Kinetic resolution of phosphoryl and sulfonyl esters of 1,1′-bi-2-naphthol via Pd-catalyzed alcoholysis of their vinyl ethers

Article abstract of DOI:10.1016/j.tetasy.2008.06.034

Kinetic resolution of phosphoryl and sulfonyl esters of 1,1′-bi-2-naphthol has been achieved via the Pd-catalyzed alcoholysis of their vinyl ethers. The highest k_rel value reached 36.8 with substrate 3c, and (R)-3c 99.0% ee was obtained in 43%

Full text of DOI:10.1016/j.tetasy.2008.06.034

Tetrahedron: Asymmetry 19 (2008) 1593–1599
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Tetrahedron: Asymmetry
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Kinetic resolution of phosphoryl and sulfonyl esters of 1,10-bi-2-naphthol
via Pd-catalyzed alcoholysis of their vinyl ethers
Takeshi Sakuma a, Eiji Yamamoto a,b, Hiroshi Aoyama b, Yasushi Obora b, Yasushi Tsuji b,
,
*
Makoto Tokunaga a,b,
*
a Department of Chemistry, Kyushu University, Hakozaki, Higashi-ku, Fukuoka 812-8581, Japan
b Catalysis Research Center, Hokkaido University and JST, CREST, Kita-ku, Sapporo 001-0021, Japan
a r t i c l e i n f o
a b s t r a c t
Kinetic resolution of phosphoryl and sulfonyl esters of 1,10-bi-2-naphthol has been achieved via the
Pd-catalyzed alcoholysis of their vinyl ethers. The highest krel value reached 36.8 with substrate 3c,
and (R)-3c 99.0% ee was obtained in 43% isolated yield.
Article history:
Received 2 May 2008
Accepted 24 June 2008
Available online 16 July 2008
Ó 2008 Elsevier Ltd. All rights reserved.
1. Introduction
2,20-dihydroxy-1,10-biaryls. Herein, we report that phosphoryl
(PO) and sulfonyl (SO2) groups act as efficient directing groups in
The hydrolysis and alcoholysis of organic molecules are funda-
mental reactions in organic synthesis. The reactions with biocata-
lysts in particular play a major role in the asymmetric synthesis
of optically active compounds.1 On the other hand, in the area of
homogeneous catalysis, fewer studies with little progress have
been made compared to those on enzymatic reactions. In recent
years, we and others have carried out research on hydrolysis2
and alcoholysis3 reactions with metal–complex catalysts. As well
as the Co-catalyzed hydrolytic kinetic resolution of epoxides,2 we
have developed transition metal-catalyzed stereoselective hydro-
lysis and alcoholysis of alkenyl ethers3a and azlactones.3c Using
the Pd-catalyzed vinyl ether alcoholysis reaction,3a an efficient
kinetic resolution of mono-vinyl, mono-acyl derivatives of axially
chiral diols, such as 2-acyloxy-20-vinyloxy-1,10-biaryls, has been
achieved.3b Enantioselective oxidative coupling of hydroxyaryls is
one of the conventional approaches to this class of compounds.4
However, this method is only applicable for 2-naphthols into
1,10-bi-2-naphthols, but not for phenols into 1,10-bi-2-phenols
due to the instability of the radical intermediate. Thus, an
advantage of our strategy is that the reaction is applicable to
1,10-bi-2-phenols as well as to 1,10-bi-2-naphthols. In our alcohol-
ysis reaction system,3b the acyl group on the substrates is indis-
pensable for obtaining high selectivity and reactivity. In addition,
the bulkiness of the acyl group significantly affected the selectivity
and reactivity. The krel value of the kinetic resolution changed as
follows: acetyl (6.1), 1-heptanoyl (14.3), pivaloyl (20.3), and
1-adamantanoyl (28.7). Thus, we have continued further the inves-
tigation on the effect of directing group at the 2-position of the
the catalytic alcoholysis reaction as well as report on the influence
of the substituents on them with regard to the selectivity and
reactivity.
2. Results and discussion
The vinyl ether substrates bearing a phosphoryl group, 1a–d,
and a sulfonyl group, 3a–e, were prepared from racemic 1,10-
bi-2-naphthol and the corresponding phosphoryl or sulfonyl chlo-
rides. The catalytic alcoholysis reactions to give 2a–d or 4a–e using
methanol as reagent were carried out under the similar conditions
to those mentioned in the previous report (Scheme 1).3b The cata-
lyst consists of 5 mol % Pd(OAc)2 and 6 mol % chiral diamine ligand
having tetraphenylphenyl group:5 (R,R)-N,N0-di[4-((20,30,40,50-tetra-
phenyl)phenyl)phenyl]-1,2-cyclohexanediamine 7 (Scheme 2).
Ph
Ph
Ph
Ph
Ph
Ph
Ph
NH HN
Ph
5
Substrate 1a, which has a dimethoxyphosphoryl group, under-
went alcoholysis of the vinyl group to give 73% ee of the product
(S)-2a in 56% yield and 95% ee of unreacted (R)-1a in 42% yield
(Table 1, entry 1). The krel value of the kinetic resolution was
calculated as 22.9, which is slightly better than that of the standard
substrate with a pivaloyl group mentioned (krel = 20.3) in our
previous study.3b The selection rule for enantiomers is same as
* Corresponding authors. Tel./fax: +81 92 642 7528 (M.T.).
E-mail address: mtok@chem.kyushu-univ.jp (M. Tokunaga).
0957-4166/$ - see front matter Ó 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tetasy.2008.06.034

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T. Sakuma et al. / Tetrahedron: Asymmetry 19 (2008) 1593–1599
5 mol% Pd(OAc)2
6 mol% 5
OH
O
O
O
O
O
O
O
O
10 equiv. MeOH
+
R
R
R
R
R
R
CH2Cl2, 20 °C
P
P
P
rac-1
(R)-1
(S)-2
O
=
1a: R = OMe
1b: R = OEt
1c: R2
O
1d: R = Cy
Scheme 1. Pd-catalyzed methanolysis of vinyl ethers 1.
5 mol% Pd(OAc)2
6 mol% 5
OH
O
O
O
O
O
O
O
O
10 equiv. MeOH
+
O
R
O
R
O
R
CH2Cl2, 20 °C
S
S
S
rac-3
3a: R = Me
3b: R =
(R)-3
(S)-4
O
3d: R =
3e: R =
Me
R
iPr
3c: R =
iPr
iPr
S
O
Scheme 2. Pd-catalyzed methanolysis of vinyl ethers 3.
3). The krel value reached 36.8. The unreacted substrate (R)-3c was
obtained with 99.0% ee in 43% isolated yield. The alcoholysis
product (S)-4c was obtained with 75.7% ee in 56% isolated yield
at the same time. In contrast to substrates 1, substrates 3 gave
higher selectivity when a sterically congested directing group
was used. A chiral substituent was introduced on the sulfonyl
group. When a (R)-camphorsulfonyl group was introduced 3d,
the selectivity factor of 6.7 was observed. On the other hand, when
an (S)-camphorsulfonyl group was introduced, 3e, the krel value
increased to 13.5. This result suggests that the chirality on the
Table 1
Kinetic resolution via palladium-catalyzed methanolysis of 1a
e
Entry
Substrate
Time
(h)
Conversion
(%)b
ee of (R)-1c
ee of (S)-2c
krel
(yield (%))d
(yield (%))d
1
2
3
4
1a
1b
1c
1d
24
48
24
24
56.5
61.1
39.1
33.2
94.8 (42.2)
98.5 (36.7)
41.0 (59.3)
27.4 (65.4)
73.0 (56.0)
62.7 (62.1)
63.8 (39.1)
55.2 (33.1)
22.9
20.0
6.7
4.8
a
A mixture of Pd(OAc)2 (0.01 mmol) and 7 (0.012 mmol) in CH2Cl2 was stirred at
20 °C for 1 h, after which the solvent was removed under reduced pressure. To this
were added CH2Cl2 (0.125 mL), 1 (0.2 mmol), and MeOH (0.081 mL, 2.0 mmol), and
then stirred at 20 °C for 24–48 h.
b
Calculated with the equation: conv = eesub/(eesub + eepro), see Ref. 3c.
Determined by HPLC analysis.
Isolated yield.
