Tetrahedron Letters 61 (2020) 152122

Contents lists available at ScienceDirect

Tetrahedron Letters
journal homepage: www.elsevier.com/locate/tetlet

Diastereoselective direct amidation/aza-Michael cascade reaction

to synthesize cis-1,3-disubstituted isoindolines
Tetsuya Tsujihara a,⇑, Hazuki Yamauchi a, Satoru Tamura a, Tsunayoshi Takehara b, Takeyuki Suzuki b,
Tomikazu Kawano a,⇑
a
Department of Medicinal and Organic Chemistry, School of Pharmacy, Iwate Medical University, Yahaba, Iwate 028-3694, Japan
b
Comprehensive Analysis Center, Institute of Scientific and Industrial Research, Osaka University, Mihogaoka, Ibaraki 567-0047, Japan

a r t i c l e i n f o a b s t r a c t

Article history: A convenient and efficient base-promoted cascade reaction for the synthesis of cis-1,3-disubstituted
Received 16 May 2020 isoindolines has been reported herein. We discovered that various N-protected imines bearing a
Accepted 4 June 2020 Michael acceptor react smoothly with several nitrogenous nucleophiles in the presence of 1,8-diazabicy-
Available online 12 June 2020
clo[5.4.0]-7-undecene under mild conditions. cis-1,3-Disubstituted isoindolines bearing aminal function-
ality were assembled as a single diastereomer in moderate to good yields (52%–94%). This cascade
Keywords: process features the direct amidation of imines followed by the intramolecular aza-Michael reaction.
Cascade reaction
Ó 2020 Elsevier Ltd. All rights reserved.
Isoindoline
Direct amidation
Aza-Michael reaction

Introduction Aminals, which are nitrogen equivalents of acetals, are attrac-

The isoindoline moiety is widely found in a variety of natural
products, biologically active molecules, and pharmaceuticals [1].
Due to the interesting biological activity and the potential applica-
tion of isoindolines, many efforts have been devoted to develop
novel synthetic methods for isoindoline [2–4]. Among such meth-
ods, cascade and domino processes [5] have been utilized in the
efficient synthesis of 1,3-disubstituted isolindolines [6,7]. Enders
et al. developed a chiral phosphoramide-catalyzed tandem aza-
Friedel-Crafts reaction/intramolecular aza-Michael reaction
(IMAMR) for the first asymmetric synthesis of 1,3-disubstituted
isoindolines [6a]. More recently, Singh et al. reported the
synthesis of enantioenriched 1,3-disubstituted isoindolines and
tetrahydroisoquinolines using a Cu-catalyzed one-pot three-
component imination/alkynylation/IMAMR sequence [6f]. In
these studies, prepared or in-situ generated N-protected aryl
aldimines bearing a Michael acceptor at the ortho position
underwent 1,2-additions by the appropriate nucleophiles to yield
intermediate nitrogenous nucleophiles, which reacted further in
IMAMR. Although such cascade and domino strategies are
suitable for the construction of 1,3-disubstituted isoindoline
scaffolds, the nucleophiles for the initial 1,2-addition are limited
to carbon nucleophiles so far [8].
⇑ Corresponding authors.
E-mail addresses: ttsujiha@iwate-med.ac.jp (T. Tsujihara), tkawano@iwate-med.
ac.jp (T. Kawano).
tive structural motifs found in natural products and pharmaceuti-
cals [9]. Recently, the catalytic asymmetric synthesis of aminals
from imines by direct amidation in the presence of chiral acids
or bases has been studied [10]. Moreover, the synthesis of cyclic
aminals by direct amidation of imines has also been reported
[11]. Hence, we envisaged that the direct amidation of imines 1
using nitrogenous nucleophiles 2 yields the intermediate nitroge-
nous anions, and the subsequent IMAMR results in a variety of
1,3-disubstituted isoindoline-aminal hybrid compounds 3
(Scheme 1) [12,13]. Due to the interesting biological activity of
isoindolines and aminals, the synthesis of novel isoindoline deriva-
tives is valuable for expanding chemical space in medicinal and
organic chemistry. Herein, we report the diastereoselective direct
amidation/IMAMR cascade process of 1 and 2 in the presence of
a base.
Results and discussion
We began our study by examining the reaction of N-tosylimine
1a and p-toluenesulfonamide 2a under basic conditions (Table 1).
After the screening of various inorganic and organic bases (entries
1–7), it was found that 1,8-diazabicyclo[5.4.0]-7-undecene (DBU)
was viable for the desired direct amidation/IMAMR cascade pro-
cess. Namely, the desired 1,3-disubstituted isoindoline 3aa was
obtained in 66% yield as a single cis-isomer (entry 7). We then
investigated the effects of the solvent to improve the yield of cis-

