Efficient routes to racemic and enantiomerically pure (s)-binol diesters

Article abstract of DOI:10.1080/00397911.2013.774017

A systematic study for esterification procedures to the synthesis of BINOL diesters is described. Reaction conditions with trifluoracetic acid anhydride (TFAA) and 85% H₃PO₄ were selected as the best procedure to prepare enantiomeric

Full text of DOI:10.1080/00397911.2013.774017

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Efficient Routes to Racemic and Enantiomerically Pure
(S)-Binol Diesters
Andrea R. Costantino a b , Romina A. Ocampo a b , María G. Montiel Schneider a b , Gustavo
Fernandez a , Liliana C. Koll a b & Sandra D. Mandolesi a
a Instituto de Química del Sur (INQUISUR), Departamento de Química, Universidad Nacional
del Sur , Bahía Blanca , Argentina
b CONICET , Argentina
Accepted author version posted online: 03 Jul 2013.
To cite this article: Synthetic Communications (2013): Efficient Routes to Racemic and Enantiomerically Pure (S)-Binol
Diesters, Synthetic Communications: An International Journal for Rapid Communication of Synthetic Organic Chemistry, DOI:
10.1080/00397911.2013.774017
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EFFICIENT ROUTES TO RACEMIC AND ENANTIOMERICALLY PURE (S)-
BINOL DIESTERS
Andrea R. Costantino1,2, Romina A. Ocampo1,2, María G. Montiel Schneider1,2, Gustavo
Fernandez1, Liliana C. Koll1,2, Sandra D. Mandolesi1
1Instituto de Química del Sur (INQUISUR), Departamento de Química, Universidad
Nacional del Sur, Bahía Blanca, Argentina 2CONICET, Argentina
Sandra D. Mandolesi E-mail: sdmando@uns.edu.ar
Abstract
A systematic study for esterification procedures to the synthesis of BINOL diesters is
described. Reaction conditions with TFAA and 85% H3PO4 were selected as the best
procedure to prepare enantiomerically pure (S)-BINOL diesters VIII to XI with almost
quantitative yields and very low reaction times.
[Supplementary materials are available for this article. Go to the publisher’s online
edition of Synthetic Communications® for the following free supplemental resource(s):
Full experimental and spectral details.]
KEYWORDS: diols, esterification, phase-transfer catalysis, diesters, BINOL, C2
symmetry.
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INTRODUCTION
Since 1990, the enantiomeric atropoisomers of 1,1´-binaphthyl-2,2´-diol (BINOL, I) have
become one of the most widely used ligands for both stoichiometric and catalytic
asymmetric reactions.[1] The preparation of racemic BINOL and its resolution has been
widely studied, and some well-established methods are reported.[2]Stereoselectivity
control is based in the utilization of molecules from the Cn or Dn groups of symmetry that
allow the prediction of enantioselectivity due to the existence of only one reactive
species. Under this supposition, chiral atropoisomers become very interesting, especially
those corresponding to binaphtyl systems. The potential of I as a ligand for metal-
mediated catalysis was first recognized in 1979 by Noyori in the reduction of aromatic
ketones and aldehydes.[1g] BINOL itself, however, does not always give satisfactory
results in asymmetric catalysis, and since Noyori’s discovery there has been an ongoing
interest in modified BINOL ligands. The rigid structure, thermal stability and the C2
symmetry of the chiral binaphthyl molecules play an important rol in assymetric
induction. In the last few years, BINOL derivatives have become attractive
moleculeswith applications in chiral supramolecular recognition, crystal engineering,
electro optical materials and polymers, among others.[3-6]These type of binaphtyl
compounds are often synthetized using enantiomerically pure BINOLas the starting
material easily transforming the 2,2´-hydroxy groups into other functional groups.[7]
RESULTS AND DISCUSSIONS
Several diastereoselective synthesis of macrocycles have been developed using chiral