Calculated with the equations: krel = ln[(1 ꢀ conv)(1 ꢀ eesub)]/ln[(1 ꢀ conv)(1 +
Table 2
c
Kinetic resolution via palladium-catalyzed methanolysis of 3a
d
e
e
Entry
Substrate
Time
(h)
Conversion
(%)b
ee of (R)-3c
ee of (S)-4c
krel
(yield (%))d
(yield (%))d
eesub)] = ln[1 ꢀ conv(1 + eepro)]/ln[1 ꢀ conv(1 ꢀ eepro)], see Ref. 3c.
1
2
3
4
5
3a
3b
3c
24
24
24
24
24
46.6
47.0
56.7
47.9
61.7
40.7 (51.7)
45.6 (51.6)
99.0 (43.3)
54.8g (49.6)
95.0j (41.8)
46.7 (48.3)
51.4 (47.8)
75.7 (55.5)
59.5h (49.7)
58.9k (57.8)
4.0
4.8
36.8
6.7
the previous reaction in terms of axial chirality.3b When the phos-
phoryl group has a slightly larger substituent, such as a diethoxy
group 1b, a little decrease in krel value (20.0) was observed (Table
1, entry 2). 2,2-Dimethyl-1,3-propylenedioxyphosphoryl 1c and
dicyclohexylphosphoryl 1d gave krel values 6.7 and 4.8, respec-
tively (Table 1, entries 3 and 4). Although a bulkier substituent
showed higher selectivity when the acyl group was employed in
the previous work,3b an opposite tendency was observed when 1
is employed as a substrate. The alcoholysis reaction was found to
be applicable to the substrates bearing a sulfonyl group, 3a–e
(Table 2). Substrate 3a, which has a methanesulfonyl group, gave
a rather low krel value (krel = 4.0, Table 2, entry 1). Slightly better
selectivity (krel = 4.8) was observed when the directing group was
changed to 4-toluenesulfonyl group 3b (Table 2, entry 2). The
highest selectivity was observed with 3c, which has a 2,4,6-tri-
isopropylphenylsulfonyl group as a directing group (Table 2, entry
3df
3ei
13.5
a
A mixture of Pd(OAc)2 (0.01 mmol) and 7 (0.012 mmol) in CH2Cl2 were stirred
at 20 °C for 1 h, after which the solvent was removed under reduced pressure. To
this were added CH2Cl2 (0.125 mL), 3 (0.2 mmol), and MeOH (0.081 mL, 2.0 mmol),
and then stirred at 20 °C for 24 h.
b
Calculated with the equation: conv = eesub/(eesub + eepro), see Ref. 3c.
Determined by HPLC analysis.
Isolated yield.
Calculated with the equations: krel = ln[(1 ꢀ conv)(1 ꢀ eesub)]/ ln[(1 ꢀ conv)-
c
d
e
(1 + eesub)] = ln[1 ꢀ conv(1 + eepro)]/ln[1 ꢀ conv(1 ꢀ eepro)], see Ref. 3c.
f
A 1:1 mixture of (aS,R)-3d and (aR,R)-3d.
Diastereomeric excess of (aR,R)-3d to (aS,R)-3d.
Diastereomeric excess of (aS,R)-4d to (aR,R)-4d.
A 1:1 mixture of (aS,S)-3e and (aR,S)-3e.
Diastereomeric excess of (aR,S)-3e to (aS,S)-3e.
Diastereomeric excess of (aS,S)-4e to (aR,S)-4e.
g
h
i
j
k

T. Sakuma et al. / Tetrahedron: Asymmetry 19 (2008) 1593–1599
1595
Me
Me
Me
5 mol% Pd(OAc)2
6 mol% 7
Me
Me
OH
O
O
Me
Me
O
O
O
Me
Me
O
O
O
OMe
OMe
OMe
OMe
10 equiv. MeOH
+
OMe
OMe
P
P
P
CH2Cl2, 20 °C, 24 h
Me
Me
Me
(R)-5a
(S)-6a
rac-5a
63.4% conv.
krel = 15.4
98.1% ee (34.4% yield)
56.6% ee (64.4% yield)
Me
Me
Me
5 mol% Pd(OAc)2
8 mol% 7
Me
Me
OH
O
O
Me
Me
O
O
O
Me
Me
O
O
O
iPr
iPr
iPr
+
O
O
O
10 equiv. MeOH
S
S
S
CH2Cl2, 20 °C, 24 h
Me
Me
Me
iPr
iPr
(S)-6b
83.0% ee (47.6% yield)
iPr
iPr
iPr
iPr
44.6% conv.
krel = 21.5
(R)-5b
rac-5b
66.9% ee (51.5% yield)
Scheme 3. Pd-catalyzed methanolysis of vinyl ethers 5.
sulfonyl substituent affects the selectivity. However, in both cases,
the fast-reacting isomer was determined based on the absolute
configuration of the binaphthyl group, therefore (aR,R)-3d and
(aR,S)-3e were obtained as an enantioenriched recovered substrate.
This result indicates that axial chirality plays more important role
in this reaction. In order to examine the applicability to 1,10-bi-2-
phenol derivatives, 5,50,6,60-tetramethyl-1,10-bi-2-phenol6 deriva-
tives having phosphoryl or sulfonyl groups were tested (Scheme
3). In both cases, good selectivities were observed. When dimeth-
oxyphosphoryl group was introduced, 5a, the krel value was found
to be 15.4; when a 2,4,6-triisopropylphenylsulfonyl group was
introduced, 5b, the krel value was 21.4. This result suggests that
this reaction is applicable to 1,10-bi-2-phenol derivatives.
4.2. Materials
CDCl3, C6D6 and acetone-d6 (Cambridge Isotope Laboratories
Inc.) were used as solvent for obtaining NMR spectra. (R,R)-N,N0-
Di[4-((20,30,40,50-tetraphenyl)phenyl)phenyl]-1,2-cyclohexanediam-
ine 7 and 5,50,6,60-tetramethyl-2,20-dihydroxy-1,10-biphenyl were
synthesized by a literature method.3a,6 Pd(OAc)2 (Wako Chemi-
cals), MeOH (Aldrich, anhydrous), and CH2Cl2 (Aldrich, anhydrous)
were used in the kinetic resolution. Benzene (Wako Chemicals,
spectrochemical analysis grade) and CHCl3 (Wako Chemicals,
spectrochemical analysis grade) were used for measurement of
optical rotation. All other chemical reagents used were of commer-
cial grade.
4.3. Synthesis of 20-vinyloxy-1,10-binaphthyl-2-yl phosphates 1
3. Conclusion
4.3.1. Dimethyl 20-vinyloxy-1,10-binaphthyl-2-yl phosphate 1a
A mixture of Cu(OAc)2 (545 mg, 3.0 mmol, 1.2 equiv) and pyr-
idine (2.02 mL, 25 mmol, 10.0 equiv) in CH2Cl2 (8 mL) was stirred
at rt for 5 min. To this were added 2a (1.25 g, 2.5 mmol, 1.0 equiv)
In conclusion, the kinetic resolution of the phosphoryl and sul-
fonyl esters of 1,10-bi-2-naphthol and 1,10-bi-2-phenol has been
achieved via Pd-catalyzed alcoholysis of their vinyl ethers using
chiral diamine 7 as ligand. The highest krel value reached 36.8 with
substrate 3c, and 99.0% ee of (R)-3c was obtained in 43% isolated
yield. The selectivity changed depending on the structure of the
substituent on phosphoryl and sulfonyl groups. Efforts are cur-
rently underway to expand this strategy to control the chirality
on the phosphoryl and sulfonyl groups.
and
vinylboronic
anhydride–pyridine
complex
(421 mg,
1.75 mmol, 0.7 equiv) and the mixture was stirred at rt under an
O2 atmosphere for 40 h. The reaction mixture was concentrated
under reduced pressure. The crude product was purified by
silica-gel chromatography to give a yellow solid (58%).; 1H NMR
(400 MHz, CDCl3)
d 3.12 (d, 3H, J = 11.2 Hz), 3.41 (d, 3H,
J = 11.2 Hz), 4.19 (dd, 1H, J = 1.8, 6.2 Hz), 4.45 (dd, 1H, J = 1.8,
13.8 Hz), 6.49 (dd, 1H, J = 6.2, 13.8 Hz), 7.23–7.45 (m, 7H), 7.73
(d, 1H, J = 8.0 Hz), 7.88 (d, 1H, J = 8.0 Hz), 7.92 (d, 1H, J = 8.2 Hz),
7.97 (d, 1H, J = 9.2 Hz), 7.98 (d, 1H, J = 8.8 Hz); 13C NMR
(150 MHz, C6D6) d 54.2 (d, J = 6.0 Hz), 54.5 (d, J = 5.6 Hz), 95.1,
119.0, 120.7, 121.9, 123.4 (d, J = 8.3 Hz), 125.5, 125.9, 126.7,
127.0, 127.5, 127.6, 128.9, 130.0, 130.6, 130.7, 131.2, 132.0,
134.8, 134.9, 147.8 (d, J = 6.4 Hz), 149.7, 153.1; 31P NMR
(243 MHz, C6D6) d ꢀ3.8; Elemental Anal. Calcd (%) for C24H21O5P:
C, 68.57; H, 5.03. Found: C, 68.47; H, 5.03.
