jˆ11.7 Hz, 1H, anti-H on C3), 2.35 (m, 2H, anti-H on C1
and syn-H on C3), 3.74 (s, 3H, OMe), 3.79 (s, 6H, OMe),
4.26 (dd, Jˆ5.9 Hz, JH±Pˆ 7.2 Hz, 1H, syn-H on C1), 5.48
(m, 1H, H on C2), 6.76±8.16 (m, 20H, aromatic). 13C{1H}
NMR (CDCl3, 125 Hz, 2208C) d 55.1 (OMe), 55,5 (OMe),
63.3 (C3), 80.5 (d, JC±Hˆ 32.1, C1), 117.4 (d, JC±Hˆ5.2, C2),
112.8±160.3 (aromatic). 31P{1H} NMR (CDCl3, 202 MHz,
2208C) d 16.5. minor isomer: 1H NMR (CDCl3, 500 MHz,
2208C) d 1.76 (d, Jˆ12.2 Hz, 1H, anti-H on C3), 2.95 (d,
3. Hayashi, T.; Iwamura, H.; Naito, M.; Matsumoto, Y.;
Uozumi, Y.; Miki, M.; Yanagi, K. J. Am. Chem. Soc. 1994, 116,
775.
4. (a) Tsuji, J.; Yamakawa, T. Teterahedron Lett. 1979, 613. (b)
Tsuji, J.; Shimizu, I.; Minami, I. Chem. Lett. 1984, 1017. (c)
Tsuji, J.; Minami, I.; Shimizu, I. Synthesis 1986, 623. (d)
Mandai, T.; Matsumoto, T.; Kawada, M.; Tsuji, J. J. Org. Chem.
1992, 57, 1326. For a review: Tsuji, J.; Mandai, T. Synthesis 1996,
1.
Jˆ6.9 Hz, 1H, syn-H on C3), 3.13 (dd, Jˆ8.8 Hz, JH±P
ˆ
13.7 Hz, 1H, anti-H on C1), 3.43 (s, 3H, OMe), 3.79 (m,
5. Oshima, M.; Shimizu, I.; Yamamoto, A.; Ozawa, F. Organo-
metallics 1991, 10, 1221.
1H, H on C2), 3.8 (s, 6H, OMe), 4.14 (dd, Jˆ5.9 Hz, JH±P
ˆ
7.0 Hz, 1H, syn-H on C1), 6.76±8.16 (m, 20H, aromatic).
13C{1H} NMR (CDCl3, 125 Hz, 2208C) d 54.9 (OMe), 55.1
(OMe), 69.5 (C3), 79.5 (d, JC±Hˆ30.0 Hz, C1), 117.1 (d,
JC±Hˆ5.2 Hz, C2), 113.9±155.7 (aromatic). 31P{1H} NMR
(CDCl3, 202 MHz, 2208C) d 14.2.
6. Hayashi, T.; Iwamura, H.; Uozumi, Y. Tetrahedron Lett. 1994,
35, 4813.
7. Hayashi, T.; Iwamura, H.; Uozumi, Y.; Matsumoto, Y.; Ozawa,
F. Synthesis 1994, 526.
8. (a) Uozumi, Y.; Hayashi, T. J. Am. Chem. Soc. 1991, 113, 9887.
(b) Uozumi, Y.; Tanahashi, A.; Lee, S.-Y.; Hayashi, T. J. Org.
Chem. 1993, 58, 1945. (c) Uozumi, Y.; Suzuki, N.; Ogiwara, A.;
Hayashi, T. Tetrahedron 1994, 50, 4293
[PdCl(p-C3H5)]L (Lˆ1b) (Arˆ3-CF3C6H4). major
1
isomer: H NMR (CDCl3, 500 MHz, 2208C) d 1.00 (d,
Jˆ12.2 Hz, 1H, anti-H on C3), 2.20 (d, Jˆ7.0 Hz, 1H,
syn-H on C3), 2.32 (dd, Jˆ10.7 Hz, JH±Pˆ13.4 Hz, 1H,
anti-H on C1), 3.76 (s, 3H, OMe), 4.36 (dd, Jˆ7.3 Hz,
JH±Pˆ9.4 Hz, 1H, syn-H on C1), 5.16 (m, 1H, H on C2),
6.97±8.00 (m, 20H, aromatic). 13C{1H} NMR (CDCl3,
9. Hayashi, T.; Kawatsura, M.; Iwamura, H.; Yamaura, Y.;
Uozumi, Y. Chem. Commun. 1996, 1767.
10. For examples: (a) Cho, H.; Iwashita, T.; Ueda, M.; Mizuno, A.;
Mizukawa, K.; Hamaguchi, M. J. Am. Chem. Soc. 1988, 110, 4832.
(b) Breutel, C.; Pregosin, P. S.; Salzmann, R.; Togni, A. J. Am.
