Synthesis of 1,1′-Spirobiindane-7,7′-Disulfonic Acid and Disulfonimide: Application for Catalytic Asymmetric Aminalization

Article abstract of DOI:10.1002/asia.201800341

1,1′-Spirobiindane-7,7′-disulfonic acid (SPISA) and 1,1′-spirobiindane-7,7′-disulfonimide were synthesized from 1,1′-spirobiindane-7,7′-diol (SPINOL) in 4 steps using a Pd-catalyzed Newman–Kwart rearrangement as a key step. These new catalysts possessing

Full text of DOI:10.1002/asia.201800341

CHEMISTRY
AN ASIAN JOURNAL
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Accepted Article
Title: Synthesis of 1,1'-Spirobiindane-7,7'-Disulfonic Acid and
Disulfonimide: Application for Catalytic Asymmetric Aminalization
Authors: Takumaru Kurihara, Shun Satake, Manabu Hatano, Kazuaki
Ishihara, Tatsuhiko Yoshino, and Shigeki Matsunaga
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10.1002/asia.201800341
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Synthesis of 1,1’-Spirobiindane-7,7’-Disulfonic Acid and
Disulfonimide: Application for Catalytic Asymmetric
Aminalization
Takumaru Kurihara,[a] Shun Satake,[a] Manabu Hatano,[b] Kazuaki Ishihara,[b] Tatsuhiko Yoshino,*[a] and
Shigeki Matsunaga*[a]
Abstract: 1,1’-Spirobiindane-7,7’-disulfonic acid (SPISA) and 1,1’-
spirobiindane-7,7’-disulfonimide were synthesized from 1,1’-
spirobiindane-7,7’-diol (SPINOL) in 4 steps using Pd-catalyzed
Newman-Kwart rearrangement as a key step. These new catalysts
possessing a rigid spirocyclic backbone were evaluated in a catalytic
asymmetric aminalization reaction, and SPISA/iPr2NEt exhibited high
enantioselectivity, demonstrating the utility of SPISA as a chiral
Brønsted acid catalyst.
Chiral Brønsted acid catalysts are powerful tools for the
stereoselective construction of C-C and C-hetero atom bonds in
modern organic synthesis.[1] Among a variety of catalysts reported
to date, chiral 1,1’-binaphthyl-2,2’-disulfonic acids (BINSAs) and
their disulfonimide derivatives (Figure 1, top)[2,3] are attractive in
terms of their stronger Brønsted acidity compared with chiral
phosphoric acids and carboxylic acids.[1] In addition to working as
Figure 1. Structures of BINSA (1,1’-binaphthyl-2,2’-disulfonic acid), SPISA
(1,1’-spirobiindane-7,7’-disulfonic acid), and their disulfonimide derivatives
a Brønsted acid, these catalysts can be used as ligands for a
metal
center[3b]
and
chiral
anions
to
control
enantioselectivity.[3c,e,k,l,4] Their versatility and efficient catalytic
activity have prompted chemists to pursue the steric and
electronic tuning of these catalysts.[3c,f,g,j] In general, catalytic
asymmetric synthesis often requires fine-tuning of the catalyst to
achieve high enantioselectivity with specific substrates, and
increasing the diversity of available catalyst structures is crucial.
Here we report the synthesis of 1,1’-spirobiindane-7,7’-
enantioselectivity in transition metal-catalyzed reactions.
Although chiral phosphoric acids possessing the spirocyclic core
were also reported,[11] syntheses of SPISA 1 and sulfonimide 2
have not yet been reported.[12]
We synthesized 1 and 2 from (R)-SPINOL 3 using a route
similar to that used for BINSA (Scheme 1).[3a,3d,13,14]
Thiocarbamoylation of the phenolic hydroxy groups of 3 under the
reported conditions for BINOL (NaH, Me2NC(S)Cl, DMF,
85 °C)[3a,3d] resulted in poor conversion, but changing the base to
DABCO[15] significantly enhanced the reactivity, providing 4 in
81% at room temperature. With the precursor for key Newman-
Kwart rearrangement (NKR) in hand, we investigated several
conditions for NKR as shown in the table in Scheme 1.[16]
Although thermal conditions, which are usually used for the
synthesis of BINSA, afforded a complex mixture, Pd-catalyzed
NKR reported by Lloyd-Jones et al.[16b] furnished the desired
product 5 in 86% yield. We also tried NKR under photo-redox
catalysis using 6 reported by Nicewicz et al.,[16c] but the reaction
barely occurred. Oxidation of 5 using N-chlorosuccinimide (NCS)
in MeOH/THF smoothly proceeded to give disulfonyl chloride 7,
and subsequent hydrolylsis and protonation afforded (R)-SPISA
1. Disulfonimide 2 was also obtained in 89% yield by treating 7
with gasous ammonia.