https://doi.org/10.1016/j.tetlet.2020.152122
0040-4039/Ó 2020 Elsevier Ltd. All rights reserved.
2 T. Tsujihara et al. / Tetrahedron Letters 61 (2020) 152122

Scheme 1. Schematic representation of the direct amidation/intramolecular aza-

Michael reaction (IMAMR) cascade.
Fig. 1. POV-ray drawing of cis-3aa with probability ellipsoids drawn at the 50%
level. Hydrogen atoms, except for important ones, are omitted for clarity. (a) Side
view and (b) front view.
Table 1
Optimization of the reaction conditions.a

Table 2
Scope of Imines 1.a

Entry Base (equiv.) Solvent cis-3aa/%b

1 KOt-Bu (1.0) THF 64
2 NaOMe (1.0) THF 43 Entry 1 EWD R1 Ar 2 cis-3/%b
3 K2CO3 (1.0) THF 13
4 NaH (1.0) THF 58 1 1a CO2Me H p-tol 2a 3aa, 89
5 Et3N (1.0) THF 0 2 1b CO2Et H p-tol 2a 3ba, 94
6 Py (1.0) THF 0 3c 1c CO2t-Bu H p-tol 2a 3ca, 81
7 DBU (1.0) THF 66 4 1d CO2Bn H p-tol 2a 3da, 92
8 DBU (1.0) 1,4-dioxane 62 5d 1e CN H p-tol 2a 3ea, 88
9 DBU (1.0) DME 53 6 1f CO2Me Me p-tol 2a 3fa, n.d.e
10 DBU (1.0) MeCN 87 7 1g CO2Me H Ph 2b 3gb, 87
11 DBU (1.0) DMF 58 8 1h CO2Me H 4-ClC6H4 2c 3hc, 91
12 DBU (1.0) CH2Cl2 76 9 1i CO2Me H p-anisyl 2d 3id, 90
13 DBU (1.0) toluene 88 a
DBU (0.075 mmol, 1.5 equiv.) was added to the solution of 1 (0.050 mmol) and 2
14c DBU (1.5) toluene 92 (89)d
(0.10 mmol, 2.0 equiv.) in dry toluene (1.0 mL) under an argon atmosphere.
15c,e DBU (0.20) toluene 80 b
Isolated yields.
16c,f DBU (0.50) toluene 83 c
For 2 h.
d
a
Base (0.050 mmol, 1.0 equiv.) was added to the solution of 1a (0.050 mmol) and In dry toluene/MeCN (2:1, 1.5 mL).
e
2a (0.055 mmol, 1.1 equiv.) in dry solvent (1.0 mL) under an argon atmosphere. Not determined due to the formation of a complex mixture.
b
Yields determined by NMR spectroscopy on the basis of benzyl 4-hydroxy-
benzoate as an internal standard.
c
2.0 equiv. of 2a was used.
d
Value in the parenthesis is isolated yield.
e
For 3 h.
cis-3aa–3ea in 81%–94% yields (entries 1–5). However, the use of
f
For 2 h. 1f, which bore a b-methyl substituent on an a, b-unsaturated ester
moiety, resulted in a complex mixture, and the desired product 3fa
was not detected (entry 6). The reactions of imines 1 g, 1 h, and 1i
3aa (entries 8–13). The desired cascade process of 1a and 2a pro- bearing benzenesulfonyl, 4-chlorobenzenesulfonyl, and p-anisole-
ceeded smoothly in toluene to result in cis-3aa in 88% yield (entry sulfonyl groups, respectively, with the corresponding arylsulfon-
13). Furthermore, 89% isolated yield of cis-3aa was obtained by amides 2b, 2c, and 2d proceeded smoothly to give cis-3gb, cis-
using 1.5 equiv. of DBU and 2.0 equiv. of 2a (entry 14). Although 3hc, and cis-3id in 87%–91% yields, respectively (entries 7–9).
the cascade reaction proved to be promoted well by the catalytic Next, the generality of the reaction was further investigated by
and substoichiometric amount of DBU (entries 15 and 16), 1.5 employing a variety of nitrogenous nucleophiles 2 (Table 3). Sev-
equiv. of DBU was selected as the optimum condition based on eral N-functionalized p-toluenesulfonamides were employed in