4. Experimental
4.1. General
1H NMR (400 MHz) and 13C NMR (100 MHz) spectra were re-
corded on JEOL JMN AL 400 instruments. 13C NMR (151 MHz)
and 31P NMR (243 MHz) spectra were recorded on Bruker DRX-
600 instruments. Column chromatography was performed on sil-
ica-gel (Kanto Chemicals, Silica Gel 60N, spherical, neutral; particle
size 40–100 lm). The enantiomeric excess (ee) was determined by
HPLC using DAICEL CHIRALPAK AD-H (1a, 2a, 4a, and 6a), CHIRAL-
CEL OD-H (1b, 2b, 2d, 3a, 3b, and 4b), and CHIRALPAK IA (1c, 1d,
2c, 4c, and 6b). The ee of 1c, 3c, 5a, and 5b were determined by
the analysis of 2c, 4c, 6a, and 6b, which were obtained by the
hydrolysis with PdCl2(MeCN)2.3a The diastereomeric excesses (de)
of 3d, 3e, 4d, and 4e were determined by 1H NMR measurement.
Recycling preparative HPLC was performed with Japan Analytical
Industry LC-918 equipped with GPC columns JAIGEL-W252.
4.3.2. Diethyl 20-vinyloxy-1,10-binaphthyl-2-yl phosphate 1b
White solid (58%); 1H NMR (400 MHz, CDCl3) d 0.83 (t, 3H,
J = 7.2 Hz), 1.07 (t, 3H, J = 7.2 Hz), 3.40–3.55 (m, 2H), 3.62–3.85
(m, 2H), 4.18 (dd, 1H, J = 1.0, 6.0 Hz), 4.43 (dd, 1H, J = 1.0,
13.6 Hz), 6.51 (dd, 1H, J = 6.0, 13.6 Hz), 7.20–7.30 (m, 4H), 7.37–
7.45 (m, 3H), 7.78 (d, 1H, J = 8.8 Hz), 7.87 (d, 1H, J = 8.0 Hz), 7.91
(d, 1H, J = 8.0 Hz), 7.95–7.99 (m, 2H); 13C NMR (150 MHz, C6D6) d

1596
T. Sakuma et al. / Tetrahedron: Asymmetry 19 (2008) 1593–1599
16.1 (d, J = 6.6 Hz), 16.3 (d, J = 6.0 Hz), 64.3 (d, J = 6.6 Hz), 64.5 (d,
J = 6.6 Hz), 95.0, 119.1, 120.6, 122.1, 123.2 (d, J = 7.8 Hz), 125.5,
125.8, 126.7, 127.1, 127.5, 127.6, 128.8, 128.9, 130.5, 130.7,
131.3, 132.0, 134.8, 134.9, 148.0 (d, 1C, J = 5.0 Hz), 149.8, 153.2;
31P NMR (243 MHz, C6D6) d ꢀ6.0; Elemental Anal. Calcd (%) for
(m, 1H), 3.94 (dq, 2H, J = 7.2, 7.2 Hz), 6.23 (s, 1H), 7.02 (d, 1H,
J = 6.0 Hz), 7.22–7.26 (m, 2H), 7.30–7.35 (m, 2H), 7.39 (d, 1H,
J = 8.8 Hz), 7.47 (dd, 1H, J = 7.4, 8.8 Hz), 7.61 (d, 1H, J = 9.2 Hz),
7.84 (d, 1H, J = 8.0 Hz), 7.90 (d, 1H, J = 8.8 Hz), 7.94 (d, 1H,
J = 8.4 Hz), 8.03 (d, 1H, J = 8.8 Hz); 13C NMR (150 MHz, CDCl3) d
15.5 (d, J = 6.9 Hz), 15.9 (d, J = 6.1 Hz), 64.4 (d, J = 6.1 Hz), 64.8 (d,
J = 6.0 Hz), 116.0, 119.6, 119.9, 122.7 (d, J = 5.8 Hz), 123.8, 124.7,
125.9, 126.0, 126.6, 127.3, 127.9, 128.2, 129.2, 130.1, 130.8,
131.6, 133.8, 147.3 (d, J = 7.2 Hz), 152.3; 31P NMR (243 MHz,
C6D6) d ꢀ4.5; Elemental Anal. Calcd (%) for C24H23O5P: C, 68.24;
H, 5.49. Found: C, 68.29; H, 5.14.
C26H25O5P: C, 69.64; H, 5.62. Found: C, 69.41; H, 5.59.
4.3.3. 2-(5,5-Dimethyl-2-oxo-1,3,2-dioxaphosphorinan-2-
yloxy)-20-vinyloxy-1,10-binaphthalene 1c
White foam (77%); 1H NMR (400 MHz, CDCl3) d 0.19 (s, 3H), 1.08
(s, 3H), 2.94 (d, 1H, J = 10.8 Hz), 3.16 (d, 1H, J = 10.8 Hz), 3.24 (ddd,
1H, J = 2.8, 10.8, 23.2 Hz), 3.47 (ddd, 1H, J = 2.8, 10.8, 23.2 Hz), 4.20
(dd, 1H, J = 1.6, 6.0 Hz), 4.43 (dd, 1H, J = 1.6, 14.0 Hz), 6.49 (dd, 1H,
J = 6.0, 14.0 Hz), 7.23–7.34 (m, 4H), 7.38–7.46 (m, 2H), 7.46 (d, 1H,
J = 8.8 Hz), 7.88–8.02 (m, 5H); 13C NMR (150 MHz, C6D6) d 19.4,
21.6, 31.5, 77.8 (d, J = 7.1 Hz), 78.1 (d, J = 7.1 Hz), 95.5, 119.2,
120.5, 121.9 (d, 1C, J = 8.8 Hz), 122.2, 125.7, 125.8, 126.4, 126.9,
127.5, 127.9, 128.8, 129.1, 130.6, 131.2, 131.3, 131.9, 134.5,
134.7, 147.6 (d, J = 5.4 Hz), 149.4, 153.2; 31P NMR (243 MHz,
C6D6) d ꢀ14.3; Elemental Anal. Calcd (%) for C27H25O5P: C, 70.43;
H, 5.47. Found: C, 70.20; H, 5.53.
4.4.3. 2-(5,5-Dimethyl-2-oxo-1,3,2-dioxaphosphorinan-2-
yloxy)-20-hydroxy-1,10-binaphthyl 2c
White solid (94%); 1H NMR (400 MHz, CDCl3) d 0.26 (s, 3H), 1.08
(s, 3H), 3.06 (d, 1H, J = 10.8 Hz), 3.11 (d, 1H, J = 10.8 Hz), 3.33 (ddd,
1H, J = 3.2, 10.8, 23.2 Hz), 3.46 (ddd, 1H, J = 3.2, 10.8, 23.2 Hz), 5.14
(s, 1H), 7.11 (d, 1H, J = 8.8 Hz), 7.24–7.39 (m, 5H), 7.47–7.54 (m,
1H), 7.86 (d, 1H, J = 6.8 Hz), 7.93 (d, 1H, J = 9.2 Hz), 7.97 (d, 2H,
J = 8.4 Hz), 8.06 (d, 1H, J = 9.2 Hz); 13C NMR (150 MHz, CDCl3) d
19.4, 21.6, 31.5 (d, J = 5.8 Hz), 77.9 (d, J = 6.8 Hz), 78.0 (d,
J = 6.8 Hz), 114.2, 118.2, 119.8, 119.9 (d, 1C, J = 5.1 Hz), 123.7,
124.9, 125.6, 126.0, 127.0, 127.7, 128.1, 128.5, 129.0, 130.3,
131.3, 131.5, 133.4, 133.6, 147.1 (d, J = 6.0 Hz), 151.9; 31P NMR
4.3.4. 20-Vinyloxy-1,10-binaphthyl-2-yl dicyclo-
hexylphosphinate 1d
White foam (54%); 1H NMR (400 MHz, CDCl3) d 0.30–1.80 (m.
