Enantioselective 1,4-addition of arylboronic acids to α,β-unsaturated carbonyl compounds catalyzed by rhodium(I)-chiral phosphoramidite complexes

Article abstract of DOI:10.1016/j.jorganchem.2006.04.042

A chiral bidentate phosphoramidite (5a) was synthesized from Shibasaki's linked-(R)-BINOL and P(NMe₂)₃ as a new ligand for rhodium(I)-catalyzed asymmetric 1,4-addition of arylboronic acids to α,β-unsaturated carbonyl compounds. The effects of 5a and Feringa's monodentate phosphoramidite (4, R¹, R² = Et) on the yields and enantioselectivities were fully investigated. The reaction was significantly accelerated in the presence of a base such as KOH and Et₃N, allowing the reaction to be completed at the lower temperatures than 50 °C. The addition to cyclic enones such as 2-cyclopentenone, 2-cyclohexenone and 2-cycloheptenone at 50 °C in the presence of an [Rh(coe)₂Cl]₂-4 (R¹, R² = Et) complex resulted in enantioselectivities up to 98%, though it was less effective for acyclic enones (0-70% ee). On the other hand, a complex between [Rh(nbd)₂]BF₄ and 5a completed the addition to cyclic enones within 2 h at room temperature in the presence of Et₃N with 86-99% yields and 96-99.8% ee. This catalyst was also effective for acyclic enones, resulting in 62-98% yields and 66-94% ee. The 1,4-additions of arylboronic acids to unsaturated lactones and acyclic esters with rhodium(I)-phosphoramidites complexes were also investigated.

Full text of DOI:10.1016/j.jorganchem.2006.04.042

Journal of Organometallic Chemistry 692 (2007) 428–435
www.elsevier.com/locate/jorganchem
Enantioselective 1,4-addition of arylboronic acids to
a,b-unsaturated carbonyl compounds catalyzed by rhodium(I)-chiral
phosphoramidite complexes
Kazunori Kurihara, Noriyuki Sugishita, Kengo Oshita, Dongguo Piao,
*
*
Yasunori Yamamoto , Norio Miyaura
Division of Chemical Process Engineering, Graduate School of Engineering, Hokkaido University, Sapporo 060-8628, Japan
Received 20 February 2006; received in revised form 7 April 2006; accepted 18 April 2006
Available online 30 August 2006
Abstract
A chiral bidentate phosphoramidite (5a) was synthesized from Shibasaki’s linked-(R)-BINOL and P(NMe
2 3
) as a new ligand for rho-
dium(I)-catalyzed asymmetric 1,4-addition of arylboronic acids to a,b-unsaturated carbonyl compounds. The effects of 5a and Feringa’s
1
2
monodentate phosphoramidite (4, R , R = Et) on the yields and enantioselectivities were fully investigated. The reaction was signifi-
cantly accelerated in the presence of a base such as KOH and Et N, allowing the reaction to be completed at the lower temperatures
than 50 °C. The addition to cyclic enones such as 2-cyclopentenone, 2-cyclohexenone and 2-cycloheptenone at 50 °C in the presence
3
1
2
of an [Rh(coe)
2
Cl]
2
-4 (R , R = Et) complex resulted in enantioselectivities up to 98%, though it was less effective for acyclic enones
]BF and 5a completed the addition to cyclic enones within 2 h at room
(
0–70% ee). On the other hand, a complex between [Rh(nbd)
2
4
temperature in the presence of Et N with 86–99% yields and 96–99.8% ee. This catalyst was also effective for acyclic enones, resulting
3
in 62–98% yields and 66–94% ee. The 1,4-additions of arylboronic acids to unsaturated lactones and acyclic esters with rhodium(I)-phos-
phoramidites complexes were also investigated.
Ó 2006 Elsevier B.V. All rights reserved.
Keywords: Arylboronic acids; Rhodium catalyst; Phosphoramidite; Asymmetric; Conjugate addition
1
. Introduction
rhodium(I) complexes of monophosphoramidites [6], chiral
P–P ligands such as chiraphos [7] and diphosphonites [8],
P–N ligands of amidomonophosphines [9], bis(alkene)
ligands based on a norbornadiene skeleton [10], and car-
bene ligands derived from biscyclophane imidazolium salts
[11]. Among these chiral auxiliaries for metal-catalyzed
conjugate additions, phosphoramidites developed by Fer-
inga [6,12], such as 4, are the only ligands for which
monodentate form exhibit high enantioselectivity for a
large number of asymmetric transformations, including
copper- and rhodium-catalyzed conjugate addition of
organozinc and -boron compounds, though the efficiency
of a bidentate ligand bridged by diamine [12a] was reported
in copper-catalyzed reaction of diethylzinc with cyclic
enones. Herein we report the performance of monodentate
and bidentate phosphoramidite ligands for asymmetric
Metal-catalyzed conjugate addition reactions of carbon
nucleophiles to a,b-unsaturated compounds are the most
widely used methods for asymmetric carbon–carbon bond
formation [1]. The reactions catalyzed by copper [2], rho-
dium [3], and palladium [4] complexes are of great value
for asymmetric syntheses because of the availability of chi-
ral ligands. Rhodium(I)-binap catalysts were found to be
excellent catalysts for 1,4-addition reactions of aryl- and
1
-alkenylboronic acids to electron-deficient alkenes [3,5].
Other catalysts that are effective for arylboronic acids are
*
Corresponding author.
E-mail address: miyaura@org-mc.eng.hokudai.ac.jp (N. Miyaura).
0
022-328X/$ - see front matter Ó 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2006.04.042

K. Kurihara et al. / Journal of Organometallic Chemistry 692 (2007) 428–435
429
addition of arylboronic acids to a,b-unsaturated carbonyl
B(OH)2
compounds (Scheme 1) [6a,13]. A bidentate bisphosph-
oramidite 5a newly synthesized from Shibasaki’s linked-
BINOL was found to be an excellent ligand for both cyclic
and acyclic enones.