auxiliary groups and rigid organic templates.[8a–d]As part of our research work on the
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behavior of diesters derived from diols with C2 symmetry and as precursors of new
macrodiolides,[8e]we now report a systematic study of some efficient and optimized
synthetic routes to saturated and unsaturated (±)-BINOL diestersthrough five different
procedures, with the aim of determining the best reaction conditions,easy to handle, with
high efficiency and minimum environmental impact, comparing the direct acylation using
carboxylic acids with those mediated by acid derivatives (Scheme 1). Once the best
selected procedure was chosen, it was applied for the synthesis ofenantiomerically pure
(S)-BINOL diestersVIII – XI starting from (S)-BINOL.[9]Among some uses, these
compounds have great application in odontology, [10] and are a source of chiral
dendrimers for use in asymmetriccatalysis.[11]
Direct acylation of alcohols with carboxylic acids is preferred over acylation with
anhydrides (poor atom economy) or acid chlorides (moisture sensitive). The main
disadvantage of direct acylation is the unfavorable chemical equilibrium that can be
overcome by a large excess of one of the reagents, or removing water by Dean-Stark
distillation. Besides, phenols or naphthols are usually too unreactive to give useful yields
by this procedure. Unlike –OH group of alcohols (pka values between 16–18), -OH
group of phenols is more acidic(pka values between 8–10) being less reactive
towards esterification and therefore requires activation of the corresponding carboxylic
acid used. This can be achieved either via conversion of carboxylic acid to more reactive
functional groupsor in situ activation in the presence of coupling reagents.[12] It is
important to remark, however, that some of these methods present some disadvantages
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related to the use of volatile and environmentally harmful organic solvents and reagents,
low or moderate yields and long reaction times.
With the aim of finding esterification procedures with high efficiency and minimum
environmental impact, we report here the results obtained in the synthesis of diestersII to
VIIcomparing the direct acylation of BINOL (I) using carboxylic acids with the reaction
mediated by acid derivatives (Scheme 1) . This initial studies were conducted using
racemic I, but the procedures were equally valid for the enantiomerically pure BINOL
diestersVIII – XI synthetized later.
First, racemic (±)-BINOL (I) was prepared according to well known procedures.[2a] (S)-
BINOL was purchased from Aldrich, although there are established methods to resolve
(±)-BINOL.[2d]The esterification of I was achieved following five different reaction
conditions (Methods A-E) and the results obtained are summarized in Table 1.[13]The
progress of the reactions was monitored by TLC of silica gel and, after completion,
quantified by GC-MS through a standard curve generated from isolated pure product.
The first method is one of the most versatile procedures of direct esterification that uses
dicyclohexylcarbodiimide (DCC) and dimethyl-aminopyridine (DMAP).[14]The reaction
probed to be insensitive to steric hindrance in the carboxylic acid and proceeded at room
temperature with reaction times between 1–4 h.In this case, the reaction was carried out
in a toluene/p-toluensulfonic acid media instead of the classical (and non
recommendable)benzene commonly used in this esterification method (Method A, Table
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1, entries 1, 6, 11, 16, 21 and 26). The yields observed in the crude reaction products are
high (between 81 - 98 % , determined by GC-MS analysis) but it has the disadvantage
that N-acylurea generated as a byproduct must be carefully separated by filtration through
celite and silica gel 60 column chromatography. This causes some lost in the final yield
about 10%.
