Convenient method for the synthesis of 6,6′-diacyl-1,1′-bi-2- naphthyl ethers

Article abstract of DOI:10.1055/s-2007-990880

Acylation of 1,1′-bi-2-naphthol (BINOL) ethers using Lewis acids aluminum(III) chloride and titanium(IV) chloride gave the corresponding 6,6′-diacyl derivatives in good yields. Georg Thieme Verlag Stuttgart.

Full text of DOI:10.1055/s-2007-990880

PAPER
3821
Convenient Method for the Synthesis of 6,6¢-Diacyl-1,1¢-bi-2-naphthyl Ethers
S
M
ynthesis of 6,6
¢
-Diacy
a
l-1,1
¢
-bi-2-
r
naphthy
i
l
Ethe
r
a
ppan Periasamy,* Miriyala Nagaraju, Neela Kishorebabu
School of Chemistry, University of Hyderabad, Hyderabad 500 046, India
Fax +91(40)23012460; E-mail: mpsc@uohyd.ernet.in
Received 27 June 2007
developed for the preparation of chiral 1,1¢-bi-2-naphthol
derived amino ethers through the opening of aziridinium
ion intermediates derived from trans (±)-2-pyrrolidin-1-
Abstract: Acylation of 1,1¢-bi-2-naphthol (BINOL) ethers using
Lewis acids aluminum(III) chloride and titanium(IV) chloride gave
the corresponding 6,6¢-diacyl derivatives in good yields.
9
ylcyclohexanol. During these investigations, we became
Key words: chiral 1,1¢-bi-2-naphthol, acylation, aluminum(III)
chloride, titanium(IV) chloride, acyl-bi-2-naphthyl ether
interested in the synthesis of 6,6¢-diacyl-1,1¢-binaphthyl
ether derivatives for further synthetic exploitation. The
,6¢-positions of 1,1¢-bi-2-naphthol can be selectively
functionalized. The most common precursor for the syn-
thesis of 6,6¢-disubstituted BINOL ligands described in
the literature is 6,6¢-dibromo-1,1¢-bi-2-naphthol. This de-
rivative is prepared by electrophilic aromatic bromination
6
Optically active 1,1¢-bi-2-naphthol (BINOL, 1) (Figure 1)
derivatives have been used both catalytically and stoichi-
ometrically in various asymmetric transformations.1
There has been immense interest in modified BINOL
ligands as the outcome of a given asymmetric transforma-
tion depends on both the steric and the electronic proper-
ties of the chiral ligand. Several 6,6¢-disubstituted 1,1¢-bi-
1
0
of BINOL. A variety of 6,6¢-disubstituted BINOLs were
1
1
prepared using 6,6¢-dibromo-1,1¢-bi-2-naphthol. How-
ever, there is no direct method available to obtain 6,6¢-di-
1
2
acyl-1,1¢-bi-2-naphthyl ether derivatives. We wish to
report here a convenient method for the synthesis of these
derivatives.
2
-naphthol derivatives have been found to be useful in
2
,3
asymmetric transformations. For example, the La–Li
complex of 6,6¢-dimethyl-1,1¢-bi-2-naphthol was used as
2
Initially, we examined the acylation of 1,1¢-bi-2-naphthol
an asymmetric catalyst for the nitro-aldol reaction and a
(
1) using various Lewis acids like anhydrous alumi-
chiral 6,6¢-dibromo-1,1¢-bi-2-naphthol–zirconium cata-
lyst used for enantioselective Mannich-type reaction.3
num(III) chloride, titanium(IV) chloride, or zirconi-
um(IV) chloride. For example, we have observed that the
reaction of 1,1¢-bi-2-naphthol (1) with acetyl chloride in
the presence of aluminum(III) chloride in nitrobenzene at
5
4
9
6
7
3
2
2
5 °C for eight hours gave the diester derivative 2a in 95%
10
1
OH
OH
8
yield (Scheme 1) instead of the desired diketone 3
(
Figure 2).
1
O
O
Figure 1
O
O
Me
Me
OH
OH
AcCl, anhyd AlCl3
PhNO2,
Previously, a simple method for the resolution of racemic
,1¢-bi-2-naphthol using boric acid and (+)-(R)-a-methyl-
benzylamine or (S)-proline was reported from this labora-
25 °C, 8 h
1
1
2a
5%
4
tory. Racemic BINOL was also resolved with an
9
optically active aminonaphthol and boric acid in acetoni-
5
Scheme 1
trile solvent. Chiral 1,1¢-bi-2-naphthol in alliance with
boric acid was utilized for the purification of diastereo-
6
meric amino alcohol derivatives and for the resolution of
O
(
±)-trans-2-pyrrolidinylcyclohexanol and its methyl ether
Me
7
O
derivative. Intramolecular oxidative coupling of phenyl-
acetic acid esters of enantiomerically pure 1,1¢-bi-2-naph-
thol was achieved by preparing the corresponding
titanium ester enolates with the titanium(IV) chloride/tri-
OH
OH
O
Me
OH
Me
O
8
ethylamine reagent system. Convenient methods were
2
b
3
SYNTHESIS 2007, No. 24, pp 3821–3826
x
x.
x
x
.