R1
R2
2
FG
FG
R1
R3
R3
Rh(I)-4 or -5 catalyst
base, aq. dioxane
R2
O
O
1
3
2
. Results and discussion
2
4
.1. Monodentate phosphoramidites for asymmetric 1,
-addition to enones
O
R1
O
O
P
N
O
O
R2
P
P
The effects of monodentate phosphoramidite ligands (4)
O
O
R R
N
N
on 1,4-addition of arylboronic acids to enones are summa-
rized in Table 1. The catalyst was prepared in situ by mix-
ing [Rh(coe) Cl] (1.5 mol%) and 4 equiv of 4 at room
R
R
4
5
a: R=Me
5b: R=Et
c: R=i-Pr
2
2
5
temperature for 1 h. The addition of arylboronic acid,
enone, and aqueous KOH was then followed at room tem-
perature. After being stirred for 6 h at 50 °C, the products
were isolated and analyzed by a chiral stationary column.
Since the enantioselectivity was reduced by raising the reac-
tion temperature, the presence of a base was critical to
carry out the reaction under mild conditions and to achieve
high enantioselective. The reaction was completed within
Scheme 1. Asymmetric 1,4-addition of arylboronic acids to enones
catalyzed by Rh(I)-phosphoramidite complexes.
N,N-diethylamine and morpholine derivative exhibited the
best enantioselectivity (91% ee, entries 2 and 8), and the
selectivities were reduced by increasing the bulkiness of
amino groups (entries 5–7). The diethylamino ligand (4,
6
h at 50 °C in the presence of 1 equiv of KOH, K PO4
1
2
3
R , R = Et) was also effective for other cyclic enones such
as 2-cyclopentenone (75–95% ee, entries 9–11) and 2-cyclo-
heptenone (94% ee, entry 12), giving yields and selectivities
comparable to those of 2-cyclohexenone. It is interesting
that the substituents on aromatic rings significantly affected
the enantioselectivity. 3-Methoxy-, 3-chloro, and 4-tolylbo-
ronic acid resulted in apparently higher enantioselectivities
than that of phenylboronic acid (entries 2–4 and 9–11). The
or K CO in striking contrast to the reaction occurring at
2
3
9
0 °C in the absence of
a
base. Rh(acac)(coe)2,
[
RhCl(C H ) ] , [Rh(OH)(cod)] and Rh(acac)(C H ) also
2
4 2 2
2
2
4 2
gave yields and enantioselectivities analogous to those of
Rh(coe) Cl] . The enantioselectivities dramatically chan-
[
2
2
ged in a series of N,N-dialkylamino derivatives for 2-
cyclohexenone (entries 1–8). Among the ligands employed,
Table 1
a
1,4-Addition of arylboronic acid to a,b-unsaturated carbonyl compounds catalyzed by Rh(I)-4 complexes
b
c
Entry
Carbonyl compound
Ligand (1)
2
ArB(OH) , X=
Product no.
Yield/%
% ee
1
2
R =
R =
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
a
2-Cyclohexenone
2-Cyclohexenone
2-Cyclohexenone
2-Cyclohexenone
2-Cyclohexenone
2-Cyclohexenone
2-Cyclohexenone
2-Cyclohexenone
2-Cyclopentenone
2-Cyclopentenone
2-Cyclopentenone
2-Cycloheptenone
Me
Et
Et
Et
CH
i-Pr
–CH
–CH
Et
Et
Et
Me
Et
Et
H
H
3-MeO
4-Me
H
H
H
H
H
3-Cl
3-MeO
H
H
H
H
H
H
H
3a
3a
3b
3c
3a
3a
3a
3a
3d
3e
3f
85
89
85
95
45
11
83
89
95
98
97
90
96
99
95
94
28
94
55
41
85 (R)
91 (R)
98
Et
96
2
Ph
CH
i-Pr
CH
NCH
2
Ph
57 (R)
4 (S)
68 (R)
91 (R)
75
81
95
94
0
16 (S)
24 (S)
10 (S)
29 (R)
35 (R)
47 (R)
70 (R)
2
CH
CH
2
CH
2
2
CH
2
–
2
2
2
CH
2
–
Et
Et
Et
Et
Et
Et
n-Pr
CH
Ph
1
1
1
1
1
1
1
1
1
1
2
Et
Et
3g
3h
3h
3h
3h
3h
3h
3h
3h
(E)-C
(E)-C
(E)-C
(E)-C
(E)-C
(E)-C
(E)-C
(E)-C
5
H
5
H
5
H
5
H
5
H
5
H
5
H
5
H
11CH@CHCOCH
11CH@CHCOCH
11CH@CHCOCH
11CH@CHCOCH
11CH@CHCOCH
11CH@CHCOCH
11CH@CHCOCH
11CH@CHCOCH
3
3
3
3
3
3
3
3
Me
Me
Me
Me
Me
Me
Me
2
Ph
i-Pr
1-Adamantyl
t-Bu
H
H
2
All reactions were carried out at 50 °C for 6 h in the presence of enone (1 mmol), arylboronic acid (1.5 mmol), [Rh(coe)Cl] (0.015 mmol, 3 mol%), 4
(
0.066 mmol) and KOH (1 mmol) in dioxane–H
2
O (6/1).
b
Isolated yields based on enones.
c
Enantiomer excess determined by a chiral stationary column.

430
K. Kurihara et al. / Journal of Organometallic Chemistry 692 (2007) 428–435
phosphoramidites derived from (R)-(+)-BINOL afforded
R)-3-phenylcyclohexanone for a series of dialkylamino
derivatives (entries 1, 2, 5, 7 and 8), though the diisopropyl
derivative exceptionally gave an S isomer with a very low
selectivity (entry 6).
In contrast to the excellent performance of the N,N-
diethylamino ligand for cyclic enones, it was not effective
for acyclic enones (entries 13–20). Acyclic enones such as
(
O
OH
HO
OH
HO
6
(
Linked-BINOL)
5
5
a: R=Me (74%)
b: R=Et (56%)
(
E)-3-nonen-2-one unfortunately resulted in a racemic
5a
product (entry 13). Since the reactions were very slow when
the bulkiness of two alkyl groups of 4 were increased (e.g.,
R , R = benzyl, i-propyl). A series of methylalkylamine
5c: R=i-Pr (11%)
[
Rh(nbd) ]BF or
2 4
1
/2[Rh(coe) Cl]2
1
2
2
derivatives was synthesized to optimize the best ligand
(
entries 14–20). The N,N-t-butylmethylamino derivative
O
was found to result in 70% ee (entry 20); however, none
of the enantioselectivities were a practical level. The abso-
lute configuration of product (3h) determined by specific
rotations was reversed from S to R by increasing bulkiness
of the ligand.