One particular transesterification methodology, which also uses carboxylic acids and
phenols mixtures as substrates, is trifluoracetic acid anhydride (TFAA) /H3PO4-mediated
direct O-acylation, that has obtained a new impulse recently.[15] Here, we extended the
method to the synthesis of BINOL diesters through this single-step and metal-free
process (Method B, Table 1, entries 2, 7, 12, 17, 22 and 27). The reactions were
performed at room temperature or with gentle warming (50ºC) depending on the
carboxylic acid used, under air atmosphere. To our pleasure, all the reactions tested were
ready between 15 to 45 minutes with almost quantitative yields of the racemic BINOL
diestersII – VII and no formation of the monoester was observed. A simple extraction
and washing with diluted NaOH solution provides the target diesters almost pure. In the
case of compounds VI and VII,yields are relatively minor probably due to some steric
hindrance in the carboxylic acid that also delayed the esterification reaction.[16]
On the other hand, it is well known that there are some advantages in the use of acyl
chlorides or acid anhydrides instead of the Fisher esterification. Some of them are
increased speed, performance, milder conditions and lack of reversibility. The main
disadvantagesare that not always the desired acid chloride is available and its preparation
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involves some special care due to its moisture sensitivity. Taking into account that
alkoxide ion treatment with acid halides and other derivatives is a common way to access
esters in some cases, NaHcan be used as a base and is very easy to handle (air
manipulation). Thus, the course of the racemic BINOL (I) esterification reaction was
analyzed using the corresponding acyl chloride, NaH and THF at room temperature
(Method C, Table 1, entries 3, 8, 13, 18, 23 and 28). Unfortunately, diestersIV, V, VI and
VII (entries 13, 18, 23 and 28, Table 1) could not be obtained and only unreacted (±)-
BINOL and the corresponding monoester was observed. This suggests the possibility
that, in these cases, the lack of reactivity is due to a strong intramolecular coordination of
the sodium cation with the alcoxide anion and the carboxylic group when the first
esterification reaction is completed and could hinder diesterification. According to
previous studies referred to etherification reactions, [17- 18] crown ethers can prevent this
undesired association by solvation of the sodium cation and increasing the nucleophilicity
of the anion.So, we decided to study the same reaction conditions (NaH / THF / r.t.) but
now adding 18-crown-6 (Scheme 2).
As can be seen from Table 1, (Method D, entries 4, 9, 14, 19, 24 and 29, Table 1) better
performance was found compared with Method C in almost every case (75–95% except
entry 24).Besides, this procedure is very suitable for its simplicity: the mixture was
stirred at room temperature and when the reaction finished,the crude product was
quenched with KBr saturated solution. Column chromatography purification on silica gel
60 provided the desired diestersII – VIIin good yields.
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Finally, the esterification procedure of (±) BINOL (I)was studied with acyl chlorides in a
phase transfer catalytic (PTC) media (Method E, Table 1, entries 5, 10, 15, 20, 25 and
30). The biphasic system wasdichloromethaneand aqueous NaOH in the presence of a
quaternary ammonium salt such as Bu4N+Cl- (Scheme 3).[19]NaOH is critical for good
performance, but its concentration cannot exceed 30% since it can result in the hydrolysis
of the resulting ester.[20]The optimum conditions for this esterification include the use of
0.03 equivalents of catalyst, dichloromethane as solvent and low temperature (0°C to r.t.).
The observed yields for this procedure ranged between good to very good (53–95%) in
moderate reaction times (12–24 h). The diestersII – VIIwere isolated by simple phase
separation, washed with aqueous sodium bicarbonate, dried and purified on silica gel 60
column chromatography.
Once the optimum conditions for the synthesis of BINOL diesterswere fixed (Method B,
TFAA/H3PO4, r.t. or 50° C, air atm.), this procedure was applied to obtain the desired
enantiomerically pure (S)-BINOL diesters VIII – XI. As expected, the products were
obtained with excellent to quantitative yields and all the reaction times were between 15
to 45 min (Scheme 4).
In summary, we present here a comparative study of different procedures modifications
leading to optimize synthetic routes to saturated and unsaturated BINOL diesters, racemic
or enantiomerically pure, with excellent yields. Some of these methods demonstrated to
be excellent and very efficient as in the case of Method B, which proved to be smooth
and free from special care on the preparation and/or preconditioning of an acyl chloride.
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In the case of Methods D and E (NaH / crown ether and NaOH / PTC respectively), both
are very appropriate not only because of the good yields observed but also for the
simplicity and mild reaction conditions. We have synthesized six racemic diesters and
four enantiomerically pure diesters (VIII–XI) which are, to our knowledge, absolutely
new. All the new compounds are characterized by a thorough analysis of their 1H, 13C-
NMR, GC-MS and IR spectra. This promising preliminar results encouraged us for future
studies with substituted BINOLs.