2
0
0
7
Figure 2
Advanced online publication: 13.11.2007
DOI: 10.1055/s-2007-990880; Art ID: Z15607SS
Georg Thieme Verlag Stuttgart · New York
©

3
822
M. Periasamy et al.
PAPER
O
O
R2
R2
R2
2
R1
R1
R1
R1
O
O
O
O
O
O
i
+
R1
R1
O
(R)-4
(R)-5
(R)-6
1
Scheme 2 Reagents and conditions (R = pentyl): (i) R OCl, CH Cl , TiCl , r.t., 24 h.
2
2
4
We have made efforts to carry out the Fries rearrangement The acylation of methyl-protected 1,1¢-bi-2-naphthol (R)-
of the diester 2a in a separate step using the Lewis acid 7 failed when titanium(IV) chloride was used as the Lewis
aluminum(III) chloride in carbon disulfide at 50 °C to ob- acid. However, (+)-(R)-2,2¢-dimethoxy-1,1¢-binaphthyl
tain 3; these attempts were not successful. Also, acylation [(R)-7] was successfully acylated with acetyl chloride in
of diester 2a did not proceed further in the presence of alu- the presence of anhydrous aluminum(III) chloride in ni-
minum(III) chloride in nitrobenzene at 25 °C. In this run, trobenzene at 0 °C to give the diketone in 84% yield.
only the starting material 2a was obtained along with the
monoester 2b in 35% yield.
To avoid difficulties in removing nitrobenzene from the
reaction mixture, we examined the reaction in dichlo-
Fortunately, protection of the hydroxy groups of BINOL romethane solvent. When the reaction was carried out us-
1
gave good results in the acylations. When the reaction ing four equivalents of acetyl chloride and (R)-7 in
was carried out using the pentyl-protected 1,1¢-bi-2-naph- dichloromethane at –45 °C, the desired diketone (R)-8a
thol (R)-4, the mono- (R)-6 and diacylated (R)-5 deriva- was obtained in 87% yield (Scheme 3). The reaction was
tives were obtained in acceptable yields (Scheme 2). The also carried out using various acid chlorides and the cor-
acylation reaction was carried out using four equivalents responding diketones were obtained in good yields. The
of acetyl chloride and pentyl-protected optically active results are summarized in Table 2.
(
+)-(R)-1,1¢-bi-2-naphthol (R)-4 in the presence of titani-
Table 2 Synthesis of (R)-8 Using Various Acid Chloridesa
um(IV) chloride in dichloromethane at 25 °C for 24 hours.
Both the 6,6¢-diacyl-1,1¢-bi-2-naphthol derived ether (R)-
b
Entry
R
Temp. Time (h) (R)-8
Yield (%)
5
a and the 6-acyl-1,1¢-bi-2-naphthol derived ether (R)-6a
were obtained in 64% and 22% yields, respectively. The
1
2
3
4
5
6
7
8
Me
Et
–45 °C
0 °C
r.t.
3
3
5
5
8
5
5
8
8
(R)-8a
(R)-8b
(R)-8c
(R)-8d
(R)-8e
(R)-8f
(R)-8g
(R)-8h
(R)-8i
87
78
75
72
68
75
72
70
71
results of the acylation of 1,1¢-bi-2-naphthol derived ether
(
R)-4 are summarized in Table 1.
i-Pr
Table 1 Acylation of (R)-4 Using Titanium(IV) Chloridea,b
CH Cl
r.t.
2
Entry R2
(R)-5
Yield (%) (R)-6
c
Yield (%)
c
4-O NC H CH
2
r.t.
2
6
4
1
2
3
4
Me
(R)-5a
(R)-5b
(R)-5c
(R)-5d
64
66
62
66
(R)-6a
(R)-6b
(R)-6c
(R)-6d
22
20
21
16
Ph
4-MeC H
r.t.
Et
r.t.
6
4
Ph
Bn
4-MeOC H
r.t.
6
4
9
1-naphthyl
r.t.
a
b
c
1
R = pentyl.
The products were identified by IR, H NMR, 13C NMR, MS data.
All reactions were carried out using: (R)-4 (2.5 mmol), R COCl (10
1
a
All reactions were carried out using: (R)-7 (5 mmol), anhyd AlCl
3
2
(20 mmol), RCOCl (20 mmol), CH Cl (30 mL).
2 2
1
b
The products were identified by IR, H NMR, 13C NMR, and MS
mmol), TiCl (2.2 mL of TiCl –CH Cl , 1:1 soln) (10 mmol); isolated
4
4
2
2
yields are based on (R)-4.
data; yields are for isolated products.
O
R
RCOCl, anhyd AlCl3,
CH2Cl2, –45 °C to r.t.
Me
Me
Me
Me
O
O
O
O
3
–8 h
R
(
R)-7
O
(R)-8
Scheme 3
Synthesis 2007, No. 24, 3821–3826 © Thieme Stuttgart · New York

PAPER
Synthesis of 6,6¢-Diacyl-1,1¢-bi-2-naphthyl Ethers
3823
The acylation of optically active, as well as racemic, 1,1¢- and brine and dried (anhyd Na
SO ). The solvent was evaporated to
4
give (R)-7 (5.3 g, 97%) as a white powder; mp 204–206 °C.