O
O
P
P
O
Rh
X
O
Me N
NMe2
2
7a: X=(nbd)(BF4)
2.2. Preparation of bidentate phosphoramidites and their
rhodium(I) complexes
7b: X=Cl
Scheme 2. Phosphoramidites based on linked-BINOL.
The use of a rigid bidentate ligand can be critical to
achieve high enantioselectivity for flexible acyclic sub-
strates. Thus, bidentate bisphosphoramidites 5 were newly
synthesized on the basis of linked-BINOL (6), which was
obtained from optically active BINOL by the procedures
of Shibasaki [14] (Scheme 2).
tion of two phosphorous atoms to a rhodium metal center.
The formation of a 1:1 complex was also confirmed by
mass spectroscopy (FAB), which showed a molecular
+
weight of 955.1913 (M ꢀBF
). The corresponding neutral
4
complex [Rh(Cl)(5a)] (7b) was synthesized by analogous
reaction of 5a with [Rh(Cl)(coe) , which exhibited a single
signal at 153.7 ppm (d, JRh–P = 296.3 Hz). A mixture of
[Rh(nbd) ]BF and 4b also gave single signal
The two methods pioneered by Feringa [15,12c] were
used for conversion of linked-BINOL to the corresponding
phosphoramidites (5). A mixture of P(NMe ) or P(NEt )
2 3
]
2 2
a
2
3
2
4
and an (R,R)-O-linked-BINOL (6) was refluxed in toluene
(142.3 ppm, d, J = 248.9 Hz) analogous to that of 5a, but
4c exhibited multiple signals at 24.8, 111.0 and 134.1 ppm
due to formation of a mixture of intra- and intermolecular
coordination.
in the presence of a catalytic amount of NH Cl to give air
4
and moisture-stable bisphosphoramidite 5a (74%) and 5b
(
56%). The protocol failed to give an N,N-diisopropyl
derivative (5c). Thus, 5c was synthesized in 11% yield by
a two-step method that involves chlorophosphonylation
of 6 at ꢀ60 °C and amidation with lithium diisopropyla-
mide [12c].
2.3. Bidentate phosphoramidites for asymmetric 1,4-addition
to enones
The reaction of 5a with [Rh(nbd) ]BF in CD Cl gave
The effects of 5, rhodium catalysts and bases in the reac-
tion of 2-cyclohexenone and phenylboronic acid in aque-
ous 1,4-dioxane are shown in Table 2. The catalysts were
prepared in situ by mixing a rhodium precursor and 10%
2
4
2
2
3
1
the desired [Rh(4a)(nbd)]BF (7a) as a fine powder.
P
4
NMR exhibited a single signal at 142.4 ppm (d, JRh–P
=
2
48.9 Hz), thus suggesting the intramolecular complexa-
Table 2
Effects of catalysts and bases
a
Entry
Rhodium complex
Base
none
°C/h
Yield/%
% ee
1
2
3
4
5
6
7
8
a
1/2[RhCl(coe)]
1/2[RhCl(coe)]
1/2[RhCl(coe)]
1/2[RhCl(coe)]
2
/5a
2
/5a
2
/5a
2
/5a
50/16
50/16
50/16
50/16
50/16
25/0.5
25/2
0
46
26
84
94
99
62
Trace
–
3
Et N
97 (R)
98 (R)
98 (R)
99 (R)
99.6 (R)
83 (R)
–
K
2
CO
KOH
3
[Rh(nbd)
[Rh(nbd)
[Rh(nbd)
[Rh(nbd)
2
2
2
2
]BF
]BF
]BF
]BF
4
4
4
4
/5a
/5a
/5b
/5c
Et
3
Et
3
Et
3
Et
3
N
N
N
N
25/2
All reactions were carried out in the presence of 2-cyclohexenone (1 mmol), phenylboronic acid (1.5 mmol), rhodium(I) catalyst (3 mol%), ligand (5,
.3 mol%), and base (if used, 1 mmol) in dioxane–H O (6/1).
3
2

K. Kurihara et al. / Journal of Organometallic Chemistry 692 (2007) 428–435
431
excess of 5 since they resulted in yields and enantioselectiv-
ities that were same as those of isolated complexes (7a, 7b).
3 mol% / 25˚C
100
The neutral complex thus prepared from [RhCl(coe)] and
2
80
60
40
20
0
5
a did not catalyze the reaction (entry 1), but the reaction
was initiated by addition of a base at 50 °C with yields
increasing in the order of basic strength (entries 2–4).
Finally, aqueous KOH was recognized to be the best base
for a neutral catalyst (entry 4), as was previously demon-
strated in analogous conjugated addition catalyzed by
Rh(I)-phosphine complexes. A combination of a cationic
rhodium(I) complex and 5 provided a much more active
catalyst than a neutral one. The reaction was completed
within 0.5 h at room temperature when [Rh(nbd) ]BF
1 mol%, 25˚C
.5 mol%, 50˚C
0
0.5 mol%, 25˚C
0.1 mol%, 50˚C
0
1
2
3
4
2
4
time/h
and 5a were used in the presence of Et N [5k] (entries 5
3
and 6). A perfect enantioselectivity that close to 100% ee
was obtained at room temperature (entry 6). On the other
hand, N,N-diethyl (5b) and N,N-diisopropyl (5c) deriva-
tives were less effective than the N,N-dimethyl ligand (5a)
Fig. 1. Amounts of catalyst loading and reaction rates.
ing high chemical yields and high enantioselectivities for
cyclic enones within 2 h at room temperature (entries 1–
7). The catalyst was especially effective for 2-cyclohexe-
none, easily achieving over 99% ee for various arylboronic
acids (entries 1–4). The catalyst was less effective for acyclic
enones; however, the selectivities were comparable to or
even higher than those of monophosphoramidites 4 or pre-
viously reported bisphosphine ligands such as BINAP [5–
11]. For example, the use of a catalyst obtained from 1/
(
entries 7 and 8).