the yield of cis-3aa and the availability of DBU (entry 14). The the reactions (entries 1–4). N-Methyl (2e), allyl (2f), but-2-yn-1-
structure and relative configuration of cis-3aa were confirmed via yl (2 g), and 2-ethoxycarbonylmethyl (2 h) groups on nucleophilic
1
H and 13C NMR spectroscopy, mass spectrometry, and single- nitrogen were viable for the reaction and the corresponding prod-
crystal X-ray analysis (Fig. 1) [14]. As indicated by the X-ray struc- ucts cis-3ae–3ah were obtained in 52%–84% yields. Then, it was
ture of cis-3aa (Fig. 1b), the substituents at the 1 and 3 positions found that p-chloroaniline (2i) was a good nucleophile for the cas-
are located anti to the p-toluenesulfonyl group on the nitrogen. cade process to synthesize cis-3ai in high yield (93%) (entry 5).
Thus, the cis-isomer of 3 would be selectively formed to avoid Moreover, benzyl carbamate (2j) could also take part in this reac-
steric repulsions between each substituent. tion, thus producing cis-3aj in 59% yield (entry 6). However, the
Based on the optimized reaction conditions of the cascade pro- attempted use of benzylamine as a nucleophile was unfruitful (en-
cess, the scope of the reaction was studied. Initially, a variety of N- try 7).
protected imines 1 were tested (Table 2). The electron-deficient Based on the reaction of imine 1a and N-functionalized p-tolue-
alkenes, including various acrylic esters (1a–1d) and a nitrile (1e) nesulfonamides (2e–2 h), the direct amidation was determined to
[15], were viable in the synthesis of the corresponding products be the initial step in the cascade process (Table 3, entries 1–4). Sev-
 T. Tsujihara et al. / Tetrahedron Letters 61 (2020) 152122 3

Table 3 Conclusion
Scope of nitrogenous nucleophiles 2.a

In summary, we have developed a DBU-promoted direct amida-

tion/aza-Michael cascade process between nitrogenous nucle-
ophiles and N-protected imines bearing a Michael acceptor. Our
protocol provides facile access to unprecedented cis-1,3-disubsti-
tuted isoindolines bearing aminal functionality in moderate to high
yields. Since the aminal functionality might be transformed via the
formation of an N-sulfonyliminium cation [17], further derivatiza-
Entry 2 PG R2 Time/h cis-3/%b tions of the products are expected. Further expanding the scope of
1 2e Ts Me 1 3ae, 84 the reaction, the development of asymmetric cascade processes
2 2f Ts allyl 1 3af, 52 and the applications of the products are currently ongoing. Such
3 2g Ts CH2C„CCH3 1 3ag, 70 results will be reported in due course.
4 2h Ts CH2CO2Et 1 3ah, 53
5 2i 4-ClC6H4 H 1 3ai, 93
6 2j Cbz H 1 3aj, 59 Declaration of Competing Interest
7 2k Bn H 3 3ak, trace
a
DBU (0.075 mmol, 1.5 equiv.) was added to the solution of 1a (0.050 mmol) and
The authors declare that they have no known competing finan-
2 (0.10 mmol, 2.0 equiv.) in dry toluene (1.0 mL) under an argon atmosphere. cial interests or personal relationships that could have appeared
b
Isolated yields. to influence the work reported in this paper.