2
bi-2-naphthyl ethers using anhydrous aluminum(III) chlo-
ride gave the corresponding 6,6¢-diacyl products (R)-8a–i [a]D +57.54 (c 1, CHCl3).
2
5
in good yields. Both mono- and diacyl products were
formed when the acylation was carried out using titani-
um(IV) chloride. The 6,6¢-dibromo-1,1¢-bi-2-naphthol
ethers have been used in the synthesis of various mono-
IR (KBr): 2955, 2837, 1618, 1249, 1147, 1089 cm–1.
1
H NMR (400 MHz, CDCl ): d = 7.97 (d, J = 9.2 Hz, 2 H), 7.85 (d,
3
J = 8.2 Hz, 2 H), 7.46 (d, J = 9.2 Hz, 2 H), 7.33–7.19 (m, 4 H), 7.10
(
d, J = 8.2 Hz, 2 H), 3.76 (s, 6 H).
1
3
meric and polymeric derivatives. The methods de-
scribed here for the synthesis of acyl derivatives of
BINOL ethers have good potential for further synthetic
exploitation as these derivatives can serve as precursors
for the preparation of various substituted 1,1¢-bi-2-naph-
13
C NMR (400 MHz, CDCl ): d = 155.0, 134.0, 131.1, 129.8, 129.4,
3
1
28.2, 119.6, 114.2, 56.9.
LCMS: m/z = 315 (M + 1).
6
,6¢-Diacyl-2,2¢-bis(pentyloxy)-1,1¢-binaphthyls (R)-5; General
1
3,14
thyl derivatives.
Procedure
The acid chloride (10 mmol) and TiCl (1.1 mL, 10 mmol) were tak-
4
en in CH Cl (30 mL) under N . The mixture was stirred for 20 min
at 25 °C. To this mixture was added (R)-4 (2.5 mmol) and it was
2
2
2
Melting points were determined using a Superfit capillary point ap-
paratus and are uncorrected. IR (KBr) spectra were recorded on Jas-
co FT-IR spectrophotometer model 5300 and IR (neat) spectra were
recorded on Shimadzu FT-IR spectrophotometer model 8300 with
polystyrene as reference. H NMR (400 MHz) and C NMR (100
MHz) were recorded on a Bruker Avance 400 spectrometer with
stirred at 25 °C for 24 h. The reaction was quenched with H O, the
2
organic layer was separated, and the aqueous layer was extracted
with CH Cl (2 × 25 mL). The combined organic layers were
2
2
1
13
washed with brine (10 mL) and dried (anhyd Na SO ). The solvent
2 4
was removed and the residue was column chromatographed (silica
gel, EtOAc–hexane, 4:96) to give compounds (R)-5 as highly vis-
cous materials.
CDCl as solvent and TMS as reference. Elemental analyses were
3
carried out using a Perkin-Elmer elemental analyzer model 240C
and Thermo Finnigan analyzer series Flash EA 1112. Mass spectral
analyses were carried out on VG 7070H mass spectrometer using EI
technique at 70 eV. Optical rotations were measured in JASCO
DIP-370 Digital polarimeter (readability = ± 0.001°). Column chro-
matography was carried out using Acme silica gel (100–200 mesh).
CH Cl was dried by distillation over CaH . All the acid chlorides,
6,6¢-Diacetyl-2,2¢-bis(pentyloxy)-1,1¢-binaphthyl [(R)-5a]
Yield: 64%.
25
[
a]D –14.3 (c 1.00, CHCl3).
–
1
IR (neat): 3063, 2953, 1682, 1618, 1273, 1051 cm .
2
2
2
anhydrous aluminium(III) chloride and titanium(IV) chloride were
supplied by E Merck (India).
1
H NMR (400 MHz, CDCl ): d = 8.50 (s, 2 H), 8.07 (d, J = 8.8 Hz,
3
2
H), 7.76 (d, J = 8.8 Hz, 2 H), 7.46 (d, J = 8.8 Hz, 2 H), 7.16 (d,
J = 8.8 Hz, 2 H), 4.01–3.92 (m, 4 H), 2.66 (s, 6 H), 1.43–1.40 (t,
J = 7.2 Hz, 4 H), 1.04 –0.88 (m, 8 H), 0.63 (t, J = 6.8 Hz, 6 H).
2
,2¢-Bis(pentyloxy)-1,1¢-binaphthyl [(R)-4]
A suspension of (+)-(R)-1,1¢-bi-2-naphthol (5.0 g, 17.4 mmol) in
MeCN (50 mL) stirred under N was added K CO (6.0 g, 43.5
mmol) and C H Br (6.5 mL, 52.2 mmol), and the mixture was re-
fluxed at 85 °C for 24 h. The solvent was removed under vacuum
and the mixture was diluted with CH Cl (30 mL). The organic layer
1
3
C NMR (400 MHz, CDCl ): d = 197.9, 156.7, 136.5, 132.3, 131.3,
3
2
2
3
1
2
30.6, 127.9, 125.5, 124.3, 119.6, 115.6, 69.2, 29.7, 28.9, 27.8,
6.6, 22.1, 13.0.