The effects of catalyst amounts and reaction rates are
shown in Fig. 1. The addition of phenylboronic acid
1.5 equiv) to 2-cyclohexenone completed within 30 min
when a 3 mol% of [Rh(nbd) ]BF -5a was used at 25 °C.
(
2
4
The use of 0.5 mol% complex completed the reaction
within 3 h at 50 °C, though it was very slow at 25 °C. How-
ever, the reaction resulted in less than 5% yields even at
temperatures higher than 50 °C when catalyst loading
was reduced to 0.1 mol%.
With these optimized conditions, the scope of reaction
was investigated by using representative arylboronic acids,
a,b-unsaturated carbonyl compounds, and an [Rh(nbd)2]
2[RhCl(coe)]
13–20), and the use of Rh(I)-BINAP catalyst resulted in
83% ee for (E)-C 11CH@CHCOCH [5k], whereas
[Rh(nbd) ]BF /5a gave 74% ee at 25 °C (entry 8) and
and 4 resulted in 0–70% ee (Table 1, entries
2
H
5
3
2
4
84% ee at 5 °C (entry 9). The enantioselectivities for acyclic
1
(E)-enones were dependent on the b-substituent (R ) and a
3
1
BF /5a catalyst (Table 3). There was no difficulty in obtain-
substituent on ketone carbonyls (R ). The effect of R
4
Table 3
a
1,4-Addition of arylboronic acid to a,b-unsaturated carbonyl compounds catalyzed by a Rh(+)-5a complex
b
c
Entry
Carbonyl compound
ArB(OH)
2
, X=
°C/h
Product no.
Yield/%
% ee
1
2
3
4
5
6
7
8
9
2-Cyclohexenone
2-Cyclohexenone
2-Cyclohexenone
2-Cyclohexenone
2-Cyclopentenone
2-Cyclopentenone
2-Cycloheptenone
H
25/0.5
25/2
25/2
25/2
25/2
25/2
25/2
25/2
5/48
25/2
5/48
25/2
25/2
25/6
25/16
25/16
25/2
25/6
25/2
25/6
3a
3b
3i
99
90
99
86
99
99
90
87
42
98
65
97
91
80
78
71
62
98
99
98
99.6 (R)
99.5 (R)
99.8
99.8
96
96
98
74
84
80
83
81
85
92 (R)
94
90
81
85
3-MeO
4-MeO
3-Cl
3-Cl
4-MeO
H
3j
3e
3k
3g
3h
3h
3l
(E)-C
(E)-C
(E)-C
(E)-C
(E)-C
(E)-C
5
5
5
5
5
5
H11CH@CHCOCH
H11CH@CHCOCH
H11CH@CHCOCH
H11CH@CHCOCH
H11CH@CHCOCH
H11CH@CHCOPh
3
3
3
3
3
H
H
10
11
12
13
14
15
16
17
18
19
20
a
3-MeO
3-MeO
3-F
3-MeO
H
3-MeO
3-F
3-MeO
3-MeO
3-MeO
3-MeO
3l
3m
3n
3o
3p
3q
3r
3s
3t
(E)-(CH
(E)-(CH
(E)-(CH
(E)-(CH
(E)-(CH
3
3
3
3
3
)
)
)
)
)
2
2
2
2
2
CHCH@CHCOCH
CHCH@CHCOCH
CHCH@CHCOCH
CHCH@CHCOC
CHCH@CHCOPh
3
3
3
6
H
11
(E)-PhCH@CHCOCH
(E)-PhCH@CHCOPh
3
78
66
3u
All reactions were carried out in the presence of enone (1 mmol), arylboronic acid (1.5 mmol), [Rh(nbd)
and Et N (1 mmol) in dioxane (2.6 ml) and H O (0.43 ml).
Isolated yields based on enones.
2 4
]BF (0.03 mmol, 3 mol%), 5a (0.033 mmol)
3
2
b
c
Enantiomer excess determined by a chiral stationary column.

432
K. Kurihara et al. / Journal of Organometallic Chemistry 692 (2007) 428–435
increased in the order of Ph < n-C H11 < isopropyl for a
3. Conclusion
5
series of methyl ketones (entries 10, 15 and 19). Steric bal-
1
3
ance between R and R was also an important factor
affecting the selectivity. The selectivities were improved
In conclusion, the effects of catalysts, phosphoramidites
(4, 5) and bases on reaction rates and enantioselectivities
in the rhodium-catalyzed 1,4-addition of arylboronic acids
to enones were investigated in detail. Although traditional
monodentate phosphoramidite ligands (4) gave good
enantioselectivities for cyclic enones, we have shown that
bidentate phosphoramidite (5a), first prepared from
Shibasaki’s linked-BINOL, is an excellent ligand for both
cyclic and acyclic enones and enable the reaction to be
completed in a short time at room temperature. Works
aimed at characterization of the catalysts by X-ray analy-
sis are in progress to elucidate the enantioselection
mechanism.
3
by increasing the bulkiness of R for enones having a pri-
mary alkyl group at the b-carbon (entries 10 and 13), but
enones possessing a hindered substituent (R = isopropyl
and phenyl) reduced the selectivity by increasing the bulk-
iness of R groups (CH > Ph > cyclohexyl) (entries 15, 17–
0). The para- and meta-substituents in arylboronic acids
affected enantioselectivities (entries 8–12). The enantiose-
lectivities of meta-substituted arylboronic acids were gener-
ally higher than that of para-substituted boronic acids, as
shown in Table 1 and as previously reported for related
rhodium- and palladium-catalyzed reactions [4,5].
1
3
3
2
2
.4. Asymmetric addition to a,b-unsaturated esters
4. Experimental
Asymmetric 1,4-additions to acyclic and cyclic a,b-
4.1. Reagents
unsaturated esters are shown in Scheme 3. The reaction
was slower than that for enones, but high enantioselectivi-
ties comparable to those of the corresponding enones were
easily obtained. Methyl crotonate, 5H-furan-2-one, and
[RhCl(coe) ] [16] and [Rh(nbd) ]BF [17] were prepared
2
2
2
4
by the reported procedures. Chiral phosphoramidites (4)
were obtained from (R)-BINOL and the corresponding
amines by the method of Feringa [15]. (R,R)-O-linked-
BINOL (6) was synthesized from (R)-BINOL by the
method of Shibasaki [14].