Acknowledgments

We thank Dr. Yasumitsu Sakamoto and Prof. Takamasa Nonaka

at Iwate Medical University for the measurement of X-ray crystal-
lographic analysis. We also acknowledge the technical staff of the
Comprehensive Analysis Center of Institute of Scientific and Indus-
trial Research, at Osaka University. This research didn’t receive any
specific grant from funding agencies in the public, commercial, or
not-for-profit sectors.

Appendix A. Supplementary data

Supplementary data (crystallographic data (Fig. S1) and full

details of structural parameters (Table S1) for cis-3aa, experimen-
tal procedures, characterization data, copies of 1H and 13C NMR
spectra for all new compounds). Supplementary data to this article
can be found online at https://doi.org/10.1016/j.tetlet.2020.
152122.

References

[1] Selected review and reports on natural products and pharmaceuticals

Scheme 2. Experiments for mechanistic study.
eral control experiments were designed to gain more insight into
the reaction mechanism of the direct amidation/IMAMR cascade
process (Scheme 2). The reaction between p-anisolesulfonyl imine
1i and 2a resulted in product cis-3ia with unexpected products
(cis-3ad, cis-3id, and cis-3aa) in 90% total yield (Scheme 2a). This
result indicated that the direct amidation step was reversible. Fur-
thermore, the reactions of isoindoline products cis-3aa and cis-3id
with 2d and 2a, respectively, under the optimized conditions,
afforded the aminal exchanged products cis-3ad and cis-3ia,
respectively (Scheme 2b and 2c). The aminal exchanges of cis-
3aa and cis-3id may have proceeded via a retro-Michael reaction
or the formation of an N-sulfonyliminium cation [16]. Although
the detailed explanation for this behavior is yet to be elucidated,
this phenomenon is an interesting feature from the perspective
of expanding product diversity.
containing isoindolines: (a) K. Speck, T. Magauer Beilstein J. Org. Chem. 9
(2013) 2048–2078;
(b) M. Goldstein, S. Kuga, N. Kusano, E. Meller, J. Dancis, R. Schwarcz, Brain Res.
367 (1986) 114–120;
(c) A.L. Jaton, R.K.A. Giger, J.M. Vigouret, A. Enz, W. Frick, A. Closse, R.
Markstein, Life Sci. 38 (1986) 155–163;
(d) Z. Hussein, D.J. Mulford, B.A. Bopp, G.R. Granneman, Br. J. Clin. Pharmacol.
36 (1993) 357–361;
(e) T. Kondo, K. Yoshida, S. Tanayama, Arzneimittelforschung 46 (1996) 839–
843;
(f) P.J. Kukkola, N.A. Bilci, T. Ikler, P. Savage, S.S. Shetty, D. DelGrande, A.Y. Jeng,
Bioorg. Med. Chem. Lett. 11 (2001) 1737–1740;
(g) G. Balandaram, L.R. Kramer, B.-H. Kang, I.A. Murray, G.H. Perdew, F.J.
Gonzalez, J.M. Peters, Toxicology 363–364 (2016) 1–9;
(h) H.J. Gim, Y.-S. Choi, H. Li, Y.-J. Kim, J.-H. Ryu, R. Jeon, Int. J. Mol. Sci. 19