5
11
LCMS: m/z = 511 (M + 1).
2
2
was further washed with H O and brine and dried (anhyd Na SO ).
2
2
4
After removal of the solvent, the residue was purified by column
chromatography (silica gel, hexane–EtOAc, 97:3) to give (R)-4
6-Acetyl-2,2¢-bis(pentyloxy)-1,1¢-binaphthyl [(R)-6a]
Yield: 22%.
(
7.03 g, 95%) as a viscous liquid.
25
[
a]D +32.8 (c 1.00, CHCl3).
25
[
a]D +53.7 (c 0.6, CHCl3).
IR (neat): 3055, 2934, 2872, 1680, 1618, 1051 cm–1.
–
1
IR (neat): 2930, 2868, 1622, 1593, 1145, 1086 cm .
1
H NMR (400 MHz, CDCl ): d = 8.50–7.11 (m, 11 H), 4.01–3.91
(m, 4 H), 2.67 (s, 3 H), 1.28–1.22 (m, 4 H), 1.04–0.98 (m, 4 H),
0.94–0.88 (m, 4 H), 0.63 (t, J = 6.8 Hz, 6 H).
3
1
H NMR (400 MHz, CDCl ): d = 7.96 (d, J = 8.8 Hz, 2 H), 7.88 (d,
3
J = 8.1 Hz, 2 H), 7.44 (d, J = 8.9 Hz, 2 H), 7.33 (d, J = 8.1 Hz, 2 H),
7
0
.22–7.19 (m, 4 H), 3.98–3.94 (m, 4 H), 1.41–1.39 (m, 4 H), 1.07–
.95 (m, 8 H), 0.78 (t, J = 7.2 Hz, 6 H).
13
C NMR (400 MHz, CDCl ): d = 198.0, 156.9, 154.6, 145.9, 136.8,
3
1
34.1, 132.4, 131.1, 130.53, 129.4, 129.3, 128.9, 128.0, 127.0,
1
3
C NMR (400 MHz, CDCl ): d = 156.7, 136.5, 132.3, 131.3, 130.6,
126.3, 126.0, 125.2, 124.2, 123.5, 120.7, 119.9, 117.9, 117.2, 116.0,
115.6, 69.7, 29.1, 28.0, 26.6, 22.2, 13.9.
3
1
27.9, 125.5, 124.3, 119.6, 115.6, 69.2, 29.7, 28.9, 27.8, 22.1, 13.0.
LCMS: m/z = 427 (M + 1).
LCMS: m/z = 469 (M + 1).
2
,2¢-Dimethoxy-1,1¢-binaphthyl [(R)-7]
2,2¢-Bis(pentyloxy)-6,6¢-dipropanoyl-1,1¢-binaphthyl [(R)-5b]
A suspension of (+)-(R)-1,1¢-bi-2-naphthol (5.0 g, 17.4 mmol) was
heated at 40 °C in acetone (150 mL) to give a homogeneous soln.
To this soln stirred under N was added K CO (8.0 g, 58 mmol) and
MeI (5.3 mL, 84 mmol). The mixture was refluxed for 24 h. An ad-
ditional portion of MeI (1.7 mL, 28 mmol) was added, and the mix-
ture was further refluxed for an additional 12 h. The solvent was
removed and H O (150 mL) was added. The mixture was allowed
to stir for 8 h and filtered and the solid was dissolved in CH Cl (50
mL). The aqueous layer was extracted with CH Cl (2 × 25 mL).
The combined CH Cl layers were successively washed with H O
Yield: 66%.
25
[
a]D –18.2 (c 1.00, CHCl3).
2
2
3
–
1
IR (neat): 3063, 2932, 2868, 1684, 1618, 1041 cm .
1
H NMR (400 MHz, CDCl ): d = 8.51 (s, 2 H), 8.07 (d, J = 8.8 Hz,
3
2
H), 7.77 (d, J = 8.8 Hz, 2 H), 7.46 (d, J = 8.8 Hz, 2 H), 7.15(d,
2
J = 8.8 Hz, 2 H), 4.01–3.92 (m, 4 H), 3.09 (q, J = 7.2 Hz, 4 H),
1.43–1.40 (m, 4 H), 1.26 (t, J = 6.8 Hz, 6 H), 1.03–0.88 (m, 8 H),
0.63 (t, J = 6.8 Hz, 6 H).
2
2
2
2
2
2
2
Synthesis 2007, No. 24, 3821–3826 © Thieme Stuttgart · New York

3
824
M. Periasamy et al.
PAPER
1
3
C NMR (400 MHz, CDCl ): d = 200.6, 156.6, 136.4, 132.0, 131.3,
2,2¢-Bis(pentyloxy)-6-(phenylacetyl)-1,1¢-binaphthyl [(R)-6d]
3
1
2
29.9, 128.0, 125.5, 124.41, 119.4, 115.6, 69.3, 31.7, 28.9, 27.8,
2.1, 13.9, 8.5.
Yield: 16%.
25
[
a]D +23.8 (c 1.00, CHCl3).
LCMS: m/z = 539 (M + 1).