EXPERIMENTAL
Unless otherwise noted, all reagents were purchased from commercial suppliers and used
without purification. Tetrahydrofuran (THF) and toluene (PhCH3) were distilled from
sodium benzophenoneketyl under nitrogen. NaH was purchased from Fluka as 80%
dispersion in mineral oil and must be rinsed with dry THF before use under inert
atmosphere. Dry CH2Cl2 was achieved by simple storage of the solvent over activated 3
A˚ molecular sieves. Thin layer chromatography was performed on Merck precoated
silica gel 60 F254 plates and visualization was accomplished with UV light and/or 5%
ethanol solution of phosphomolibdic acid. Silica gel (Merck, 230–400 mesh) was used
for column chromatography. Melting points were recorded on a Büchi Melting Point B-
545 instrument and are uncorrected. NMR spectra were recorded in CDCl3 on a 300 MHz
spectrometer (300.1 MHz for 1H and 75.5 MHz for 13C) at 23º C. Chemical shifts (δ) are
given in ppm downfield relative to TMS (1H and 13C) and coupling constants (J) are in
Hz. Mass spectra were obtained with a GC/MS instrument (HP5-MS capillary column, 30
m / 0.25 mm / 0.25 mm) equipped with 5972 mass selective detector operating at 70 eV
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(EI).High resolution mass spectra (HRMS) were recorded on a Finnigan Mat 900 (HR-
EI-MS).Compounds described in the literature were characterized by comparison of their
1H, and/or 13C NMR spectra to the previously reported data. Infrared spectra were
recorded with a Nicolet Nexus 470 FT spectrometer. Optical rotations were measured on
a Polar L- P, IBZ Messtechnikpolarimeter at 589 nm. Elemental analyses (C, H) were
performed in an EXETER CE-440 instrument at UMYMFOR (Argentina).
General Procedure For The Esterification Reactions Of (±)-BINOL (I)
A solution of (±)-BINOL (I), solvent, esterification agent and the corresponding
carboxylic acid or acyl chloride were combined according to Methods A to E, resumed in
Table 1 (see Supporting Information for complete details). The reactions were monitored
by thin-layer chromatography (TLC).
Selected Data
Esterification reactions of (S)-BINOL. General Procedure for the Synthesis of
enantiomerically pure (S)-1,1′-binaphthyl-2-2′-diyl dimetacrylate (IX). Method B
(TFAA, H3PO4, r.t. or 50°C). A mixture of methacrylic acid (0.228 mL, 2.6mmol), (S)-
BINOL (0.342 g, 1.2mmol) and 85% orthophosphoric acid (H3PO4, 0.012 mL,
0.24mmol) was stirred under air atmosphere. To this solution, trifluoroacetic anhydride
(TFAA, 1.41 mL, 10.0mmol) was added dropwise and the resulting mixture was allowed
to stir at room temperature (see Table 1). The progress of the reaction was monitored by
TLC. The reaction mixture was added to a little crushed ice, extracted with diethyl ether
(3 x 8 mL), washed with 10% NaOH solution (2 x 8 ml) followed by water (2 x 8 mL),
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dried over anhydrous sodium sulphate and concentrated to afford the desired
diesterIX(0.507 g, quantitative yield) as a white solid, purified by recrystallization in
ethanol, mp54-56°C. [α]D25 -56.1 (c 1.6, CHCl3); 1H NMR (300 MHz, CDCl3) δ 1.48
(6H, d, J= 1.1 Hz CH3), 5.19 (2H, dd, J= 2.4, 1.2 Hz, CH2), 5.54 (2H, dd, J= 2.4, 1.2 Hz,
CH2), 7.19 – 7.27 (4H, m, Ar-H), 7.31 – 7.48 (4H, m, Ar-H), 7.78 – 7.96 (4H, m, Ar-H);
13C NMR (75.4 MHz, CDCl3) δ 16.8, 120.7, 122.6, 124.6, 125.0, 125.6, 125.7, 126.9,
128.3, 130.4, 132.4, 134.4, 145.9, 164.3; MS (EI): m/z (relative intensity) 422.1 (M+,
100), 284.1 (1.8), 282.1(13), 268.1 (40), 255.1 (15), 239.0 (19), 228.1 (8), 226.0 (37),
69.0 (87); Anal. Calcd for C28H22O4: C, 79.60; H , 5.25. Found: C, 79.57; H, 5.20.
