Trans -1,2-Diaminocyclohexane-based sulfonamides as effective hydrogen-bonding organocatalysts for asymmetric Michael-hemiacetalization reaction

Article abstract of DOI:10.1039/c8cy01199k

An easily attainable bifunctional monosulfonamide derivative of DACH was an effective catalyst for Michael addition-hemiacetalization reactions, providing products with ees exceeding 99% under optimized conditions. High enantioselectivities were achieved with just 0.2% mol catalyst loading. The sulfonamide outperformed analogous thiourea and squaramide-based organocatalysts.

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ISSN 2044-4753
PAPER
Qingzhu Zhang et al.
Catalytic mechanism of C–F bond cleavage: insights from QM/MM
analysis of fluoroacetate dehalogenase
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trans-1,2-Diaminocyclohexane-based sulfonamides as effective
hydrogen-bonding organocatalysts for asymmetric Michael-
hemiacetalization reaction
Received 00th January 20xx,
Accepted 00th January 20xx
Maciej Dajek,a Rafał Kowalczyk,a* and Przemysław J. Boratyński a*
DOI: 10.1039/x0xx00000x
www.rsc.org/
An easily attainable bifunctional monosulfonamide derivative of DACH was an effective catalyst for Michael addition-
hemiacetalization reactions providing products with ees exceeding 99% under optimized conditions.
enantioselectivities were achieved with just 0.2 %mol catalyst loading. The sulfonamide outperformed analoguous
thiourea and squaramide-based organocatalysts.
High
intricate catalysts derived from Cinchona alkaloids
(aminoquinine and aminocupreine) where the sulfonamide NH
is additionally activated by a quinoline-8-sulfonyl residue.3
Introduction
Hydrogen bonds are of primary relevance to metal-free
catalysis including enzymatic reactions as well as that of many
small molecules known as organocatalysts. The strength of
these interactions is collective and the most effective
organocatalysts often contain congeners capable of multiple
H-donations such as thiourea and squaramide motifs. In
general, such planar units donating two or more hydrogens are
effective in a wide variety of reactions.1 While the increase in
acidity translates to stronger binding to the reactants, the
transition state interactions determine the outcome of the
catalyzed processes. Also, there is no direct relationship
between the acidity of the catalyst and the obtained
two
Three-point binding organocatalysts with
hydrogen bonding units
CF3
N
CF3
S
S
OCH3
N
H
N
CF3
H
F3C
N
N
H
N
H
N
thioureas
OCH3
N
CF3
O
O
O
O
N
H
N
H
N
N
CF3
H
H
F3C
N
enantioselectivity.
Therefore, application of otherwise
N
overlooked classes of hydrogen bond donors may be effective
in certain types of enantioselective reactions.
CF3
squaramides
In bifunctional compounds with a sulfonamide group, the
hydrogen-bonding unit is not planar (as observed in the X-ray
structures of most sulfonamides in CCDC database) and thus
stereogenic center can be induced at the nitrogen atom much
closer to the reaction site. Also, computational work suggests
that in such compounds the stabilization of an electrophile in
the transition state can be accomplished with only a single
hydrogen-bonding site.2 Furthermore, the additional basic
nitrogen atom in close proximity to the reaction site can
facilitate nucleophile activation and, with the appropriate
geometry, could provide effective chirality transfer. However,
there are very few successful applications of sulfonamides in
asymmetric catalysis, and these are mostly limited to rather
one
Two-point binding organocatalysts with
N
hydrogen bonding unit
this work
O
O
OCH3
O
O
S
CF3
S
N
N
H
N
H
N
N
CF3
sulfonamides
Figure 1. Structures of classical bifunctional thiourea and squaramide catalysts and
sulfonamides derived from Cinchona alkaloids and diaminocyclohexane. Hydrogen
bond donor and basic sites are marked with arrows.
Sulfonamides of chiral amines without aromatic groups, such
as 1,2-trans-diaminocyclohexane (DACH), have not been
exploited in asymmetric catalysis despite their wide
availability.4
These scaffolds were however remarkably
successful when modified with other hydrogen binding units.1,5
Therefore, we decided to explore the applicability of DACH
sulfonamides in asymmetric organocatalytic processes.
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chosen model reaction was expected to allow comparison of
various types of hydrogen bond donating sites and the
interplay of structural components in the catalyst.
Results and Discussion
Sulfonamides are usually easy to obtain from many
commercially available sulfonyl chlorides and are quite
resistant to various reaction conditions. A simple synthesis
was devised for an array of sulfonamides
1
-
4
by simplification
DACH was
of literature precedents (Scheme 1).
monoprotected with a Boc group,6 and cyclized with α,ω-
dihalides7 to form pyrrolidine, piperidine, azepane, and
morpholine rings. Without purification of the intermediates,
the Boc group was removed with aqueous HCl and primary-
tertiary diamines were obtained by distillation. The process
was rather efficient (70-86% yield), with the exception for
seven-membered ring where the yield was moderate (44%).