5
,6-dihydro-2H-pyran-2-one afforded 3v (75% ee), 3w
77% ee), 3x (89% ee) and 3y (91% ee), respectively, in
the presence of [Rh(nbd) ]BF -5a and Et N at room tem-
(
2
3
3
perature. On the other hand, the use of monodentate phos-
1
2
phoramidites such as 4 (R , R = Et) resulted in no
reaction for 5H-furan-2-one and 35% yield and 72% ee
for 5,6-dihydro-2H-pyran-2-one at 50 °C in the presence
of Rh(acac)(coe) and Et N in dioxane-H O (6/1).
4.2. Bidentate phosphoramidites (5, Scheme 2)
4.2.1. N,N-Dimethyl (R,R)-O-linked-phosphoramidite (5a)
0
00
3,3 -(Oxydimethylene)-di-1,1 -bi-2-naphthol (6, (R,R)-
2
3
2
O-linked-BINOL) (1 mmol), NH Cl (0.01 g) and
4
P(NMe ) (2.8 mmol) in dry toluene (10 ml) were refluxed
2
3
for 12 h under nitrogen. The crude solid obtained by evap-
oration of the solvent was crystallized from CH Cl /pen-
2
2
1
tane to give 5a as white crystals (74%). H NMR
400 MHz, CD Cl ): d = 2.23–2.39 (m, 12 H), 4.82 (d,
MeO
(
2
2
J = 13.3 Hz, 2H), 5.02 (d, J = 13.3 Hz, 2H), 7.07–7.39
Me
B(OH)2
MeO
13
(m, 14H), 7.76–7.86 (m, 6H), 8.15 (s, 2H); C NMR
(1)
OMe
(100 MHz, CD Cl ) d = 35.7, 35.9, 69.2, 122.1, 122.9,
[
Rh(nbd) ]BF -5a
2
2
2
4
o
OMe
O
Et N, 25 C, 24 h
Me
3
124.2, 125.1, 126.2, 126.5, 126.8, 127.0, 128.2, 128.7,
dioxane-H O (6/1)
O
2
1
1
29.3, 130.6, 130.9, 131.0, 131.8, 132.3, 133.1, 148.0,
3
v, 57%, 75%ee
3
1
48.1, 149.7; P NMR (161.7 Hz, CD Cl ) d = 149.4;
2
2
O
O
MS (m/z) 46 (33), 136 (31), 154 (41), 266 (27), 282 (47),
O
B(OH)2
+
329 (100), 388 (25), 716 (28), 761 (16, [M+H] ); exact mass
(2)
O
O
calcd for C H N O P : 760.2256; found 760.2275;
[
Rh(nbd) ]BF -5a
46 38
2
5 2
2
4
o
21
Et N, 25 C, 6 h
3
½aꢁD ¼ ꢀ522:5 (c 0.56, CHCl3).
dioxane-H O (6/1)
2
3
w, 68%, 77%ee
4
.2.2. N,N-Diethyl (R,R)-O-linked-phosphoramidite (5b)
An analogous method used for preparation of 5a gave
O
O
O
B(OH)2
FG
1
5b in 56% yield. H NMR (400 MHz, CD Cl ) d = 0.75–
2
2
(3)
0.91 (m, 12H), 2.64–2.95 (m, 8H), 4.89 (d, J = 13.6 Hz,
[
Rh(nbd) ]BF -5a
2
4
o
Et N, 25 C, 16 h
FG
2H), 5.06 (d, J = 13.6 Hz, 2H), 7.09–7.41 (m, 14H), 7.79–
3
1
3
dioxane-H O (6/1)
2
7.87 (m, 6H), 8.15 (d, J = 8.8 Hz, 2H);
C NMR
3x: FG=H, 72%, 89%ee
(
100 MHz, CD Cl ) d = 15.0, 39.1, 39.3, 69.1, 122.3,
2
2
3y: FG=3-MeO, 61%, 91%ee
124.3, 125.0, 125.1, 126.0, 126.4, 126.9, 127.1, 127.8,
Scheme 3. Asymmetric 1,4-addition to unsaturated esters.
128.7, 130.3, 130.6, 130.9, 131.2, 131.7, 132.3, 133.1,

K. Kurihara et al. / Journal of Organometallic Chemistry 692 (2007) 428–435
433
3
1
1
48.4, 148.5, 149.9;
P NMR (161.7 MHz, CD Cl )
4.4. General procedure for asymmetric 1,4-addition (Table
1)
2
2
d = 150.1; MS (m/z) 72 (31), 266 (38), 282 (51), 329
100), 416 (15), 744 (28), 817 (10, [M+H] ); exact mass
+
(
+
1
calcd for C H N O P ([M+H] ): 817.2961; found
A flask charged with [Rh(coe) Cl] (0.015 mmol), 4 (R ,
5
2
0
47
2
5
2
2
2
2
2
8
17.2981; ½aꢁD ¼ ꢀ414:4 (c 0.50, CHCl3).
R = Et) (0.066 mmol) was flushed with argon. 1,3-Diox-
ane (2.6 ml) was then added. After being stirred for 1 h
at room temperature, arylboronic acid (1.5 mmol), enone
(1.0 mmol), and aqueous KOH (2.4 M, 0.43 ml, 1 mmol)
were added. The resulting mixture was stirred for 6 h at
50 °C. Isolated yields determined by chromatography on
silica gel are shown in Table 1. Enantiomer excess was
determined by HPLC analyses using a chiral stationary col-
umn (Dicel Chiralpak AD and Chiralcel OD-H or OB-H).
We previously reported the spectral data of 3a [5l], 3b
[5l], 3c [5l], 3d [5a], 3e [5l], 3f [4f], 3g [5a], and 3h [5l].