22H), 4.19 (dd, 1H, J = 1.8, 6.2 Hz), 4.46 (dd, 1H, J = 1.8, 13.8 Hz),
6.52 (dd, 1H, J = 6.2, 13.8 Hz), 7.20–7.31 (m, 4H), 7.38–7.40 (m,
2H), 7.43 (d, 1H, J = 8.8 Hz), 7.89 (d, 2H, J = 8.0 Hz), 7.90 (d, 1H,
J = 8.8 Hz), 7.96 (d, 1H, J = 8.8 Hz), 8.05 (d, 1H, J = 9.2 Hz); 13C
NMR (150 MHz, C6D6); d 25.2 (d, J = 3.0 Hz), 25.7 (d, J = 4.3. Hz),
25.9 (d, J = 3.0 Hz), 26.0, 26.2, 26.6 (d, J = 7.6 Hz), 26.6, 26.7 (d,
J = 7.6 Hz), 26.9 (d, J = 7.5 Hz), 27.0 (d, J = 62.2 Hz), 37.1 (d,
J = 87.3 Hz), 37.3 (d, 1C, J = 87.9 Hz), 94.8, 121.2 (d, J = 6.0 Hz),
121.5, 122.7, 125.2, 125.5, 126.4, 127.1, 127.3, 127.6, 128.8,
128.9, 129.1, 130.3, 130.6, 131.4, 131.5, 134.8, 135.0, 149.6, 150.7
(d, J = 9.0 Hz), 153.0; 31P NMR (243 MHz, C6D6) d 58.43; Elemental
Anal. Calcd (%) for C34H37O3P: C, 77.84; H, 7.11. Found: C, 77.42; H,
7.11.
(243 MHz, C6D6);
d
ꢀ13.8; Elemental Anal. Calcd (%) for
C25H23O5P: C, 69.12; H, 5.34. Found: C, 69.03; H, 5.36.
4.4.4. 20-Hydroxy-1,10-binaphthyl-2-yl dicyclohexylphosphinate
2d
White powder (80%); 1H NMR (400 MHz, CDCl3) d 0.78–1.25 (m,
11H), 1.25–1.64 (m, 11H), 6.00 (s,1H), 7.05 (d, 1H, J = 8.4 Hz), 7.22–
7.50 (m, 6H), 7.83 (d, 1H, J = 7.6 Hz), 7.85 (d, 1H, J = 6.4 Hz), 7.91 (d,
1H, J = 8.8 Hz), 7.92 (d, 1H, J = 8.4 Hz), 7.98 (d, 1H, J = 8.8 Hz); 13C
NMR (150 MHz, CDCl3)
d 24.9 (d, 1C, J = 3.8 Hz), 25.1 (d,
J = 2.5 Hz), 25.2, 25.4 (d, 1C, J = 2.8 Hz), 25.6, 25.7, 26.0 (2C), 26.1
(d, J = 5.6 Hz), 26.2 (d, J = 5.6 Hz), 36.5 (d, J = 86.5 Hz), 37.0 (d,
J = 85.2 Hz), 116.1, 119.1, 120.9, 121.0 (d, J = 4.5 Hz), 123.5, 124.8,
125.5, 125.6, 126.6, 127.4, 128.0, 128.2, 129.3, 130.0, 130.6,
131.0, 133.7, 133.8, 149.0 (d, J = 9.9 Hz), 152.2; 31P NMR
(243 MHz, C6D6) d 62.3; Elemental Anal. Calcd (%) for C32H35O3P:
C, 77.09; H, 7.08. Found: C, 76.71; H, 7.17.
4.4. Synthesis of 20-hydroxy-1,10-binaphthyl-2-yl phosphates 2
4.4.1. Dimethyl 20-hydroxy-1,10-binaphthyl-2-yl phosphate 2a
To a mixture of 1,10-bi-2-naphthol (2.86 g, 10.0 mmol, 1 equiv)
and dimethyl chlorophosphate (1.45 g, 10.0 mmol, 1 equiv) in
CH2Cl2 (20 mL) was added Et3N (2.09 mL, 15.0 mmol, 1.5 equiv)
at 0 °C and the mixture was stirred at rt for 20 h. The reaction
mixture was quenched by adding HCl (1 N, 40 mL) and extracted
with CH2Cl2. The resulting extracts were washed with brine, and
dried with Na2SO4, and concentrated under reduced pressure.
The crude product was purified by silica-gel column chromatogra-
phy to give white powder (2.17 g, 55%); 1H NMR (400 MHz, CDCl3)
d 3.15 (d, 3H, J = 11.4 Hz), 3.59 (d, 3H, J = 11.4 Hz), 6.08 (s, 1H),
7.03 (d, 1H, J = 9.2 Hz), 7.25–7.34 (m, 4H), 7.40 (d, 1H,
J = 8.8 Hz), 7.48 (dd, 1H, J = 7.0, 7.0 Hz), 7.59 (d, 1H, J = 8.8 Hz),
7.85 (d, 1H, J = 8.0 Hz), 7.91 (d, 1H, J = 8.8 Hz), 7.95 (d, 1H,
J = 8.4 Hz), 8.04 (d, 1H, J = 8.8 Hz); 13C NMR (150 MHz, C6D6) d
54.4 (d, J = 6.0 Hz), 54.9 (d, J = 6.0 Hz), 115.6, 119.5, 119.9, 122.7
(d, J = 5.6 Hz), 123.6, 124.7, 125.8, 126.1, 126.7, 127.6, 128.0,
128.2, 129.1, 130.2, 130.9, 131.7, 133.7, 133.8, 147.1 (d, 1C,
J = 7.2 Hz), 152.3; 31P NMR (243 MHz, C6D6) d ꢀ2.6; Elemental
Anal. Calcd (%) for C22H19O5P: C, 67.00; H, 4.86. Found: C, 67.31;
H, 5.26.
4.5. Synthesis of 20-vinyloxy-1,10-binaphthyl-2-yl sulfonates 3
Similar procedures to the synthesis of 1 were used.
4.5.1. 20-Vinyloxy-1,10-binaphthyl-2-yl methanesulfonate 3a
White foam (42%); 1H NMR (400 MHz, CDCl3) d 2.39 (s, 3H), 4.27
(dd, 1H, J = 2.0, 6.4 Hz), 4.51 (dd, 1H, J = 2.0, 14.0 Hz), 6.54 (dd, 1H,
J = 6.4, 14.0 Hz), 7.18 (d, 1H, J = 8.4 Hz), 7.20–7.55 (m, 6H), 7.70 (d,
1H, J = 9.2 Hz), 7.91 (d, 1H, J = 8.4 Hz), 7.96 (d, 1H, J = 8.0 Hz), 8.02
(d, 1H, J = 8.8 Hz), 8.03 (d, 1H, J = 9.2 Hz); 13C NMR (150 MHz, C6D6)
d 38.2, 95.9, 118.6, 120.9, 122.6, 125.5, 125.6, 126.6, 126.7, 127.1,
127.7, 128.0, 128.9, 129.0, 130.8, 131.0, 131.1, 132.9, 134.4,
134.6, 146.9, 149.2, 153.1; Elemental Anal. Calcd (%) for
C23H18O4S: C, 70.75; H, 4.65. Found: C, 70.58; H, 4.76.
4.5.2. 20-Vinyloxy-1,10-binaphthyl-2-yl 4-toluenesulfonate 3b
White foam (56%); 1H NMR (400 MHz, CDCl3) d 2.21 (s, 3H), 4.22
(dd, 1H, J = 2.0, 6.2 Hz), 4.44 (dd, 1H, J = 2.0, 13.8 Hz), 6.45 (dd, 1H,
J = 6.2, 13.8 Hz), 6.73 (d, 2H, J = 8.0 Hz), 6.83 (d, 1H, J = 8.8 Hz), 7.02
(d, 2H, J = 8.1 Hz), 7.09–7.14 (m, 2H), 7.22–7.26 (m, 1H), 7.30 (d,
1H, J = 8.8 Hz), 7.32–7.38 (m, 1H), 7.40–7.48 (m, 1H), 7.78 (d, 1H,
J = 8.8 Hz), 7.80 (d, 1H, J = 8.6 Hz), 7.88 (d, 1H, J = 8.8 Hz), 7.92 (d,
1H, J = 8.0 Hz), 7.99 (d, 1H, J = 8.8 Hz); 13C NMR (150 MHz, C6D6)
d 21.6, 95.7, 118.8, 120.7, 122.7, 125.0, 125.8, 126.5, 127.1, 127.4,
4.4.2. Diethyl 20-hydroxy-1,10-binaphthyl-2-yl phosphate 2b
White solid (82%); 1H NMR (400 MHz, CDCl3); d 0.86 (t, 3H,
J = 7.2 Hz), 1.20 (t, 3H, J = 7.2 Hz), 3.30–3.36 (m, 1H), 3.50–3.58

T. Sakuma et al. / Tetrahedron: Asymmetry 19 (2008) 1593–1599
1597
127.5, 128.1, 128.4, 128.6, 128.8, 129.0, 129.6, 130.69, 130.71,
4.6.2. 20-Hydroxy-1,10-binaphthyl-2-yl 4-toluenesulfonate
130.9, 132.9, 134.4, 134.5, 134.6, 144.2, 147.1, 149.6, 153.3; Ele-
mental Anal. Calcd (%) for C29H22O4S: C, 74.66; H, 4.75. Found: C,
74.52; H, 5.00.