Subsequent reactions with an array of sulfonyl chlorides were
nearly quantitative. Most products were obtained as solids
which could be further purified by crystallization. The
exclusion of chromatography makes the entire process easily
Scheme 2. Asymmetric Michael hemiacetaization reaction
Table 1. Enantioselectivities in asymmetric reaction catalyzed by various sulfonamides
2a-y: the role of sulfonyl groupa)
scalable. Additionally, compounds
as reference (Figure 2).
5-8 were obtained to serve
Entry
Catalyst
R
Aryl sulfonamides
3,5-(CF3)2C6H3
3,5-(CF3)2C6H3
3,5-(CF3)2C6H3
3-FC6H4
ee, %a)
1
2
2a
2a
ent-2a4b
2b
2c
99.4b)
93
90c)
3
4
87
5
3,5-(MeSO2)2C6H3
3,5-F2C6H3
84
6
2d
2e
84
7
3,5-Cl2C6H3
4-CH3C6H4
83
9
2f
79
9
2g
3-NO2C6H4
78
Scheme 1. Syntheses of DACH-based bifunctional sulfonamides
10
11
12
13
14
15
16
17
18
19
20
21
2h
2i
4-NO2C6H4
78d)
C6H5
74
2j
4-FC6H4
70
2k
3,5-(CH3)2C6H3
2-Naphthyl
2-FC6H4
68
68d)
2l
2m
2n
2o
2p
2q
2r
53
2,3,4-F3C6H2
2,4-F2C6H3
44
41d)
33d)
4d)
C6F5
8-quinolinyl
2,6-Cl2C6H3
2,4,6-(iPr)2C6H3
Alkyl sulfonamides
CH3
3d)
2c)d)
2s
22
23
24
2t
2u
2v
72
CF3
44d)
39d)
cyclohexyl
Figure 2. Studied DACH sulfonamide classes
Dimeric sulfonamides
benzene-1,3-diyl
biphenyl-4,4'-diyl
sulfamide
25
26
27
2w
2x
86
72
63
A Michael-hemiacetalization cascade reaction (Scheme 2) was
used for the screening of chiral sulfonamide performance
(Figure 1). This reaction leads to intermediates relevant to the
synthesis of amino acids and hydropyridine derivatives.8,9 The
chosen dicarbonyl Michael acceptor 9a could interact with a
catalyst through two sites.10 The process can be catalyzed
either by a base or a Lewis acid.9 Nevertheless, substantial
enantioselectivity has been achieved using elaborate
derivatives of alkaloids.11 However, bifunctional catalysis
exploiting tertiary amines and hydrogen bond donating sites
was also effective. Successful examples of such catalysts
include thiourea derivatives of aliphatic amino acids, as
opposed to more complex Cinchona alkaloids.12 Therefore the
2y
a)Reaction conditions: 10 %mol catalyst in toluene at room temperature for 24 h,
catalytic product (4S)-11a. b)Under optimized conditions: 1 %mol catalyst in PhCl
at −20°C for 72h. c)Major product (4R)-11a. d)Incomplete conversions
For the entire class of the catalysts the obtained
enantioselectivities were good, and with few exceptions
exceeded 65%, also in most cases complete conversions were
observed (Table 1). The most effective catalysts 2a4b
-2e had
inductively electron-withdrawing substituents at positions 3
and 5 of the benzenesulfonamide residue. At these meta
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positions, the substituent’s size had very little effect on the enantioselectivity considerably. (However, they did influence
enantioselectivity as judged by the similar performance of the outcome of less successful sulfonamides, for the details,
catalysts with fluorine and methylsulfonyl substituents (2d vs. see ESI)
2c). The 3,5-substitution with methyl groups in 2k had no
Table 2. Enantioselectivities in asymmetric reaction catalyzed by various sulfonamides
effect compared to unmodified benzenesulfonate 2i. Thereby
1a-8a: the role of basic centera)
any steric interactions involving substituents at the meta
positions did not affect the chirality transfer. On the other
hand, ortho-substitution of the benzenesulfonamides had a
detrimental effect on the obtained enantioselectivities. The
2,6-disubstituted catalysts 2r-s and 8-quinoline sulfonamide 2q
gave mostly racemates. Consequence of ortho substitution
was less pronounced for fluorine, thus, it indicates that steric
interactions were involved. Methanesulfonamide 2t was
Entry
Catalyst
1a
NR2
pyrrolidine
piperidine
azepane
Ee, %a)
90
1
2
3
4
5
6
7
8
comparable in performance to benzenesulfonamide 2i
;
2a
93
3a
90
however, both bulkier and more electron withdrawing
4a
morpholine
dimethylamine
NH2
90
aliphatic sulfonamides 2u-v exhibited inferior catalytic
5a
86
performance.