IR (neat): 3059, 2932, 1672, 1618, 1269, 1051 cm–1.
1
H NMR (400 MHz, CDCl ): d = 8.22–8.66 (m, 16 H), 4.40 (s, 2 H),
.08–3.94 (m, 4 H), 1.47 (t, J = 7.2 Hz, 4 H), 0.96–1.09 (m, 8 H),
.71 (t, J = 7.2 Hz, 6 H).
2
,2¢-Bis(pentyloxy)-6-propanoyl-1,1¢-binaphthyl [(R)-6b]
3
4
0
Yield: 20%.
25
[
a]D +41.2 (c 1.00, CHCl3).
1
3
C NMR (400 MHz, CDCl ): d = 197.4, 157.0, 154.6, 144.5, 136.8,
–
1
3
IR (neat): 3055, 2934, 2872, 1680, 1618, 1051 cm .
1
35.2, 134.2, 131.8, 131.2, 130.9, 129.3, 129.3, 128.7, 128.6, 128.4,
1
H NMR (400 MHz, CDCl ): d = 8.54–7.19 (m, 11 H), 4.05–3.65
m, 4 H), 3.06 (q, J = 7.2 Hz, 4 H), 1.53–1.42 (m, 4 H), 1.31 (t,
128.01, 126.8, 126.3, 126.1, 125.2, 124.6, 123.6, 121.2, 115.9,
115.5, 69.4, 45.5, 29.0, 27.9, 22.2, 14.1.
3
(
J = 6.8 Hz, 3 H), 1.29–1.23 (m, 4 H), 1.10–0.72 (m, 4 H), 0.66 (t,
J = 6.8 Hz, 6 H).
LCMS: m/z = 543 (M – 1).
1
3
C NMR (400 MHz, CDCl ): d = 200.3, 156.6, 154.4, 136.6, 134.0,
6,6¢-Diacetyl-2,2¢-dimethoxy-1,1¢-binaphthyl [(R)-8a]; Typical
3
1
1
2
31.9, 130.9, 129.7, 129.3, 129.2, 127.9, 127.8, 126.1, 125.8, 125.1,
24.0, 123.3, 120.4, 119.6, 115.7, 115.3, 69.4, 31.5, 29.0, 27.8,
2.0, 13.7, 8.4.
Procedure
Anhyd AlCl (2.66 g, 20 mmol) and AcCl (1.42 mL, 20 mmol) were
3
added to CH Cl (30 mL) at 0 °C. To this mixture, (R)-7 (1.57 g, 5
2
2
mmol) was added, and the mixture was stirred at –45 °C for 3 h. The
LCMS: m/z = 483 (M + 1).
mixture was poured into ice-cold H O and it was shaken with
2
CH Cl (25 mL). The aqueous layer was extracted with CH Cl (2
2
2
2
2
6
,6¢-Dibenzoyl-2,2¢-bis(pentyloxy)-1,1¢-binaphthyl [(R)-5c]
×
25 mL) and the combined organic phases were washed with brine
Yield: 62%.
(
10 mL) and dried (anhyd Na SO ). The solvent was removed and
2
4
[
a
]
2
5
–
1
0
.
0
(
c
1
.
0
0
,
C
H
C
l
)
.
D
3
the residue was column chromatographed (silica gel, hexane–
EtOAc, 80:20); yield: 1.73 g (87%); mp 184–186 °C.
–
1
IR (neat): 3061, 2955, 2870, 1653, 1616, 1051 cm .
2
5
1
[a]D –100.3 (c 1.00, CHCl3).
H NMR (400 MHz, CDCl ): d = 8.35–7.26 (m, 20 H), 4.04–3.97
m, 4 H), 1.46 (t, J = 6.8 Hz, 4 H), 1.09–0.95 (m, 8 H), 0.68 (t,
3
(
IR (KBr): 2935, 2837, 1666, 1614, 1174, 1057 cm–1.
J = 7.2 Hz, 6 H).
1
H NMR (400 MHz, CDCl ): d = 8.52 (s, 2 H), 8.13 (d, J = 9.2 Hz,
3
1
3
C NMR (400 MHz, CDCl ): d = 196.6, 156.7, 138.3, 136.3,
3
2 H), 7.76 (d, J = 8.2 Hz, 2 H), 7.52 (d, J = 8.2 Hz, 2 H), 7.11 (d,
J = 9.2 Hz, 2 H), 3.80 (s, 6 H), 2.68 (s, 6 H).
1
6
32.6, 132.5, 132.1, 130.0, 128.4, 127.8, 126.2, 125.5, 119.7, 115.7,
9.3, 29.7, 28.9, 27.9, 22.1, 13.9.
1
3
C NMR (400 MHz, CDCl ): d = 195.3, 154.5, 133.7, 129.9, 129.1,
3
LCMS: m/z = 635 (M + 1).
1
28.1, 125.4, 122.7, 122.0, 116.2, 111.8, 54.0, 24.0.
LCMS: m/z = 399 (M + 1).
6
-Benzoyl-2,2¢-bis(pentyloxy)-1,1¢-binaphthyl [(R)-6c]
Yield: 21%.