4b
White powder (56%); 1H NMR (400 MHz, CDCl3) d 2.30 (s, 3H),
5.01 (s, 1H), 6.83 (d, 1H, J = 8.0 Hz), 6.91 (d, 2H, J = 8.0 Hz), 7.13
(ddd, 1H, J = 1.2, 6.8, 8.4 Hz), 7.18 (d, 2H, J = 8.4 Hz), 7.24–7.29
(m, 3H), 7.34 (ddd, 1H, J = 1.2, 6.8, 8.0 Hz), 7.52 (ddd, 1H, J = 1.2,
6.8, 8.4 Hz), 7.73 (d, 1H, J = 9.2 Hz), 7.78 (d, 1H, J = 8.0 Hz), 7.85
(d, 1H, J = 9.2 Hz), 7.97 (d, 1H, J = 8.4 Hz), 8.07 (d, 1H, J = 9.2 Hz);
13C NMR (150 MHz, CDCl3) d 21.7, 113.8, 118.1, 121.8, 123.4,
123.9, 124.7, 125.9, 126.3, 126.7, 126.8, 127.6, 127.7, 127.9,
128.4, 129.0, 129.4, 130.5, 131.1, 132.6, 132.8, 133.5 (2C), 144.8,
146.4, 151.7; Elemental Anal. Calcd (%) for C27H20O4S: C, 73.62;
H, 4.58. Found: C, 73.31; H, 4.93.
4.5.3. 20-Vinyloxy-1,10-binaphthyl-2-yl 2,4,6-triisopropyl-
benzenesulfonate 3c
White foam (71%); 1H NMR (400 MHz, CDCl3) d 1.01 (d, 6H,
J = 6.6 Hz), 1.03 (d, 6H, J = 6.6 Hz), 1.24 (d, 6H, J = 7.2 Hz), 2.88
(qq, 1H, J = 6.8, 6.8 Hz), 3.78 (qq, 2H, J = 6.8, 7.2 Hz), 4.17 (dd, 1H,
J = 1.8, 6.0 Hz), 4.44 (dd, 1H, J = 1.8, 13.8 Hz), 6.49 (dd, 1H, J = 6.0,
13.8 Hz), 7.07 (s, 2H), 7.16–7.46 (m, 8H), 7.85 (d, 1H, J = 8.8 Hz),
7.87–7.94 (m, 3H); 13C NMR (150 MHz, C6D6) d 24.0 (2C), 25.0
(2C), 25.2 (2C), 30.6 (2C), 34.9, 95.4, 118.7, 121.1, 121.7, 124.3,
125.3, 126.5, 127.22, 127.25, 127.4, 127.5, 127.6, 128.4, 128.6,
128.8, 128.9, 130.4, 131.0, 131.2, 132.8, 133.4, 134.89, 134.91,
147.2, 149.8, 151.5, 153.4, 154.2; Elemental Anal. Calcd (%) for
4.6.3. 20-Hydroxy-1,10-binaphthyl-2-yl 2,4,6-triisopropyl-
benzenesulfonate 4c
White powder (90%); 1H NMR (400 MHz, CDCl3) d 1.00 (d, 6H,
J = 6.8 Hz), 1.06 (d, 6H, J = 6.4 Hz), 1.24 (d, 6H, J = 7.2 Hz), 2.88
(qq, 1H, J = 6.8, 6.8 Hz), 3.81 (qq, 2H, J = 6.8, 6.8 Hz), 5.28 (s, 1H),
6.92 (d, 1H, J = 8.0 Hz), 7.07 (s, 2H), 7.18 (ddd, 1H, J = 1.2, 6.8,
8.0 Hz), 7.22–7.30 (m, 3H), 7.33 (ddd, 1H, J = 1.2, 6.8, 8.4 Hz),
7.38 (d, 1H, J = 9.2 Hz), 7.50 (ddd, 1H, J = 1.2, 6.8, 8.0 Hz), 7.80 (d,
1H, J = 8.0 Hz), 7.83 (d, 1H, J = 8.8 Hz), 7.94 (d, 1H, J = 8.0 Hz),
7.98 (d, 1H, J = 8.8 Hz); 13C NMR (150 MHz, CDCl3) d 23.6 (2C),
24.4 (2C), 24.5 (2C), 29.8 (2C), 34.3, 114.6, 118.6, 121.4, 123.5,
123.6, 124.5, 125.0, 125.9, 126.2, 126.4, 126.6, 126.7, 127.7,
128.0, 128.4, 129.2, 130.4, 130.7, 130.9, 132.4, 133.7, 133.8,
146.7, 150.5, 151.9, 154.0; Elemental Anal. Calcd (%) for
C37H38O4S: C, 76.78; H, 6.62. Found: C, 76.78; H, 6.64.
4.5.4. (aS,R)-20-Vinyloxy-1,10-binaphthyl-2-yl
camphorsulfonate (aS,R)-3d
White foam (56%); 1H NMR (400 MHz, CDCl3) d 0.38 (s, 3H), 0.68
(s, 3H), 1.20–1.39 (m, 2H), 1.77–1.88 (m, 2H), 1.91 (dd, 1H, J = 4.3,
4.3 Hz), 2.01–2.09 (m, 1H), 2.05 (d, 1H, J = 14.9 Hz), 2.20 (ddd, 1H,
J = 3.9, 4.1, 18,5 Hz), 3.09 (d, 1H, J = 14.9 Hz), 4.26 (dd, 1H, J = 1.8,
6.1 Hz), 4.51 (dd, 1H, J = 1.8, 13.9 Hz), 6.56 (dd, 1H, J = 6.1,
13.9 Hz), 7.19 (d, 1H, J = 6.0 Hz), 7.22–7.35 (m, 3H), 7.31 (ddd,
1H, J = 1.2, 6.8, 6.8 Hz), 7.46–7.53 (m, 2H), 7.71 (d, 1H, J = 9.0 Hz),
7.88 (d, 1H, J = 8.3 Hz), 7.95 (d, 1H, J = 8.0 Hz), 7.99 (d, 1H,
J = 9.0 Hz), 8.01 (d, 1H, J = 9.0 Hz); 13C NMR (150 MHz, C6D6) d
19.6, 20.1, 25.6, 27.1, 42.5, 43.3, 47.6, 49.5, 58.2, 96.0, 118.9,
120.8, 122.8, 125.5, 125.7, 126.6, 126.9, 127.1, 127.6, 127.9,
128.6, 128.9, 129.0, 130.7, 131.2, 131.3, 132.9, 134.5, 147.0,
149.4, 153.4, 212.3; Elemental Anal. Calcd (%) for C32H30O5S: C,
72.98; H, 5.74. Found: C, 72.88; H, 5.50.
C35H36O4S: C, 76.06; H, 6.56. Found: C, 75.85; H, 6.13.