6a
31
In the dimeric C2-symmetric sulfonamides (Figure 3, Table 1
entries 25-27) the individual units seem to operate
independently and offer no boost in enantioselectivity. The
4,4’-biphenyl disulfonamide 2x was almost identical in
7a
cyclohexylamine
1,2,3-triazole
11
9b)
8a
a) Reaction conditions: 10 %mol catalyst in toluene at room temperature for 24 h,
catalytic product (4S)-11a, with one exception the conversions were complete.
b) In this case conversion of 9a was approx. 15%.
performance to the unsubstituted benzenesulfonamide 2i
.
Benzene-1,3-disulfonamide 2w was a noticeably more
selective catalyst, but its increased performance could be
equally well explained by the role of the meta-sulfonamide
group as an electron withdrawing residue. Also, the smallest
of the dimers, sulfamide 2y exhibited moderate
enantioselectivity.
When 2a was compared with analogous thiourea and
squaramide derivatives (Figure 1) it was found to be a more
selective catalyst, although by a narrow margin (93 %ee vs 92
and 90 %ee, respectively). This marks one of the first cases
where these classical catalysts are quite effective but still
outperformed by a rather simple sulfonamide.
The same configuration of catalytic product (4S)-11a obtained
with different analogues of
2 including three-point binding
catalysts suggest related activation pathways.8c,10 It can be
assumed that the role of the tertiary amine is to bind and
deprotonate nucleophile 10, while the acidic NH interacts with
the 1,2-dicarbonyl unit of 9a, arranging it for attack from the Si
face. Aryl sulfonyl groups may additionally shield 9a from the
Re side (Figure 4).
Figure 3. Structures of dimeric sulfonamides and sulfamide
In contrast, the type of tertiary amine had a negligible impact
on the enantioselectivity.
derivatives were slightly better than all the other groups
tested (Table 2). It was surprising to see an almost equal
performance by morpholine derivatives , despite their very
Nevertheless, the piperidine
2
4
different basicity. Still, replacement of the tertiary amine with
a secondary amine of comparable size or with a triazole ring
were both detrimental to the observed enantioselectivity.
Also, a catalyst with a primary amine 6a led to a poor
stereochemical outcome. These results indicate that an
aliphatic tertiary amine unit was essential for the
enantioselectivity, but neither the bulkiness of the surrounding
groups nor altering their electronic character affected the
Figure 4. Plausible explanation of stereochemistry observed in the Michael-
hemiacetalization sequence
Attempts to observe interaction between the catalyst 2a, and
1
the substrates of the catalytic reaction using H NMR titration
were not conclusive. Only the broad resonance attributed to
the NH group of 2a was affected by addition of dimedone,
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while no spectral changes were observed by separate addition within 4 days. These results were reproduced on scales
of benzylidenepyruvate 9a (For the details, see: ESI). ranging from 0.1 to 3 mmoles with 98% preparative yield
We correlated the catalyst performance in terms of selectivity (Scheme 3). Alternatively, product of such purity could be
with the highest calculated oscillation frequency, obtained by enrichment of samples by slow recrystallization
corresponding to the N-H stretching band, at the from tert-butyl methyl ether. However, the efficiency of such
DFT/B3LYP/CC-pVDZ level of theory. This value can be treated crystallization was rather low (ca. 45%).
as one of the predictors of intrinsic acidity.13 It turned out that
there exists a trend within this class of catalysts that the lower
the calculated frequency the higher the enantioselectivity
(Figure 5, for details, see ESI).
Figure 6. The effect of catalyst 2a loading on enantioselectivity of (4S)-11a in
chlorobenzene at room temperature. Reactions with 0.5-10 %mol loading were run for
24 h, reactions with 0.05-0.5 %mol loading were run for 96 h.
Figure 5. Correlation between enantiomeric excess for 11a and DFT calculated unscaled
Also, a short study on the scope of substrates was performed
frequency of the N-H stretching band. The Pearson coefficient for the fitted line is
employing the catalyst 2a (Table 4). High enantioselectivities
were achieved with acceptors of varied aromatic substitution
(entries 2-5) or with a different ester (entry 6). However,
replacement of the phenyl group with cyclohexyl in the
acceptor led to a new product 11b with incomplete conversion
(45% isolated yield) and only moderate enantioselectivity.