Anal. Calcd for C H O : C, 78.37; H, 5.57. Found: C, 78.25; H,
2
6
22
4
25
5.53.
[
a]D +39.7 (c 1.00, CHCl3).
–
1
IR (neat): 3063, 2953, 2870, 1616, 1464, 1089 cm .
2
,2¢-Dimethoxy-6,6¢-dipropanoyl-1,1¢-binaphthyl [(R)-8b]
1
Yield: 78%; mp 156–158 °C.
H NMR (400 MHz, CDCl ): d = 8.33–7.30 (m, 16 H), 4.02–3.91
m, 4 H), 1.43 (t, J = 6.8 Hz, 4 H), 1.27–0.92 (m, 8 H), 0.67 (t,
3
(
25
[
a]D –86.4 (c 0.5, CHCl3).
J = 7.2 Hz, 6 H).
–
1
IR (KBr): 2966, 2839, 1678, 1616, 1172, 1041 cm .
1
3
C NMR (400 MHz, CDCl ): d = 196.7, 156.7, 154.5, 138.4, 136.5,
3
1
H NMR (400 MHz, CDCl ): d = 8.55 (s, 2 H), 8.15 (d, J = 8.8 Hz,
3
1
1
1
2
34.5, 134.1, 133.7, 132.5, 132.3, 132.0, 130.9, 130.6, 130.2, 130.0,
29.4, 129.3, 128.9, 128.5, 128.2, 127.9, 127.8, 127.3, 126.2, 126.0,
25.8, 123.5, 120.6, 19.8, 115.9, 115.6, 69.6, 69.3, 29.1, 28.9, 27.9,
7.8, 22.2, 22.1, 13.9.
2
H), 7.81 (d, J = 8.8 Hz, 2 H), 7.55 (d, J = 8.8 Hz, 2 H), 7.14 (d,
J = 8.8 Hz, 2 H), 3.79 (s, 6 H), 3.12 (q, J = 7.2 Hz, 4 H), 1.29 (t,
J = 7.2 Hz, 6 H).
1
3
C NMR (400 MHz, CDCl ): d = 200.6, 157.0, 136.2, 132.3, 131.6,
3
LCMS: m/z = 531 (M + 1).
1
30.0, 128.1, 125.4, 124.6, 118.9, 114.4, 56.6, 31.7, 8.5.
2
5
,2¢-Bis(pentyloxy)-6,6¢-bis(phenylacetyl)-1,1¢-binaphthyl [(R)-
LCMS: m/z = 427 (M + 1).
d]
Anal. Calcd for C H O : C, 78.85; H, 6.14. Found: C, 78.73; H,
2
8
26
4
Yield: 66%.
6
.15.
25
[
a]D +33.7 (c 1.00, CHCl3).
–
1
2,2¢-Dimethoxy-6,6¢-bis(2-methylpropanoyl)-1,1¢-binaphthyl
(R)-8c]
Yield: 75%; mp 126–128 °C.
IR (neat): 3050, 2926, 1675, 1610, 1469, 939 cm .
[
1
H NMR (400 MHz, CDCl ): d = 8.73–7.13 (m, 20 H), 4.38 (s, 4 H),
.03–3.97 (m, 4 H), 1.04 (t, J = 6.0 Hz, 4 H), 1.06–0.92 (m, 8 H),
.65 (t, J = 7.2 Hz, 6 H).
3
4
0
2
5
[
a]D –90.6 (c 0.5, CHCl3).
–
1
1
3
IR (KBr): 2968, 2841, 1674, 1616, 1271, 1062 cm .
C NMR (400 MHz, CDCl ): d = 197.5, 156.8, 136.6, 135.0, 131.5,
29.8, 129.5, 129.0, 128.7, 128.0, 126.8, 125.7, 124.8, 119.6, 115.6,
9.2, 45.4, 28.9, 27.8, 22.1, 13.9.
3
1
1
6
H NMR (400 MHz, CDCl ): d = 8.55 (s, 2 H), 8.16 (d, J = 9.0 Hz,
3
2 H), 7.80 (d, J = 8.9 Hz, 2 H), 7.55 (d, J = 9.0 Hz, 2 H), 7.15 (d,
J = 8.9 Hz, 2 H), 3.83 (s, 6 H), 3.72 (m, J = 6.8 Hz, 2 H), 1.28 (d,
J = 6.8 Hz, 12 H).
LCMS: m/z = 663 (M + 1).
Synthesis 2007, No. 24, 3821–3826 © Thieme Stuttgart · New York

PAPER
Synthesis of 6,6¢-Diacyl-1,1¢-bi-2-naphthyl Ethers
LCMS: m/z = 551 (M + 1).
3825
1
3
C NMR (400 MHz, CDCl ): d = 204.2, 157.0, 136.2, 131.6, 131.5,
3
1
30.2, 128.2, 125.5, 118.9, 114.4, 56.6, 35.2, 19.4.
Anal. Calcd for C H O : C, 82.89; H, 5.49. Found: C, 82.65; H,
3
8
30
4
LCMS: m/z = 455 (M + 1).
5.42.