disulfonic acid (SPISA)
1
and 1,1’-spirobiindane-7,7’-
disulfonimide 2 (Figure 1, bottom). The 1,1’-spirobiindane
structure is an axially chiral backbone that is more rigid and less
flexible than a 1,1‘-binaphthyl backbone. The rigidity is sometimes
beneficial in asymmetric catalysis because the conformational
ambiguity in an enantio-determining step can be omitted. A variety
of chiral ligands were synthesized from 1,1’-spirobiindane-7,7’-
diol (SPINOL) 3 by Zhou[5-8] and others,[9,10] and exhibited
excellent
[a]
[b]
T. Kurihara, S. Satake, Dr. T. Yoshino, Prof. Dr. S. Matsunaga
Faculty of Pharmaceutical Sciences
Hokkaido University
Kita-12 Nishi-6, Kita-ku, Sapporo 060-0812 (Japan)
E-mail: tyoshino@pharm.hokudai.ac.jp;
smatsuna@pharm.hokudai.ac.jp
Dr. M. Hatano, Prof. Dr. K. Ishihara
Graduate School of Engineering
To evaluate the catalytic activity as a Brønsted acid as well as
the stereoinduction efficiency of 1 and 2, we selected catalytic
asymmetric aminalization of Cbz-protected imines with
Nagoya University
Furo-cho, Chikusa, Nagoya 464-8603 (Japan)
Supporting information for this article is given via a link at the end of
the document.
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10.1002/asia.201800341
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Scheme 1. Synthesis of (R)-SPISA 1 and disulfonimide 2 from (R)-SPINOL 3.
carboxamides, which were previously reported using BINSA,[3i,17]
as a model reaction. Optimization of the reaction conditions using
8a and 9a is summarized in Table 1. The use of 1 or 2 as a sole
catalyst promoted the reaction in the presence of MgSO4 as
desiccant in CH2Cl2 at 0 °C, but low enantioselectivities were
observed (entries 1 and 2). We next investigated the effect of
amine additives using disulfonic acid 1 as the catalyst. Formation
of the mono ammonium salt of 1 was expected to improve the
enantioselectivity because the ammonium moiety can increase
steric bulkiness around the catalytic site without introducing ortho-
substituents.[3i,18] Screening of various amines (entries 3–8)
revealed that iPr2NEt was the best additive, affording 10aa in 84%
ee. In the previous report using BINSA,[3i] 2,6-diarylpyridines were
effective additives in terms of enantioselectivity. In contrast, bulky
trialkylamines were clearly better than 2,6-Ph2-pyridine (entry 3,
14% ee) in this case, indicating that the chiral environment of
SPISA 1 differs somewhat from that of BINSA. Although neither
changing the solvent nor changing the dessicant further improved
the result (entries 9–13),[19] higher enantioselectivity was obtained
by performing the reaction at –40 °C for 12 h (entry 14). Under the
optimized conditions, 10aa was obtained in 75% yield and 93%
ee.[20]
The substrate scope of the (R)-SPISA 1-catalyzed
enantioselective aminalization under the optimized conditions is
shown in Scheme 2. The substituent of the aromatic
carboxamides had almost no effect on the enantioselectivity, and
the products were obtained in moderate to good yield and with
high enantioselectivity (10aa–10ac).[21] Acrylamide 9d was also
compatible under the same conditions, although the
enantioselectivity was slightly diminished (10ad). In addition to
imine 8a, both electron-rich and electron-deficient imines gave
high enantioselectivity (10ba–10bc, 10ca).
Brønsted acid catalysis as well as asymmetic counteranion-
directed catalysis.[4] Further application of (R)-SPISA 1 and
disulfonimide 2 as well as their structural tuning at the 6,6’-
positions are ongoing.