(S)-1,1′-binaphthyl-2-2′-diyl diacrylate (VIII): [α]D25 -25.6 (c 1.00, CHCl3); mp 71-
73°C.
(S)-1,1′-binaphthyl-2-2′-diyl-(Z)-2-methyl-3-phenyl-2-propenoate (X): [α]D25 -34.9 (c
0.95, CHCl3), mp 100-102°C.
(S)-1,1′-binaphthyl-2-2′-diyl di-(Z)-2,3-diphenyl-2-propenoate (XI): [ ]D25 -38.2 (c
0.90, CHCl3); mp 90-92°C.
SUPPORTING INFORMATION
Full experimental detail, 1H and 13C spectra. This material can be found via the
“Supplemantary Content” section of this article webpage.
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ACKNOWLEDGMENTS
This work was supported by grants from ANPCyT (Buenos Aires, Argentina), CONICET
(Buenos Aires, Argentina) and Universidad Nacional del Sur (Bahía Blanca, Argentina).
A fellowship from CONICET to ARC and GMS is acknowledged.
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(e) Gerbino, D. C.; Koll, L. C.; Mandolesi, S. D.; Podestá, J. C. Stereoselective radical
tandem cyclohydrostannation of optically active di-unsaturated esters of TADDOL.
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9. (S)- and (R)-1,1´-bi-2-naphtyl diacetate are purchased by Richest Group Ltd (China)
and Aldrich respectively. (S)- and (R)-1,1´bi-2-naphtyl dibenzoate are purchased by
Tetrahedron® and Across respectively
10 Patent: International Publication Number: WO 2010/027676 A2, March, 2010.
PCT/US2009/054392.
11.(a) Hu, Q-S.; Pugh, V.; Sabat, M.; Pu, L. Structurally rigid and optically active
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2,2´diyl diacetate solutions at 308.15 K. E-Journal of Chemistry. 2011, 8(2), 762-766; (c)
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montmorillonite-enwrapped titanium as a heterogeneous acid catalyst. Tetrahedron Lett.
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for the direct acetylation of alcohols with acetic acid. J. Mol. Catal. A: Chem. 2004, 217,
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27-29; (e) Ishihara, K.;Nakagawa, S.; Sakakura, A. Bulky
diarylammoniumarenesulfonates as selective esterification catalysts. J. Am. Chem. Soc.
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TiO(acac)2. J. Org. Chem. 2005, 70, 8625-8627; (g) Peng, Z.; Orita, A.; An, D.; Otera,
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13.(a) It is important to note that compound II has been reported previously in very good
yields but the synthesis was achieved using acetic anhydride. For further information see
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2009, 30, 1071-1076; (b) Compound III was obtained through benzoylation under
extreme conditions with benzoic anhydride and no characterization is informed. For
further information seeOrita, A.;Tanahashi, C.; Kakuda, A.; Otera, J. Highly powerful and
practical acylation of alcohols with acid anhydride catalyzed by Bi(OTf)3. J. Org. Chem.
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2001, 66, 8926-8934; (c) Badr, M. Z. A.; Aly, M. M.; Abdel-Latif, F. F. Molecular
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Chem. 1979, 44, 3244-3247.
14. Hassner, A.; Alexanian, V. Direct room temperature esterification of carboxylic
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using benzoic anhydrides with Lewis acid catalysts. Tetrahedron. 2004, 60, 1587-1599;
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acids with alcohols in the presence of di-t-butyl dicarbonate. Synlett. 2004, 263-266; (c)
Dauvergne, J.; Wellington, K.; Chibale, K; (d) Montiel-Smith, S.; Meza-Reyes, S.; Viñas-
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trifluoroacetyl moiety. Application to the esterification of colesterol and phenol. Arkivoc.
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from phenols. Journal of Fluorine Chemistry. 2009, 130, 505-508.
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binaphtol. Tetrahedron Lett. 2002, 43, 4055-4057.