Anal. Calcd for C H O : C, 79.27; H, 6.65. Found: C, 79.34; H,
30
30
4
2
[
,2¢-Dimethoxy-6,6¢-bis(4-methoxybenzoyl)-1,1¢-binaphthyl
(R)-8h]
Yield: 70%; mp 132–134 °C.
6
.77.
6
,6¢-Bis(chloroacetyl)-2,2¢-dimethoxy-1,1¢-binaphthyl [(R)-8d]
2
5
Yield: 72%; mp 178–180 °C.
[a]D –65.2 (c 1.00, CHCl3).
25
IR (KBr): 2964, 2847, 1768, 1643, 1599, 1022 cm–1.
[
a]D –42.0 (c 0.2, CHCl3).
–
1
1
IR (KBr): 2935, 2841, 1695, 1682, 1616, 1350 cm .
H NMR (400 MHz, CDCl ): d = 8.32 (s, 2 H), 8.12 (d, J = 9.0 Hz,
3
1
2 H), 7.92 (d, J = 8.6 Hz, 4 H), 7.70 (d, J = 8.8 Hz, 2 H), 7.56 (d,
J = 9.0 Hz, 2 H), 7.22 (d, J = 8.8 Hz, 2 H), 7.02 (d, J = 8.6 Hz, 4 H),
3
13C NMR (400 MHz, CDCl
1
1
H NMR (400 MHz, CDCl ): d = 8.5 (s, 2 H), 7.91–7.89 (d, J = 8.4
Hz, 2 H), 7.57–7.55 (d, J = 8.4 Hz, 2 H), 7.50–7.48 (d, J = 8.7 Hz,
H), 7.28–7.26 (d, J = 8.7 Hz, 2 H), 4.79 (s, 4 H), 3.79 (s, 6 H).
3
.92 (s, 6 H), 3.72 (s, 6 H).
2
1
3
3
): d = 195.3, 163.0, 156.8, 135.8, 133.3,
32.5, 131.8, 131.3, 130.6, 127.8, 127.6, 126.5, 125.2, 118.9, 114.4,
13.6, 113.5.
C NMR (400 MHz, CDCl ): d = 193.6, 155.5, 134.6, 129.6, 128.1,
27.9, 126.8, 125.7, 124.8, 123.6, 114.3, 56.7, 50.6.
3
1
LCMS: m/z = 468 (M + 1).
LCMS: m/z = 583 (M + 1).
Anal. Calcd for C H Cl O : C, 66.82; H, 4.31; Cl, 15.17. Found:
26
20
2
4
Anal. Calcd for C H O : C, 78.33; H, 5.19. Found: C, 78.39; H,
5
3
8
30
6
C, 66.79; H, 4.33; Cl, 15.09.
.12.
2
[
,2¢-Dimethoxy-6,6¢-bis[(4-nitrophenyl)acetyl]-1,1¢-binaphthyl
(R)-8e]
Yield: 68%; mp 156–158 °C.
2
,2¢-Dimethoxy-6,6¢-di-1-naphthoyl-1,1¢-binaphthyl [(R)-8i]
Yield: 71%; mp 138–140 °C.
2
5
25
[a]
IR (KBr): 2937, 2843, 1768, 1685, 1602, 1265 cm .
1H NMR (400 MHz, CDCl
): d = 8.29 (s, 4 H), 8.28–7.26 (m, 20 H),
.74 (s, 6 H).
13C NMR (400 MHz, CDCl
D
–52.4 (c 0.6, CHCl ).
3
[
a]D –54.2 (c 1.00, CHCl3).
–
1
–
1
IR (KBr): 2939, 2839, 1674, 1606, 1514, 1344 cm .
1
3
H NMR (400 MHz, CDCl ): d = 8.6 (s, 2 H), 8.2–7.06 (m, 16 H),
3
3
4
.51 (s, 4 H), 3.82 (s, 6 H).
1
3
3
): d = 173.0, 156.2, 143.9, 134.6, 134.0,
33.7, 132.9, 131.8, 130.9, 130.4, 129.6, 129.1, 128.6, 128.3, 127.9,
27.6, 127.2, 126.6, 118.7, 118.6, 114.6.
C NMR (400 MHz, CDCl ): d = 195.6, 157.5, 154.9, 147.0, 142.4,
3
1
1
1
1
36.7, 133.7, 131.4, 129.2, 128.1, 126.5, 124.8, 123.7, 119.7, 118.4,
14.7.
LCMS: m/z = 623 (M + 1).
LCMS: m/z = 641 (M + 1).
Anal. Calcd for C H O C, 84.87; H, 4.86. Found: C, 84.65; H,
4
4
30 4:
Anal. Calcd for C H N O : C, 71.24; H, 4.41; N, 4.37. Found: C,
3
8
28
2
8
4
.89.
7
1.20; H, 4.45; N, 4.39.
6
,6¢-Dibenzoyl-2,2¢-dimethoxy-1,1¢-binaphthyl [(R)-8f]
Acknowledgment
Yield: 75%; mp 152–154 °C.
2
5
M.N.R. and N.K.B. are thankful to CSIR (New Delhi) for a fel-
lowship. Support of the UGC (New Delhi) under the ‘University of
Potential for Excellence’ (UPE) and ‘Centre for Advance Study’
(CAS) programs are gratefully acknowledged. We are also thankful
to the DST (New Delhi) for providing the 400 MHz NMR facility
under the FIST program. A research grant to M.P. from ILS-UOH-
MOU is also gratefully acknowledged.