The specific rotations of these compounds were 3a
4
(
.2.3. N,N-Diisopropyl (R,R)-O-linked-phosphoramidite
5c)
To a mixture of PCl (2 mmol) and Et N (4 mmol) in
toluene (3 ml) was added a solution of 3,3 -(oxydimethyl-
ene)-di-1,1 -bi-2-naphthol (6, (R,R)-O-linked-BINOL)
3
3
00
0
(
1 mmol) in toluene (10 ml) at ꢀ60 °C. After being stirred
for 2 h, the reaction mixture was allowed to warm up to
room temperature. The precipitates were removed by filtra-
tion. The filtrate was treated with n-BuLi (2 mmol) and i-
Pr NH (3 mmol) at ꢀ40 °C. After being stirred for 16 h
2
2
D
1
22
D
at room temperature, the crude solids obtained by evapora-
tion of the solvent was crystallized from CH Cl /pentane
(½aꢁ ¼ þ20:4 (c 1.03, CHCl )), 3b (½aꢁ ¼ þ13:6 (c 0.98,
3
2
D
2
21
D
CHCl )), 3c (½aꢁ ¼ þ17:3 (c 0.96, CHCl )), 3d (½aꢁ
¼
2
2
3
3
1
21
to give 5c as white crystals (11%). H NMR (400 MHz,
CD Cl ); d 0.75–1.36 (m, 24H), 3.24–3.32 (m, 4H), 5.03
s, 4H), 7.12–7.39 (m, 14H), 7.92–7.97 (m, 6H), 8.23 (s,
H); C NMR (100 MHz, CD Cl ) d = 24.4, 24.5, 24.6,
4.7, 45.2, 45.3, 69.1, 69.2, 122.6, 124.7, 125.1, 126.1,
26.2, 127.0, 127.3, 128.6, 128.8, 129.1, 130.0, 131.0,
þ79:9 (c 1.13, CHCl )), 3e (½aꢁ ¼ þ71:4 (c 0.92, CHCl )),
3
D
3
22
23
D
3f (½aꢁ ¼ þ58:8 (c 1.07, CHCl )), 3g (½aꢁ ¼ þ59:3 (c 1.00,
2
2
D
3
21
(
CHCl )), and 3h (½aꢁ ¼ þ16:1 (c 0.97, CHCl )).
3
D
3
1
3
2
2
1
1
2 2
4.5. General procedure for asymmetric 1,4-addition (Table 3
and Scheme 3)
3
1
31.2, 131.4, 132.6, 132.8, 133.1, 148.7, 150.9, 167.9;
P
NMR (161.7 MHz, CD Cl ) d = 150.7; MS (m/z) 43 (31),
A flask charged with [Rh(nbd) ]BF (0.03 mmol,
2
2
2
4
5
3
7 (32), 71 (26), 149 (100), 266 (27), 281 (49), 329 (87),
3 mol%) and 5a (0.033 mmol) was flushed with argon.
1,3-Dioxane (2.6 ml) and water (0.43 ml) were then added.
After being stirred for 0.5 h, arylboronic acid (1.5 mmol),
a,b-unsaturated carbonyl compound (1.0 mmol) and tri-
ethylamine (1 mmol) were successively added. The resulting
mixture was stirred at 5 °C or 25 °C. Isolated yields deter-
mined by chromatography on silica gel are shown in Table
+
91 (28), 444 (50), 772 (18), 873 (43, [M+H] ); exact mass
+
calcd for C H N O P ([M+H] ): 873.3586; found
5
4
55
2
5 2
8
73.3604.
4
.3. Rhodium complexes (7, Scheme 2)
.3.1. Complex between [Rh(nbd) ]BF and 5a (7a)
2
. Enantiomer excess was determined by HPLC analyses
4
2
4
using a chiral stationary column (Dicel Chiralpak AD
and Chiralcel OD-H or OB-H).
To a solution of 5a (0.05 mmol) in CD Cl was added
2
2
[
Rh(nbd) ]BF (0.05 mmol) under atmosphere of argon.
2 4
The solvent was evaporated to dryness in vacuo to give sol-
ids of 7a. All attempts at synthesizing single crystals were
4
.5.1. 4-(3-Fluorophenyl)nonan-2-one (3m)
1
2
1
½
aꢁ ¼ þ14:8 (c 1.00, CHCl ); H NMR (400 MHz,
D
3
3
1
failed. P NMR (161.7 MHz, CD Cl ) d = 142.4 (d, J
2
2
Rh–P
CDCl ) d 0.74–0.77 (m, 3H), 1.02–1.18 (m, 6H), 1.43–
1.54 (m, 2H), 1.96 (s, 3H), 2.63 (d, J = 7.3 Hz, 2H), 3.02–
3.09 (m, 1H), 6.78–6.89 (m, 3H), 7.13–7.19 (m, 2H);
NMR (100 MHz, CDCl ) d 14.0, 22.4, 26.9, 30.6, 31.6,
36.2, 40.9, 50.6, 113.1 (d, J = 20.7 Hz), 114.1 (d,
J = 21.5 Hz), 123.3 (d, J = 2.5 Hz), 129.8 (d, J = 8.3 Hz),
147.4, 162.9 (d, J = 245.6 Hz), 207.4; MS (m/z) 43 (54),
3
=
248.9 Hz); exact mass calcd for C H BF N O P Rh
53 46 4 2 5 2
+
1
3
(
[M ꢀBF ]): 955.1938; found 955.1913.
4
C
3
4
.3.2. Complex between [Rh(coe) Cl] and 5a (7b)
2 2
3
1
P NMR (161.7 MHz) of a mixture between 5a
(
2
0.05 mmol) and [RhCl(coe)2]2 (0.025 mmol) in CD Cl2
exhibited a signal at d = 153.7 (d, JRh–P = 296.3 Hz).
55 (9), 109 (43), 122 (64), 135 (19), 165 (63), 178 (100),
+
2
36 (11, M ); exact mass calcd for C H FO: 236.1576;
1
5
21
4
.3.3. Complex between [Rh(nbd) ]BF and 5b
2
4
found 236.1575.
3
1
P NMR (161.7 MHz) of a mixture between 5b
0.05 mmol) and [Rh(nbd) ]BF4 (0.05 mmol) in CD Cl
(
2
2
2
4.5.2. 3-(4-Methoxyphenyl)-1-phenyloctan-1-one (3n)
1
22
exhibited a signal at d = 142.3 (d, JRh–P = 248.9 Hz).