−0.83. Results for 2,6-disubstituted benzenesulfonates and quinoline-sulfonamide
providing nearly racemic products were excluded from the fit (marked in red
)
The enantioselectivity of the catalytic reaction using 2a was
improved to 96% after replacing solvent with chlorobenzene
(Table 3). Also, the amount of catalyst 2a could be reduced
from the original 10 %mol (Figure 6). To our delight, we have
found that lowering the catalyst loading down to 0.25 %mol
did not significantly affect the enantioselectivity (93%) and
yield (90%). A drop in catalyst performance was eventually
observed at loadings below 0.1 %mol. Nevertheless, even at
0.05 %mol (500 ppm) moderate enantioselectivity was
achieved, albeit after an extended reaction time. The
experiments with both 10 and 0.5 %mol catalyst 2a were
repeated using an enantiomer ent-2a and the enantiomeric
ratios were consistently reversed.
Table 4. Application of different Michael acceptors
O
O
OH
CO2R1
O
*
2a
(10%mol)
PhCl
O
+
R
CO2R1
rt
O
R
9b-e
10
11b-e
Entry
1
R
OR1
Product
11b
Yield, %
45
Ee, %a)
79b)
cyclohexyl
4-FC6H4
4-FC6H4
4-ClC6H4
4-ClC6H4
Ph
OMe
OMe
OMe
OMe
OMe
OBn
2
3d)
11c
92
96 (43)c)
11c
79
95 [>99]d)
93 (96)c)
91 [>99]d)
96
4
11d
93
Table 3. Effect of solvent on stereoselectivity
5d)
6
11d
91
Entry
Solvent
toluene
Ee, %a
93
11e
93
1
2
3
4
a)
Reaction conditions: 0.1-mmol scale, 10 %mol 2a in chlorobenzene at room
α,α,α-trifluorotoluene
chlorobenzene
dichloromethane
93
temperature for 24 h, all products of 4S configuration. b) Reaction run for 96 h up
96
c)
to 50% conversion. Values in parentheses were obtained in reactions run for
96
120 h at −20°C. d) Reaction conditions: 3-mmol scale, 1 %mol 2a in chlorobenzene
at room temperature for 96 h, values in square parentheses indicate ee after
single recrystallization from tert-butyl methyl ether.
a)
Reaction conditions: 10 %mol catalyst 2a at room temperature for 24 h,
catalytic product (4S)-11a, complete conversion
A few different nucleophiles were also tested. At room
temperature the enantioselectivities achieved starting from
coumarins and pyrone were slightly lower compared to
By lowering the reaction temperature down to −20 °C the
enantioselectivity increased above 99% for reactions using 1
%mol of the catalyst 2a. Complete conversions were achieved
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dimedone (Figure 7). However, these could be significantly
improved to no less than 95 %ee by lowering the temperature
to −40 °C.
Conclusion
We have demonstrated the first successful application of chiral
diaminocyclohexane-derived sulfonamides in catalytic
a
Michael-hemiacetalization reaction. It was proved that a
single site hydrogen bond donor in combination with a tertiary
amine can provide simple catalysts enabling high
OH
CO2Me
OH
CO2Me
OH
CO2Me
O
O
O
O
O
stereoselectivity for the Michael-adducts.
performances were observed when
The best
O
Ph
O
Ph
O
Ph
the catalyst
11f
11g
11h
99 % yield,
95 (82) %ee
99 % yield,
96 (88) %ee
99 % yield,
98 (90) %ee
benzenesulfonyl group possessed inductively electron
withdrawing substituents at the meta positions. High
Figure 7. Products obtained from different nucleophiles and 9a with 10 %mol 2a in
chlorobenzene at −40 °C for 48 h. Values in parentheses indicate %ee obtained for
reactions run at room temperature
enantioselectivity was maintained even at exceptionally low
catalyst loadings.
The synthetic utility of the asymmetric adduct 11a was proved
in reactions leading to enantioenriched dihydropyridine and
tetrahydropyridine derivatives 12 and 13 (Scheme 3). Both
products are amino acid derivatives analogous to biologically
active molecules.14 The formation of a hydroquinoline ring in
12 was accomplished by heating of the chiral adduct with an
excess of ammonium acetate.11 Compound 13 was obtained
from 11a in a one-pot sequence of transformations involving
Conflicts of interest
There are no conflicts to declare
Acknowledgements
The research was founded by NCN, Poland No.
2016/22/E/ST5/00046 for hydrogen bond donor; and No.
2013/11/D/ST5/02909 for heterocyclic chemistry parts. The
authors are grateful to Mr. Nicholas Swisher, Caltech, and dr.
Ingo Schiffers, RWTH Aachen, for comments on the
manuscript.
imine formation, transamination and
a final cyclization.
Overall, both processes occurred with little erosion of optical
purity, and in the case of 13 with high diastereoselectivity.8a
The relative configuration was established by a combined DFT
and NMR approach (for the details, see ESI)
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Experimental Section
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1
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Catalysis Science & Technology
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DOI: 10.1039/C8CY01199K
TOC entry
Simple sulfonamide organocatalysts delivers unparalleled efficiency in the asymmetric Michael-
hemiacetalization cascade.