4.6.4. (aS,R)-20-Hydroxy-1,10-binaphthyl-2-yl camphorsulfonate
(aS,R)-4d
White foam (72%); 1H NMR (400 MHz, CDCl3) d 0.51 (s, 3H),
0.67 (s, 3H), 1.24 (ddd, 1H, J = 3.6, 9.2, 12.8 Hz), 1.36 (ddd, 1H,
J = 4.4, 9.2, 13.6 Hz), 1.74–1.85 (m, 2H), 1.94 (dd, 1H,
J = 3.6, 3.6 Hz), 1.98–2.08 (m, 1H), 2.24 (ddd, 1H, J = 3.6, 3.6,
16.0 Hz), 2.32 (d, 1H, J = 15.0 Hz), 3.23 (d, 1H, J = 15.0 Hz), 5.18 (s,
1H), 7.03 (d, 1H, J = 7.6 Hz), 7.26–7.41 (m, 5H), 7.54 (ddd, 1H,
J = 1.4, 6.6, 8.3 Hz), 7.73 (d, 1H, J = 7.6 Hz), 7.84 (d, 1H, J = 7.6 Hz),
7.92 (d, 1H, J = 9.2 Hz), 7.98 (d, 1H, J = 8.0 Hz), 8.08 (d, 1H,
J = 9.2 Hz); 13C NMR (150 MHz, CDCl3) d 19.2, 19.3, 24.7, 26.8,
42.3, 42.7, 47.6, 48.7, 57.8, 114.3, 118.5, 122.2, 123.9, 124.0,
124.7, 126.1, 126.8, 127.1, 127.7, 128.2, 128.4, 129.2, 130.8,
131.1, 132.6, 133.5, 133.6, 146.3, 151.8, 214.0; Elemental Anal.
Calcd (%) for C30H28O5S: C, 71.98; H, 5.64. Found: C, 71.61;
H, 5.62.
4.5.5. (aS,S)-20-Vinyloxy-1,10-binaphthyl-2-yl camphorsulfonate
(aS,S)-3e
White foam (72%); 1H NMR (400 MHz, CDCl3) d 0.53 (s, 3H), 0.81
(s, 3H), 1.19–1.27 (m, 2H), 1.77–1.88 (m, 2H), 1.94 (dd, 1H, J = 4.6,
4.6 Hz), 1.96–2.04 (m, 1H), 2.21 (ddd, 1H, J = 3.9, 4.0, 18.8 Hz), 2.45
(d, 1H, J = 14.9 Hz), 2.91 (d, 1H, J = 14.9 Hz), 4.23 (dd, 1H, J = 1.7,
6.2 Hz), 4.48 (dd, 1H, J = 1.7, 13.9 Hz), 6.54 (dd, 1H, J = 6.2,
13.9 Hz), 7.19 (d, 1H, J = 8.5 Hz), 7.25–7.35 (m, 3H), 7.39 (ddd,
1H, J = 1.4, 6.6, 8.4 Hz), 7.46 (d, 1H, J = 8.8 Hz), 7.48 (ddd, 1H,
J = 1.4, 6.6, 8.4 Hz), 7.76 (d, 1H, J = 9.0 Hz), 7.89 (d, 1H, J = 8.0 Hz),
7.97 (d, 1H, J = 8.1 Hz), 8.00 (d, 1H, J = 8.7 Hz), 8.02 (d, 1H,
J = 9.0 Hz); 13C NMR (150 MHz, C6D6) d 19.6, 20.1, 25.6, 27.6,
42.5, 43.3, 47.7, 49.5, 58.2, 96.1, 118.8, 120.9, 122.5, 125.5, 125.6,
126.6, 126.9, 127.1, 127.6, 128.0, 128.8, 129.1, 130.8, 131.2,
131.3, 132.9, 134.5, 134.6, 147.1, 149.4, 153.3, 212.2; Elemental
Anal. Calcd (%) for C32H30O5S: C, 72.98; H, 5.74. Found: C, 72.70;
H, 6.04.
4.6.5. (aS,S)-20-Hydroxy-1,10-binaphthyl-2-yl camphorsulfonate
(aS,S)-4e
White foam (86%); 1H NMR (400 MHz, CDCl3) d 0.61 (s, 3H), 0.85
(s, 3H), 1.23–1.38 (m, 2H), 1.80–1.89 (m, 2H), 1.98 (dd, 1H, J = 4.4,
4.8 Hz), 1.98–2.07 (m, 1H), 2.25 (ddd, 1H, J = 3.6, 4.0, 18.8 Hz), 2.42
(d, 1H, J = 14.8 Hz), 3.11 (d, 1H, J = 14.8 Hz), 5.20 (s, 1H), 7.05 (d,
1H, J = 8.0 Hz), 7.26–7.38 (m, 5H), 7.54 (ddd, 1H, J = 1.2, 6.8,
8.4 Hz), 7.73 (d, 1H, J = 8.8 Hz), 7.85 (d, 1H, J = 7.6 Hz), 7.93 (d,
1H, J = 8.8 Hz), 7.99 (d, 1H, J = 8.4 Hz), 8.09 (d, 1H, J = 9.2 Hz); 13C
NMR (150 MHz, C6D6) d 19.4, 19.5, 24.8, 26.8, 42.3, 42.8, 47.8,
48.7, 57.7, 114.2, 118.3, 122.1, 123.8, 123.9, 124.6, 126.1, 126.9,
127.2, 127.8, 128.1, 128.5, 129.1, 130.8, 131.1, 132.6, 133.4,
133.5, 146.3, 151.8, 213.7; Elemental Anal. Calcd (%) for
4.6. Synthesis of 20-Hydroxy-1,10-binaphthyl-2-yl sulfonates 4
4.6.1. 20-Hydroxy-1,10-binaphthyl-2-yl methanesulfonate 4a
White powder (35%); 1H NMR (400 MHz, CDCl3) d 2.45 (s, 3H),
5.10 (s, 1H), 7.04 (d, 1H, J = 8.4 Hz), 7.28 (ddd, 1H, J = 1.4, 6.8,
8.4 Hz), 7.33–7.42 (m, 4H), 7.55 (ddd, 1H, J = 1.2, 6.4, 8.4 Hz),
7.70 (d, 1H, J = 9.2 Hz), 7.86 (d, 1H, J = 10.0 Hz), 7.95 (d, 1H,
J = 8.8 Hz), 7.99 (d, 1H, J = 8.4 Hz), 8.09 (d, 1H, J = 9.2 Hz); 13C
NMR (150 MHz, CDCl3) d 38.4, 113.7, 118.0, 121.9, 123.6, 123.9,
124.5, 126.0, 126.9, 127.2, 127.9, 128.0, 128.4, 128.9, 130.9,
131.2, 132.6, 133.3, 133.4, 146.3, 151.7; Elemental Anal. Calcd (%)
for C21H16O4S: C, 69.21; H, 4.43. Found: C, 69.01; H, 4.26.
C30H28O5S: C, 71.98; H, 5.64. Found: C, 71.81; H, 5.84.
4.7. Synthesis of 20-vinyloxy-(5,50,6,60-tetramethyl-1,10-
biphenyl)-2-yl phosphate and sulfonate 5
Similar procedures to the synthesis of 1 were used.

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T. Sakuma et al. / Tetrahedron: Asymmetry 19 (2008) 1593–1599
4.7.1. Dimethyl 20-vinyloxy-(5,50,6,60-tetramethyl-1,10-
biphenyl)-2-yl phosphate 5a
130.9, 135.4, 136.0, 138.8, 146.1, 150.3, 150.8, 153.6; Elemental
Anal. Calcd (%) for C31H40O4S: C, 73.19; H, 7.93. Found: C, 73.07;
H, 7.86.
Colorless oil (76%); 1H NMR (400 MHz, CDCl3) d 1.90 (s, 3H),
1.91 (s, 3H), 2.27 (s, 3H), 2.29 (s, 3H), 3.35 (d, 3H, J = 11.2 Hz),
3.53 (d, 3H, J = 11.2 Hz), 4.20 (dd, 1H, J = 1.6, 6.0 Hz), 4.49 (dd,
1H, J = 1.6, 14.0 Hz), 6.43 (dd, 1H, J = 6.0, 14.0 Hz), 6.81 (d, 1H,
J = 8.0 Hz), 7.10 (d, 1H, J = 8.0 Hz), 7.14 (d, 1H, J = 8.0 Hz), 7.16 (d,
1H, J = 8.0 Hz); 13C NMR (150 MHz, acetone-d6) d 16.7, 16.7, 19.9,
19.9, 54.4 (d, J = 6.8 Hz), 54.7 (d, J = 6.8 Hz), 94.2, 114.5, 117.1,
127.9, 129.5 (d, J = 7.2 Hz), 130.2, 130.4, 132.3, 133.7, 137.7,
137.9, 147.4 (d, J = 6.0 Hz), 150.0, 153.6; 31P NMR (243 MHz, ace-
tone-d6) d ꢀ3.5; Elemental Anal. calcd (%) for C20H25O5P: C,
63.82; H, 6.69. Found: C, 63.75; H, 6.68.