½aꢁ ¼ ꢀ2:9 (c 0.97, CHCl ); H NMR (400 MHz,
D
3
CDCl ) d 0.81–0.84 (m, 3H), 1.21–1.27 (m, 6H), 1.59–
3
4
.3.4. Complex between [Rh(nbd) ]BF and 5c
2
4
1.73 (m, 2H), 3.17–3.34 (m, 3H), 3.78 (s, 3H), 6.71–
3
1
P NMR (161.7 MHz) of a mixture between 5c
0.05 mmol) and [Rh(nbd) ]BF4 (0.05 mmol) in CD Cl
6
.84 (m, 3H), 7.18–7.55 (m, 4H), 7.89–7.91 (m, 2H);
C NMR (100 MHz, CDCl ) d 14.06, 22.51, 27.17,
1
3
(
2
2
2
3
exhibited three signals at d = 24.8, 111.0, 134.1.
31.78, 36.20, 41.31, 45.93, 55.11, 111.14, 113.58, 119.98,

434
K. Kurihara et al. / Journal of Organometallic Chemistry 692 (2007) 428–435
1
1
1
28.1, 128.5, 129.35, 132.90, 137.23, 146.77, 159.58,
4.5.7. 4-Phenyldihydrofuran-2-one (3w)
1
2
2
99.15 ; MS (m/z) 55 (13), 77 (44), 105 (75), 121 (11),
½aꢁ ¼ ꢀ39:2 (c 0.99, CHCl ); H NMR (400 MHz,
D
3
+
35 (27), 190 (100), 205 (33), 239 (49), 310 (29, M );
CDCl ) d2.60 (dd, J = 9.3, 17.6 Hz, 1H), 2.85 (dd,
3
exact mass calcd for C H O : 310.1933; found
J = 8.8, 8.8 Hz, 1H), 3.68–3.76 (m, 1H), 4.60 (dd, J = 7.8,
9.02 Hz, 1H), 4.20 (dd, J = 7.8, 8.8 Hz, 1H), 7.15–7.32
2
1
26
2
3
10.1931.
1
3
(
m, 5H); C NMR (100 MHz, CDCl ) d 35.7, 41.0, 74.0,
3
4
.5.3. 5-Methyl-3-(3-fluorophenyl)hexan-2-one (3q)
1
126.7, 127.7, 129.1, 139.4, 176.4; MS (m/z) 51 (12), 78
(12), 104 (100), 162 (23, M ); exact mass calcd for
2
1
+
½
aꢁ ¼ þ25:7 (c 0.95, CHCl ); H NMR (400 MHz,
D
3
CDCl ) d 0.67 (d, J = 6.95 Hz, 3H), 0.86 (d, J = 6.95 Hz,
C H O : 162.0681; found 162.0695.
3
10 10
2
3
2
H), 1.69–1.78 (m, 1H), 1.93 (s, 3H), 2.65–2.77 (m, 2H),
.83–2.89 (m, 1H), 6.76–6.86 (m, 3H), 7.12–7.19 (m, 2H);
4.5.8. 4-Phenyltetrahydropyran-2-one (3x)
1
1
3
22
C NMR (100 MHz, CDCl ) d 20.3, 20.6, 30.6, 33.2,
½aꢁ ¼ ꢀ2:8 (c 1.01, CHCl ); H NMR (400 MHz,
3
D
3
4
1
7.4, 47.6, 113.1 (d, J = 21.5 Hz), 114.9 (d, J = 21.5 Hz),
24.0 (d, J = 3.3 Hz), 129.5 (d, J = 8.3 Hz), 146.1 (d,
CDCl ) d 1.91–2.01 (m, 1H), 2.07–2.14 (m, 1H), 2.56 (dd,
3
J = 10.7, 17.6 Hz, 1H), 3.15 (ddd, J = 17.6, 5.9, 1.7 Hz,
1H), 3.12–3.20 (m, 1H), 4.31 (ddd, J = 11.8, 10.9, 3.9 Hz,
J = 6.6 Hz), 162.7 (d, J = 245.7 Hz), 207.7; MS (m/z) 43
(
(
70), 109 (23), 123 (32), 135 (11), 150 (100), 166 (15), 208
1H), 4.43 (ddd, J = 11.5, 5.0, 3.9 Hz, 1H), 7.13–7.22 (m,
+
13
4, M ); exact mass calcd for C H FO: 208.1263; found
3H), 7.26–7.30 (m, 2H). C NMR (100 MHz, CDCl ) d
1
3
17
3
2
08.1264.
30.2, 37.3, 47.4, 68.6, 126.4, 127.1, 128.9, 142.7, 170.6;
MS (m/z) 51 (9), 78 (20), 92 (26), 104 (65), 117 (87), 130
+
4
1
.5.4. 1-Cyclohexyl-4-methyl-3-(3-methoxyphenyl)pentan-
-one (3r)
(16), 158 (16), 176 (100, M ); exact mass calcd for
C H O 176.0837; found 176.0836.
1
2
14
2
22
1
½
aꢁ ¼ þ54:5 (c 0.50, CHCl ); H NMR (400 MHz,
D
3
CDCl ) d 0.74 (d, J = 6.8 Hz, 3H), 0.92 (d, J = 6.6 Hz,
4.5.9. 4-(3-Methoxyphenyl)tetrahydropyran-2-one (3y)
1
3
22
3
1
7
H), 1.06–1.29 (m, 4H), 1.56–1.85 (m, 7H), 2.19–2.21 (m,
H), 2.79 (d, J = 7.3 Hz, 2H), 2.93 (dt, J = 7.3 Hz,
.1 Hz, 1H), 3.79 (s, 3H), 6.68–6.74 (m, 3H), 7.15–7.26
½aꢁ ¼ þ4:0 (c 0.51, CHCl ); H NMR (400 MHz,
D
3
CDCl ) d 1.98–2.08 (m, 1H), 2.14–2.21 (m, 1H), 2.63 (dd,
3
J = 10.7, 17.6 Hz, 1H), 2.92 (ddd, J = 17.7, 5.85, 1.46 Hz,
1H), 3.17–3.25 (m, 1H), 4.38 (ddd, J = 11.0, 11.0, 3.7 Hz,
1H), 4.50 (ddd, J = 11.5, 4.6, 3.9 Hz, 1H), 6.74–6.83 (m,
3H), 7.14–7.36 (m, 1H). C NMR (100 MHz, CDCl ) d
30.2, 37.4, 55.2, 68.6, 112.1, 112.7, 118.6, 130.0, 144.4,
1
3
(
m, 1H); C NMR (100 MHz, CDCl ) d 20.4, 20.8,
3
2
1
5
5.59, 25.61, 25.8, 28.1, 28.2, 33.0, 44.8, 47.5, 51.2, 55.1,
11.0, 114.3, 120.8, 128.9, 145.6, 159.3, 213.1; MS (m/z)
5 (22), 83 (51), 121 (30), 162 (100), 177 (17), 288 (16,
1
3
3
+
M ); exact mass calcd for C H O : 288.2089; found
2
160.0, 170. 6; MS (m/z) 65 (18), 77 (19), 91 (35), 121 (38),
134 (86), 150 (31), 163 (25), 206 (100, M ); exact mass calcd
1
9
28
2
+
88.2099.