[
a]D –52.3 (c 0.6, CHCl3).
–
1
IR (KBr): 2935, 2835, 1718, 1653, 1616, 1062 cm .
1
H NMR (400 MHz, CDCl ): d = 8.33 (s, 2 H), 8.10 (d, J = 8.9 Hz,
H), 7.86 (m, J = 8.2 Hz, 4 H), 7.74 (d, J = 8.7 Hz, 2 H), 7.60 (d,
J = 7.7 Hz, 2 H), 7.54 (m, J = 8.7 Hz, 4 H), 7.50 (d, J = 7.7 Hz, 2
H), 7.20 (d, J = 8.9 Hz, 2 H), 3.83 (s, 6 H).
3
2
1
3
C NMR (400 MHz, CDCl ): d = 196.2, 155.1, 143.6, 138.7, 133.4,
3
1
1
29.5, 128.9, 128.4, 127.5, 126.7, 126.6, 125.7, 125.3, 125.2, 119.4,
14.4.
References
(
1) (a) Noyori, R. Asymmetric Catalysis in Organic Synthesis;
Wiley: New York, 1994. (b) Rosini, C.; Franzini, L.;
Raffaelli, A.; Salvatori, P. Synthesis 1992, 503. (c) Noyori,
R. Chem. Soc. Rev. 1989, 18, 187; and references cited
therein. (d) Noyori, R.; Suga, S.; Kawai, K.; Okada, S.;
Kitamura, M. Pure Appl. Chem. 1988, 60, 1597.
LCMS: m/z = 523 (M + 1).
Anal. Calcd for C H O : C, 82.74; H, 5.01. Found: C, 82.59; H,
36
26
4
5
.04.
2
8
,2¢-Dimethoxy-6,6¢-bis(4-methylbenzoyl)-1,1¢-binaphthyl [(R)-
g]
(2) Sasai, H.; Tokunaga, T.; Watanbe, S.; Suzuki, T.; Itoh, N.;
Shibasaki, M. J. Org. Chem. 1995, 60, 7388.
(3) Kobayashi, S.; Ueno, M.; Saito, S.; Mizuki, Y.; Ishitani, H.;
Yamashita, Y.; Trost, B. Proc. Natl. Acad. Sci. U.S.A. 2004,
Yield: 72%; mp 128–130 °C.
25
[
a]D –67.2 (c 0.6, CHCl3).
–
1
IR (KBr): 2935, 2843, 1763, 1651, 1616, 1041 cm .
101, 5476.
1
H NMR (400 MHz, CDCl ): d = 7.31 (s, 2 H), 8.10–7.16 (m, 16 H),
(4) (a) Venkatraman, L.; Periasamy, M. Tetrahedron:
Asymmetry 1996, 7, 2471. (b) Periasamy, M.; Venkatraman,
L.; Kumar, S. S.; Kumar, N. S.; Ramanathan, C. R. J. Org.
Chem. 1999, 64, 7643.
3
3
.82 (s, 6 H), 2.45 (s, 6 H).
1
3
C NMR (400 MHz, CDCl ): d = 196.2, 156.9, 142.9, 135.9, 135.4,
3
1
5
32.9, 132.3, 131.4, 130.2, 128.9, 127.8, 126.5, 125.2, 118.9, 114.3,
6.6, 21.6.
Synthesis 2007, No. 24, 3821–3826 © Thieme Stuttgart · New York

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M. Periasamy et al.
PAPER
(5) Periasamy, M.; Kumar, N. S.; Ramanathan, C. R.
Tetrahedron: Asymmetry 1999, 10, 2307.
(10) Sogah, G. D. Y.; Cram, D. J. J. Am. Chem. Soc. 1979, 101,
3035.
(6) Periasamy, M.; Kumar, N. S.; Kumar, S. S.; Rao, V. D.;
Ramanathan, C. R.; Venkatraman, L. J. Org. Chem. 2001,
(11) Ishitani, H.; Ueno, M.; Kobayashi, S. J. Am. Chem. Soc.
2000, 122, 8180.
6
6, 3828.
(12) Sartori, G.; Maggi, R. Chem. Rev. 2006, 106, 1077.
(13) Huang, W.-E.; Hu, Q.-S.; Zheng, X.-F.; Anderson, J.; Pu, L.
J. Am. Chem. Soc. 1997, 119, 4313.
(
(
(
7) Periasamy, M.; Reddy, M. N.; Anwar, S. Tetrahedron:
Asymmetry 2004, 15, 1809.
8) Rao, V. D.; Periasamy, M. Tetrahedron: Asymmetry 2000,
(14) Zhang, H.-C.; Huang, W.-S.; Pu, L. J. Org. Chem. 2001, 66,
481.
11, 1151.
9) Periasamy, M.; Seenivasaperumal, M.; Rao, V. D.
Tetrahedron: Asymmetry 2004, 15, 3847.
Synthesis 2007, No. 24, 3821–3826 © Thieme Stuttgart · New York