4.9. Kinetic resolution
4.9.1. Typical procedure (Table 1, entry 1): dimethyl 20-
(vinyloxy)-1,10-binaphthyl-2-yl phosphate 1a
A mixture of Pd(OAc)2 (2.2 mg, 10
N,N0-di[4-((20,30,40,50-tetraphenyl)phenyl)phenyl]-1,2-cyclohexane-
diamine (7) (12.3 mg, 12 mol, 6 mol %) in CH2Cl2 was stirred at rt
lmol, 5 mol %) and (R,R)-
l
under N2 atmosphere for 1 h. The mixture was concentrated under
reduced pressure and dried in vacuo. After 2 h, to this was added
1a (104.9 mg, 0.2 mmol, 1 equiv) and MeOH (81.0
lL, 2.0 mmol,
4.7.2. 20-Vinyloxy-(5,50,6,60-tetramethyl-1,10-biphenyl)-2-yl
2,4,6-triisopropylbenzenesulfonate 5b
10 equiv) in CH2Cl2 (125 L) and the mixture was stirred at 20 °C
l
under ambient atmosphere for 24 h. Silica-gel column chromatog-
White foam (86%); 1H NMR (400 MHz, CDCl3) d 1.13 (d, 6H,
J = 6.8 Hz), 1.14 (d, 6H, J = 6.8 Hz), 1.25 (d, 6H, J = 6.8 Hz), 1.91 (s,
3H), 1.93 (s, 3H), 2.26 (s, 3H), 2.28 (s, 3H), 2,90 (h, 1H, J = 6.8 Hz),
3.91 (h, 2H, J = 6.8 Hz), 4.15 (dd, 1H, J = 1.6, 6.0 Hz), 4.45 (dd, 1H,
J = 1.6, 14.0 Hz), 6.40 (dd, 1H, J = 6.0, 14.0 Hz), 6.67 (d, 1H,
J = 8.2 Hz), 6.75 (d, 1H, J = 8.2 Hz), 7.02 (d, 1H, J = 8.2 Hz), 7.09 (d,
1H, J = 8.2 Hz), 7.13 (s, 2H); 13C NMR (100 MHz, acetone-d6) d
16.8, 17.0, 20.1, 20.2, 23.7 (2C), 24.9 (2C), 24.8 (2C), 30.4 (2C),
34.8, 94.3, 114.7, 119.3, 124.8, 127.5 (2C), 130.2, 130.8, 132.2,
132.6, 136.1, 138.1, 138.6, 147.1, 150.3, 151.5, 153.8, 155.1; Ele-
mental Anal. Calcd (%) for C33H42O4S: C, 74.12; H, 7.92. Found: C,
74.05; H, 7.91.
raphy was carried out to give (R)-1a (42.2%, 94.8% ee) and (S)-2a
(56.0%, 73.0% ee); (R)-1a: ½a D23
¼ þ29:5 (c 1.00, C6H6), (S)-2a:
ꢁ
½
a 2D4
ꢁ
¼ ꢀ25:2 (c 1.00, CHCl3); HPLC analysis: Chiralpak AD-H,
hexane/2-propanol = 10:1, flow rate = 1.0 mL/min, retention time;
12.8 min (S)-1a, 18.6 min (R)-1a; Chiralpak AD-H, hexane/2-propa-
nol = 10:1, flow rate = 1.0 mL/min, retention time; 16.9 min (S)-2a,
23.8 min (R)-2a.
4.9.2. Diethyl 20-vinyloxy-1,10-binaphthyl-2-yl phosphate 1b
(Table 1, entry 2)
(R)-1b (36.7%, 98.5% ee): ½a D28
¼ þ39:6 (c 1.00, C6H6), (S)-2b
ꢁ
(62.1%, 62.7% ee): ½a D25
¼ ꢀ32:2 (c 1.00, CHCl3); HPLC analysis: Chi-
ꢁ
ralcel OD-H, hexane/2-propanol = 20:1, flow rate = 1.0 mL/min,
retention time; 10.3 min (R)-1b, 12.1 min (S)-1b; Chiralcel OD-H,
hexane/2-propanol = 20:1, flow rate = 1.0 mL/min, retention time;
13.7 min (R)-2b, 16.6 min (S)-2b.
4.8. Synthesis of 20-hydroxy-(5,50,6,60-tetramethyl-1,10-
biphenyl)-2-yl phosphate and sulfonate 6
4.8.1. Synthesis of dimethyl 20-hydroxy-(5,50,6,60-tetramethyl-
1,10-biphenyl)-2-yl phosphate 6a
4.9.3. 2-(5,5-Dimethyl-2-oxo-1,3,2-dioxaphosphorinan-2-
yloxy)-20-vinyloxy-1,10-binaphthalen 1c (Table 1, entry 3)
To
a
mixture of 5,50,6,60-tetramethyl-2,20-dihydroxy-1,10-
biphenyl (0.48 g, 2.0 mmol, 1 equiv) and dimethyl chlorophos-
phate (0.29 g, 2.0 mmol, 1 equiv) in CH2Cl2 (5 mL) was added
Et3N (0.25 mL, 2.0 mmol, 1 equiv) at 0 °C and the mixture was
stirred at rt for 20 h. The reaction mixture was quenched by add-
ing HCl (1 N, 10 mL) and extracted with CH2Cl2. The resulting ex-
tracts were washed with brine, and dried with Na2SO4, and
concentrated under reduced pressure. The crude product was
purified by silica-gel column chromatography to give colorless
oil (37%); 1H NMR (400 MHz, CDCl3) d 1.84 (s, 3H), 1.91 (s, 3H),
2.24 (s, 3H), 2.31 (s, 3H), 3.26 (d, 3H, J = 11.6 Hz), 3.66 (d, 3H,
J = 11.6 Hz), 5.50 (s, 1H), 6.83 (d, 1H, J = 8.0 Hz), 7.04 (d, 1H,
J = 8.0 Hz), 7.07 (d, 1H, J = 8.0 Hz), 7.19 (d, 1H, J = 8.0 Hz); 13C
(R)-1c (59.3%, 41.0% ee): ½a D28
¼ þ2:7 (c 1.00, C6H6), (S)-2c
ꢁ
(39.1%, 63.8% ee): ½a D25
¼ ꢀ8:5 (c 1.00, CHCl3); HPLC analysis: Chir-
ꢁ
alpak IA, hexane/2-propanol = 20:1, flow rate = 0.5 mL/min, reten-
tion time; 43.4 min (S)-2c, 67.5 min (R)-2c.
4.9.4. 20-Vinyloxy-1,10-binaphthyl-2-yl dicyclohexyl-
phosphinate 1d (Table 1, entry 4)
(R)-1d (65.4%, 27.4% ee): ½a D28
¼ ꢀ0:6 (c 1.00, C6H6), (S)-2d
ꢁ
(33.1%, 55.2% ee): ½a D25
¼ ꢀ26:9 (c 1.00, CHCl3). HPLC analysis:
ꢁ
Chiralpak IA, hexane/2-propanol = 20:1, flow rate = 0.5 mL/min,
retention time; 8.5 min (S)-1d, 11.9 min (R)-1d; Chiralcel OD-H,
hexane/2-propanol = 20:1, flow rate = 1.0 mL/min, retention time;
9.0 min (R)-2d, 10.7 min (S)-2d.
NMR (150 MHz, CDCl3)
d 16.3, 16.4, 19.8, 20.1, 54.1 (d,
J = 6.5 Hz), 54.7 (d, J = 6.5 Hz), 114.8, 117.3, 125.1, 128.6 (d,
J = 5.6 Hz), 128.8, 130.0, 130.4, 134.6, 135.9, 138.4, 146.6 (d, J =
6.9 Hz), 151.6; 31P NMR (243 MHz, CDCl3) d ꢀ2.2; Elemental
Anal. Calcd (%) for C18H23O5P: C, 61.71; H, 6.61. Found: C, 61.83;
H, 6.62.
4.9.5. 20-Vinyloxy-1,10-binaphthyl-2-yl methanesulfonate 3a
(Table 2, entry 1)
(R)-3a (51.7%, 40.7% ee): ½a D28
¼ ꢀ4:4 (c 1.00, C6H6), (S)-4a
ꢁ
(48.3%, 46.7% ee): ½a D24
¼ ꢀ13:7 (c 1.00, CHCl3); HPLC analysis: Chi-
ꢁ
ralcel OD-H, hexane/2-propanol = 20:1, flow rate = 1.0 mL/min,
retention time; 15.3 min (R)-3a, 17.6 min (S)-3a; Chiralpak AD-H,
hexane/2-propanol = 10:1, flow rate = 1.0 mL/min, retention time;
31.5 min (S)-4a, 35.7 min (R)-4a.