17.Cookson, R., Crumbie, R. L. Conversion of ketones into vinyl-oxiranes. Tetrahedron
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18. Although 15-crown-5- is the specific ether to coordinate Na cation, 18-crown-6 is
equally efficient and substantially cheaper.
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19. Liu, K. T., Kuo, M.-Y. A convenient procedure for phase transfer catalyzed
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20. The low yield (Table 1, entry 5) could be attributed to the easily hydrolysable acetyl
chloride.
21. Bradley, D.; Williams, G.; Lawton, M. Drying of organic solvents: quantitative
evaluation of the efficiency of several desiccants. J. Org. Chem. 2010, 75, 8351–8354.
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Table 1. (±)-BINOL diesters II – VII obtained in the esterification of (±)-BINOL (I)
under different reaction conditions.
Entr Acylating reagent
y
Reaction Conditions a
Time
(h) b
Product
%
Yield
c
1
acetic acid
DCC, DMAP, PhCH3,TsOH,
r.t.d
1
92.5
2
3
4
5
TFAA, H3PO4, 50°C, air atm. e 0.25
98
75
92
53
acetyl chloride
NaH, THF, r.t. f
12
12
24
NaH, THF, 18-crown-6, r.t.g
NaOH, Bu4N+Cl-, H2O,
CH2Cl2, r.t., air atm.h
DCC, DMAP, PhCH3, TsOH,
r.t., d
6
benzoic acid
2
88
7
8
TFAA, H3PO4, 50°C, air atm. e 0.25
99
83
94
92
benzoyl chloride
NaH, THF, r.t. f
12
8
12
9
NaH, THF, 18-crown-6, r.t. g
NaOH, Bu4N+Cl-, H2O,
CH2Cl2, r.t., air atm. h
DCC, DMAP, PhCH3, TsOH,
r.t. d
10
11 acrylic acid
4
93
12
TFAA, H3PO4, r.t., air atm. e
0.25
--
100
i
13 acryloyl chloride
NaH, THF, r.t. f
14
15
NaH, THF, 18-crown-6, r.t.
NaOH, Bu4N+Cl-, H2O,
CH2Cl2, r.t., air atm. h
DCC, DMAP, PhCH3, TsOH,
r.t. d
12
95
95
12
16 methacrylic acid
1
98
17
TFAA, H3PO4, r.t., air atm. e
NaH, THF, r.t. f
0.25
--
100
i
18 methacryloyl chloride
19
20
NaH, THF, 18-crown-6, r.t. g
NaOH, Bu4N+Cl-, H2O,
CH2Cl2, r.t., air atm. h
12
80
78
12
21 (Z)-2-methyl-3-phenyl-2- DCC, DMAP, PhCH3, TsOH,
2.5
84
propenoic acid
r.t. d
22
TFAA, H3PO4, 50°C, air atm. e 0.75
85
23 (Z)-2-methyl-3-phenyl-2- NaH, THF, r.t. f
propenoyl chloride
--
i
24
25
NaH, THF, 18-crown-6, r.t. g
14
12
67
69
NaOH, Bu4N+Cl-, H2O,
CH2Cl2, r.t., air atm. h
DCC, DMAP, PhCH3, TsOH,
r.t. d
26 (Z)-2,3-diphenyl-
propenoic acid
3
81
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27
TFAA, H3PO4, 50°C, air atm. e 0.75
70
28 ( (Z)-2,3-diphenyl-propenoyl NaH, THF, r.t. f
chloride
--
i
29
30
NaH, THF, 18-crown-6, r.t. g
12
12
75
80
NaOH, Bu4N+Cl-, H2O,
CH2Cl2, r.t., air atm. h
a Inert atmosphere of Ar unless otherwise is indicated. b Determined by TLC analysis. c
Determined by CG-MS analysis of crude reaction through a standard curve generated
from isolated pure product. d Method A.e Method B. f Method C. g Method D. h Method E.
i Unreacted BINOL and BINOL-monoester were observed.
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Scheme 1.
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21

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Scheme 2.
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Scheme 3.
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Scheme 4.
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