Table 1. Optimization for enantioselective aminalization.[a]
Entry
Catalyst
Amine
none
none
Desiccant
MgSO4
Solvent
CH2Cl2
CH2Cl2
% Yield[b]
% ee[c]
7[d]
1
2
1
2
82
88
MgSO4
31
2,6-Ph2-
pyridine
3
1
MgSO4
CH2Cl2
84
14
4
1
1
1
1
1
1
1
1
1
1
1
Me2NBu
Me2NCy
Bu3N
MgSO4
MgSO4
MgSO4
MgSO4
MgSO4
MgSO4
MgSO4
MgSO4
MS4A
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
toluene
THF
>95
49
42
64
75
54
58
68
70
81
75
66
73
75
83
84
67
43
75
79
83
93
5
6
7
Cy2NMe
iPr2NEt
iPr2NEt
iPr2NEt
iPr2NEt
iPr2NEt
iPr2NEt
iPr2NEt
8
9
10
11
12
13
14[e]
DCE
CH2Cl2
CH2Cl2
CH2Cl2
In summary, we synthesized (R)-SPISA 1 and disulfonimide 2 in
4 steps from (R)-SPINOL 3 using Pd-catalyzed Newman-Kwart
rearrangement as a key step. These new chiral Brønsted acid
catalysts were evaluated in the catalytic asymmetric aminalization
of imines 8 and carboxamides 9, and the combination of 1 and
iPr2NEt exhibited high enantioselectivity. These catalysts can be
a useful and good option for the development of asymmetric
Drierite®
MgSO4
[a] Reactions were run using 8a (0.30 mmol), 9a (0.20 mmol), catalyst (0.01 mmol,
5 mol %), amine (0.01 mmol, 5 mol %), and MgSO4 (0.34 mmol), MS4A (40 mg), or
Drierite® (40 mg) in solvent (1.0 mL) at 0 °C for 1 h unless otherwise noted. [b]
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Isolated yield. [c] Determined by chiral HPLC analysis. See Supporting Information
for more details. [d] The opposite enantiomer was obtained as a major product. [e] –
40 °C, 12 h.
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L.-X. Wang, Q.-L. Zhou, Tetrahedron: Asymmetry 2006, 17, 634-641; c)
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S. Li, Q.-L. Zhou, J. Am. Chem. Soc. 2006, 128, 12886-12891; b) J.-B.
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Scheme 2. Substrate scope of (R)-SPISA 1-catalyzed asymmetric
aminalization.
Acknowledgements
This work was supported in part by JSPS KAKENHI Grant
Number JP15H05802 and 15H05810 in Precisely Designed
[9]
J. Zheng, W.-J. Cui, C. Zheng, S.-L. You, J. Am. Chem. Soc. 2016, 138,
5242-5245.
Catalysts with Customized Scaffolding, JSPS KAKENHI Grant
Number JP17K15417, and The Uehara Memorial Foundation
(S.M.).
[10] A chiral phosphine was used as a organocatalyst: Y. K. Chung, G. C. Fu,
Angew. Chem. 2009, 121, 2259-2261; Angew. Chem. Int. Ed. 2009, 48,
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[12] Although the pKa of 2 was estimated by DFT calculations, the synthesis
has not been reported: C. Yang, X.-S. Xue, X. Li, J.-P. Cheng, J. Org.
Chem. 2014, 79, 4340-4351.
Keywords: chiral Brønsted acid • 1,1’-spirobiindane • disulfonic
acid • disulfonimide • aminalization
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further investigation.
[19] The effect of Mg2+ as a Lewis acid cannot be ruled out, but would be
limited, because almost comparable results were obtained with other
desiccants.
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[20] When we performed a reaction for 20 min under the optimized conditions
(Table 1, entry 14), 10aa was obtained in 28% yield and 93% ee,
indicating that no racemization of 10aa occurred under these conditions.
[21] The optical rotation of 10ab was opposite to that of the (S)-isomer
reported in reference [3i]. Thus, the absolute configuration of 10ab was
determined to be (R).
[18] Although 2 showed better enantioselectivity than 1, we considered 1
would be suitable for this acid-base combined catalysis because 1 has
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Entry for the Table of Contents (Please choose one layout)
COMMUNICATION
New chiral Brønsted acid catalysts
with a spirocyclic backbone were
developed. SPISA and its
disulfonimide were synthesized from
SPINOL using Pd-catalyzed Newman-
Kwart rearrangement as a key step,
and evaluated in a catalytic
asymmetric aminalization reaction.
These new catalysts can provide a
new good option for the development
of asymmetric catalysis.
Takumaru Kurihara, Shun Satake,
Manabu Hatano,Kazuaki Ishihara,
Tatsuhiko Yoshino,* and Shigeki
Matsunaga*
Page No. – Page No.
Synthesis of 1,1’-Spirobiindane-7,7’-
Disulfonic Acid and Disulfonimide:
Application for Catalytic Asymmetric
Aminalization
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