4.8.2. 20-Hydroxy-5,50,6,60-tetramethyl-1,10-biphenyl-2-yl 2,4,6-
triisopropylbenzenesulfonate 6b
White foam (75%); 1H NMR (400 MHz, CDCl3) d 1.13 (d, 6H,
J = 6.8 Hz), 1.16 (d, 6H, J = 6.8 Hz), 1.26 (d, 6H, J = 6.8 Hz), 1.78
(s, 3H), 1.90 (s, 3H), 2.20 (s, 3H), 2.30 (s, 3H), 2,91 (h, 1H,
J = 6.8 Hz), 3.90 (h, 2H, J = 6.8 Hz), 4.67 (s, 1H), 6.73 (d, 1H,
J = 8.2 Hz), 6.74 (d, 1H, J = 8.2 Hz), 7.02 (d, 1H, J = 8.2 Hz), 7.11
(d, 1H, J = 8.2 Hz), 7.14 (s, 2H); 13C NMR (100 MHz, CDCl3) d
16.6, 16.7, 20.0, 20.5, 23.7 (2C), 24.5 (2C), 24.7 (2C), 29.8 (2C),
34.3, 113.5, 119.1, 123.5 (2C), 123.7, 128.4, 130.1, 130.1, 130.2,
4.9.6. 20-Vinyloxy-1,10-binaphthyl-2-yl 4-toluenesulfonate 3b
(Table 2, entry 2)
(R)-3b (51.6%, 45.6% ee): ½a D28
¼ þ4:26 (c 1.00, C6H6), (S)-4b
ꢁ
(47.8%, 51.4% ee): ½a D25
¼ ꢀ25:9 (c 1.00, CHCl3); HPLC analysis: Chi-
ꢁ
ralcel OD-H, hexane/2-propanol = 20/1, flow rate = 1.0 mL/min,
retention time; 10.7 min (S)-3b, 12.1 min (R)-3b; Chiralcel OD-H,

T. Sakuma et al. / Tetrahedron: Asymmetry 19 (2008) 1593–1599
1599
hexane/2-propanol = 20:1, flow rate = 1.0 mL/min, retention time;
24.7 min (R)-4b, 32.1 min (S)-4b.
4.10.2. Determination of the relative and absolute
configuration of 3d, 3e, 4d, and 4e
Determination of the relative configuration was performed by
1H NMR measurement of authentic samples: (aS,R)-3d, (aS,S)-3e,
(aS,R)-4d, and (aS,S)-4e, which were derived from enantiomerically
4.9.7. 20-Vinyloxy-1,10-binaphthyl-2-yl 2,4,6-triisopropyl-
benzenesulfonate 3c (Table 2, entry 3)
(R)-3c (44.3%, 99.0% ee): ½a D23
ꢁ
¼ þ28:0 (c 1.00, C6H6), (S)-4c
pure (S)-1,10-bi-2-naphthol. (aS,R)-3d: ½a 1D9
¼ þ5:4 (c 1.00, C6H6);
ꢁ
(55.5%, 75.7% ee): ½a D23
ꢁ
¼ ꢀ54:6 (c 1.00, CHCl3); HPLC analysis:
(aS,S)-3e: ½a 1D9
ꢁ
¼ þ19:0 (c 1.00, C6H6); (aS,R)-4d: ½a D19
¼ ꢀ38:2 (c
ꢁ
Chiralpak IA, hexane/2-propanol = 1000:1, flow rate = 0.5 mL/min,
1.00, CHCl3); (aS,S)-4e: ½a D19
¼ ꢀ66:3 (c 1.00, CHCl3).
ꢁ
retention time; 15.3 min (R)-4c, 18.7 min (S)-4c.
4.10.3. Determination of the absolute configurations of 5a, 5b,
6a and 6b
4.9.8. (aS,R)-20-Vinyloxy-1,10-binaphthyl-2-yl camphor-
sulfonate 3d (Table 2, entry 4)
Determination of the absolute configuration was performed by
the comparison of retention time of HPLC (6aand6b) with that of
optically active samples derived from (R)-5,50,6,60-tetramethyl-
2,20-dihydroxy-1,10-biphenyl (86.7% ee), which were synthesized
by hydrolysis of (R)-5,50,6,60-tetramethyl-2-vinyloxy-20-pivaloyl-
oxy-1,10-biphenyl (86.7% ee).3a,b
(aR,R)-3d (49.6%, 54.8% de to (aS,R)-3d): ½a D23
¼ ꢀ11:8 (c 1.00,
ꢁ
C6H6), (aS,R)-4d (49.7%, 59.5% de to (aR,R)-4d): ½a D23
¼ ꢀ22:1 (c
ꢁ
1.00, CHCl3).
4.9.9. (aS,S)-20-Vinyloxy-1,10-binaphthyl-2-yl camphorsulfonate
3e (Table 2, entry 5)
(aR,S)-3e (41.8%, 95.0% de to (aS,S)-3e): ½a D23
ꢁ
¼ ꢀ2:9 (c 1.00,
Acknowledgments
C6H6), (aS,S)-4e (57.8%, 58.9% de to (aR,S)-4e): ½a D23
¼ ꢀ36:0 (c
ꢁ
1.00, CHCl3).
The present work is supported by Grant-in-Aid for Global-COE
program, ‘Science for Future Molecular Systems’ from the Ministry
of Education, Culture, Science, Sports and Technology of Japan. We
appreciate Professor Katsuki and his research group for permitting
the use of NMR equipment.
4.9.10. Dimethyl 20-vinyloxy-(5,50,6,60-tetramethyl-1,10-
biphenyl)-2-yl phosphate 5a (Scheme 3)
(R)-5a (34.4%, 98.1% ee): ½a D24
¼ þ21:6 (c 2.30, C6H6), (S)-6a
ꢁ
(64.4%, 56.6% ee): ½a D25
¼ ꢀ18:4 (c 1.00, CHCl3); HPLC analysis:
ꢁ
Chiralpak AD-H, hexane/2-propanol = 20:1, flow rate = 1.0 mL/
References
min, retention time; 10.8 min (R)-6a, 12.1 min (S)-6a.
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5. (a) Tsuji, Y.; Fujihara, T. Inorg. Chem. 2007, 46, 1895–1902; (b) Iwasawa, T.;
Komano, T.; Tajima, A.; Tokunaga, M.; Obora, Y.; Fujihara, T.; Tsuji, Y.
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4.9.11. 20-Vinyloxy-(5,50,6,60-tetramethyl-1,10-biphenyl)-2-yl
2,4,6-triisopropylbenzenesulfonate 5b (Scheme 3)
(R)-5b (51.5%, 66.9% ee): ½a D24
¼ ꢀ28:7 (c 1.00, C6H6), (S)-6b
ꢁ
(47.6%, 83.0% ee): ½a D24
¼ ꢀ48:3 (c 1.00, CHCl3); HPLC analysis:
ꢁ
Chiralpak IA, hexane/2-propanol = 1000:1, flow rate = 0.5 mL/min,
retention time; 16.2 min (R)-6b, 19.6 min (S)-6b.
4.10. Determination of the absolute configuration
4.10.1. Determination of the absolute configurations of 1d, 2a,
2b, 2c, 2d, 4a, 4b, and 4c
Determination of absolute configuration was performed by the
comparison of retention time of HPLC (1d, 2a, 2b, 2c, 2d, 4a, 4b,
and 4c) and specific rotation (1d, 2a, 2c, 4b, and 4c) with those
of authentic samples derived from enantiomerically pure (S)-1,10-
bi-2-naphthol. Specific rotation values were as follows: (S)-1d:
½
a 2D3
ꢁ
¼ þ4:10 (c 1.00, C6H6), (S)-2a: ½a D24
¼ ꢀ42:0 (c 1.00, CHCl3),
ꢁ
(S)-2c: ½a 2D5
ꢁ
¼ ꢀ13:6 (c 1.00, CHCl3), (S)-4b: ½a 23
¼ ꢀ39:4 (c 1.00,
ꢁ
D
CHCl3), (S)-4c: ½a D23
¼ ꢀ80:7 (c 1.00, CHCl3). Absolute configura-
ꢁ
tions of 1a, 1b, 1c, 3a, 3b, and 3c were estimated based on the prin-
ciple of kinetic resolution.
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