Chem. Soc. 1994, 116, 4067. (c) Hayashi, T.; Kawatsura, M.;
Uozumi, Y. J. Am. Chem. Soc. 1998, 120, 1681.
11. Auburn, P. R.; Mackenzie, P. B.; Bosnich, B. J. Am. Chem.
Soc. 1985, 107, 2033.
125 Hz, 2208C) d 55.4 (OMe), 60.0 (C3), 81.3 (d, JC±H
ˆ
31.0 Hz, C1), 117.9 (d, JC±Hˆ5.2 Hz, C2), 113.7±155.6
(aromatic). 31P{1H} NMR (CDCl3, 202 MHz, 2208C) d
1
19.8. minor isomer: H NMR (CDCl3, 500 MHz, 2208C)
d 1.71 (d, Jˆ12.2 Hz, 1H, anti-H on C3), 2.90 (d, Jˆ6.4 Hz,
1H, syn-H on C3), 3.20 (dd, Jˆ9.1 Hz, JH±Pˆ13.7 Hz, 1H,
anti-H on C1), 3.41 (s, 3H, OMe), 3.63 (m, 1H, H on C2),
4.23 (dd, Jˆ7.0 Hz, JH±Pˆ9.4 Hz, 1H, syn-H on C1), 6.97±
8.00 (m, 20H, aromatic). 13C{1H} NMR (CDCl3, 125 Hz,
2208C) d 55.0 (OMe), 64.7 (C3), 80.0 (d, JC±Hˆ29.0, C1),
117.9 (d, JC±Hˆ7.2, C2), 113.7±155.6 (aromatic). 31P{1H}
NMR (CDCl3, 202 MHz, 2208C) d 17.1.
12. Ukai, T.; Kawazura, H.; Ishii, Y. J. Organomet. Chem. 1974,
65, 253.
13. Bellucci, C.; Glualtieri, F.; Scapecchi, S.; Teodori, E.;
Budriesi, R.; Chiarini, A. Farmaco 1989, 44, 1167.
14. Bussas, R.; Muenster, H.; Kresze, G. J. Org. Chem. 1983, 47,
2828.
15. Kagabu, S.; Shimizu, Y.; Ito, C.; Moriya, K. Synthesis 1992,
830.
16. Yashima, E.; Yamamoto, C.; Okamoto, Y.; J. Am. Chem. Soc.,
1996, 118, 4036, and references cited therein.
Acknowledgements
17. Tsuji, J.; Shimizu, I.; Minami, I.; Ohashi, Y.; Sugita, T.;
Takahashi, K. J. Org. Chem. 1985, 50, 1523.
This work was supported by `Research for the Future'
Program, the Japan Society for the Promotion of Science
and a Grant-in-Aid for Scienti®c Research, the Ministry of
Education, Japan.
18. Obora, Y.; Tsuji, Y. J. Org. Chem. 1995, 60, 4647.
19. Masuyama, Y.; Maekawa, K.; Kurusu, Y. Bull. Chem. Soc.
Jpn. 1991, 64, 2311.
20. (a) Hayashi, T.; Konishi, M.; Mise, T.; Kagotani, M.;
Takaji, M.; Kumada, M. J. Am. Chem. Soc. 1982, 104, 180. (b)
Cram, D. J. J. Am. Chem. Soc. 1952, 74, 2141.
21. Denmark, S. E.; Marble, L. K. J. Org. Chem. 1990, 55, 1984.
22. Arigoni, D.; Jeger, O. Helv. Chim. Acta 1945, 37, 881.
23. (a) Folli, U.; Iarossi, D.; Montanari, F.; Torre, G. J. Chem. Soc.
(C) 1968, 1317. (b) Fredga, A. Ark. Kemi. 1956, 9, 322.
24. Aaron, C.; Dull, D. L.; Schmiegel, J. L.; Jaeger, D.; Ohashi, Y.;
Mosher, H. S. J. Org. Chem. 1967, 32, 2797.
References
1. For a review on catalytic allylic substitutions, see: J. Tsuji,
Palladium Reagents and Catalysts, Chichester 1995. For reviews
on catalytic asymmetric allylic substitutions, see: (a) Trost, B. M.;
Van Vranken, D. L. Chem. Rev. 1996, 96, 395. (b) Hayashi, T. In
Catalytic Asymmetric Synthesis; Ojima, I., Ed.; VCH: New York,
1993; p 325. (c) Frost, C. G.; Howarth, J.; Williams, J. M.
J. Tetrahedron Asymmetry 1992, 3, 1089. (d) Consiglio, G.;
Waymouth, M. Chem. Rev. 1989, 89, 257.
25. Hoberg, H.; Guhl, D. Angew. Chem. 1989, 101, 1091.
26. Hoberg, H.; Baerhausen, D. J. Organomet. Chem. 1991, 403,
401.