for C H O : 206.0943; found 206.0937.
1
2
14
3
4
(
.5.5. 4-Methyl-3-(3-methoxyphenyl)-1-phenylpentan-1-one
3s)
The spectral data of 3i [5l], 3j [5l], 3k [5b], 3l [5l], 3o [5l],
3p [5l], 3t [4f] and 3u [4f] were reported previously. The spe-
21
1
22
½
aꢁ ¼ ꢀ1:8 (c 0.92, CHCl ); H NMR (400 MHz,
cific rotations of these compounds were 3i (½aꢁ ¼ þ17:5 (c
D
3
D
21
CDCl ) d 0.800 (d, J = 6.6 Hz, 3H), 0.98 (d, J = 6.8 Hz,
0.97, CHCl )), 3j (½aꢁ ¼ þ16:4 (c 0.93, CHCl )), 3k
3
3
D
3
2
D
2
23
D
3
1
3
7
H), 1.86–1.97 (m, 1H), 3.11–3.17 (dd, J = 7.2, 14.3 Hz,
H), 3.34 (d, J = 6.8 Hz, 2H), 3.76 (s, 3H), 6.68–6.79 (m,
H), 7.16 (t, J = 7.8 Hz, 1H), 7.39–7.43 (m, 2H), 7.50–
(½aꢁ ¼ þ70:8 (c 1.02, CHCl )), 3l (½aꢁ ¼ þ15:9 (c 0.93,
3
2
D
1
CHCl )), 3o (½aꢁ ¼ þ32:4 (c 0.98, CHCl )), 3p
3
3
21
23
D
(½aꢁ ¼ þ18:2 (c 0.51, CHCl )), 3t (½aꢁ ¼ ꢀ1:6 (c 0.51,
D
3
1
3
22
D
.54 (m, 1H), 7.84–7.94 (m, 2H); C NMR (100 MHz,
CHCl )) and 3u (½aꢁ ¼ ꢀ4:4 (c 0.91, CHCl )).
3
3
CDCl ) d 20.5, 20.9, 33.3, 42.5, 47.8, 55.1, 111.1, 114.4,
3
1
1
20.8, 128.0, 128.5, 129.0, 132.8, 137.3, 145.4, 159.3,
Acknowledgement
99.4; MS (m/z) 77 (35), 105 (100), 162 (91), 177 (8), 239
+
(
8), 282 (10, M ); exact mass calcd for C H O :
This work was supported by Grant-in-Aid for Scientific
Research on Priority Areas (No. 14078101, ‘‘Reaction
Control of Dynamic Complexes’’) from Ministry of Educa-
tion, Culture, Sports, Science and Technology, Japan.
1
9
22
2
2
82.1620; found 282.1623.
4
.5.6. Methyl-3-(3-methoxyphenyl)butanoate (3v)
1
2
D
1
½
aꢁ ¼ þ23:0 (c 0.56, CHCl ); H NMR (400 MHz,
3
CDCl ) d 1.29 (d, J = 7.1 Hz, 3H), 2.56 (dd, J = 8.3,
References
3
1
5.2 Hz, 1H), 2.63 (dd, J = 6.6, 15.3 Hz, 1H), 3.21–3.30
[
1] For reviews, see: (a) N. Krause, A. Hoffmann-R o¨ der, Synthesis
(2001) 171;
(
m, 1H), 3.63 (s, 3H), 3.80 (s, 3H), 6.74–6.83 (m, 3H),
1
3
7
3
1
.20–7.26 (m, 2H); C NMR (100 MHz, CDCl ) d 21.7,
3
(
b) K. Tomioka, Y. Nagaoka, in: E.N. Jacobsen, A. Pfalts, H.
6.4, 42.6, 51.5, 55.1, 111.4, 112.7, 119.0, 129.5, 147.4,
Yamamoto (Eds.), Comprehensive Asymmetric Catalysis, Springer-
Verlag, Berlin, 1999 (Chapter 31.1).
59.6, 172.8; MS (m/z) 77 (10), 91 (13), 105 (26), 121
+
(
11), 135 (84), 148 (100), 208 (57, M ); exact mass calcd
[2] (a) A. Alexakis, C. Benhaim, Eur. J. Org. Chem. (2002) 3221;
b) B.L. Feringa, Acc. Chem. Res. 33 (2000) 346.
(
for C H O : 208.1099; found 208.1091.
1
2
16
3

K. Kurihara et al. / Journal of Organometallic Chemistry 692 (2007) 428–435
435
[
[
3] For reviews, see: (a) T. Hayashi, K. Yamasaki, Chem. Rev. 103
(e) A. Duursma, J.-G. Boiteau, L. Lefort, J.A.F. Boorgers, A.H.M.
de Vries, J.G. de Vries, A.J. Minnard, B.L. Feringa, J. Org. Chem. 69
(2004) 8045;
(f) S.L.X. Martina, A.J. Minnaard, B. Hessen, B.L. Feringa,
Tetrahedron Lett. 46 (2005) 7159.
(
(
2003) 2829;
b) K. Fagnou, M. Lautens, Chem. Rev. 103 (2000) 169.
4] (a) T. Nishikata, Y. Yamamoto, N. Miyaura, Angew. Chem., Int.
Ed. 42 (2003) 2768;
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