(2018) 3032.
[2] For reviews: (a) M.I. Calaza, F.J. Sayago, P. Laborda, C. Cativiela Eur. J. Org.
Chem. (2015) 1633–1658;
(b) G. Albano, L.A. Aronica, Eur. J. Org. Chem. (2017) 7204–7221;
(c) A.M. Starosotnikov, M.A. Bastrakov, Chem. Heterocycl. Comp. 53 (2017)
1181–1183;
(d) G. Albano, L.A. Aronica, Synthesis 50 (2018) 1209–1227, and references
cited therein.
[3] Recent reports on the synthesis of isoindoline derivatives in racemic forms: (a)
G. Qiu, Z.-F. Chen, W. Xie, H. Zhou Eur. J. Org. Chem. (2019) 4327–4333;
(b) C. Tian, U. Dhawa, A. Scheremetjew, L. Ackermann, ACS Catal. 9 (2019)
7690–7696;
(c) M. Xu, Y. Yuan, Y. Wang, Q. Tao, C. Wang, Y. Li, Org. Lett. 21 (2019) 6264–
6269;
(d) M. Ratushnyy, N. Kvasovs, S. Sarkar, V. Gevorgyan, Angew. Chem. Int. Ed.
(2020), https://doi.org/10.1002/anie.201915962.
4 T. Tsujihara et al. / Tetrahedron Letters 61 (2020) 152122
[4] Recent reports on the asymmetric synthesis of isoindoline derivatives: (a) V.
Bisai, A. Suneja, V.K. Singh Angew. Chem. Int. Ed. 53 (2014) 10737–10741;
(b) M.S. Joshi, F.C. Pigge, ACS Catal. 6 (2016) 4465–4469;
(c) Z. Kang, D. Zhang, J. Shou, W. Hu, Org. Lett. 20 (2018) 983–986;
(d) T. Li, C. Zhou, X. Yan, J. Wang, Angew. Chem. Int. Ed. 57 (2018) 4048–4052;
(e) R.A. Unhale, M.M. Sadhu, S.K. Ray, R.G. Biswas, V.K. Singh, Chem. Commun.
54 (2018) 3516–3519.
[5] For relevant reviews: (a) L.F. Tietze, U. Beifuss Angew. Chem. Int. Ed. 32 (1993)
131–163;
(b) L.F. Tietze, Chem. Rev. 96 (1996) 115–136;
(c) H. Pellissier, Adv. Synth. Catal. 354 (2012) 237–294;
(d) C.M.R. Volla, I. Atodiresei, M. Rueping, Chem. Rev. 114 (2014) 2390–2431;
(e) F. Vetica, R.M. de Figueiredo, M. Orsini, D. Tofani, T. Gasperi, Synthesis 47
(2015) 2139–2184.
[6] Asymmetric synthesis of 1,3-disubstituted isoindolines by cascade or domino
process: (a) D. Enders, A.A. Narine, F. Toulgoat, T. Bisschops Angew. Chem. Int.
Ed. 47 (2008) 5661–5665;
(b) S. Fustero, J. Moscardó, M. Sánchez-Roselló, E. Rodríguez, P. Barrio, Org.
Lett. 12 (2010) 5494–5497;
(c) S. Takizawa, N. Inoue, S. Hirata, H. Sasai, Angew. Chem. Int. Ed. 49 (2010)
9725–9729;
(d) E.E. Maciver, P.C. Knipe, A.P. Cridland, A.L. Thompson, M.D. Smith, Chem.
Sci. 3 (2012) 537–540;
(e) S. Takizawa, M. Sako, M.A. Abozeid, K. Kishi, H.D.P. Wathsala, S. Hirata, K.
Murai, H. Fujioka, H. Sasai, Org. Lett. 19 (2017) 5426–5429;
(f) B.G. Das, S. Shah, V.K. Singh, Org. Lett. 21 (2019) 4981–4985.
[7] Recent reports on the synthesis of 1,3-disubstituted isoindolines: (a) B. Qian, S.
Guo, C. Xia, H. Huang Adv. Synth. Catal. 352 (2010) 3195–3200;
(b) F.J. Williams, E.R. Jarvo, Angew. Chem. Int. Ed. 50 (2011) 4459–4462;
(c) Z. He, T. Liu, H. Tao, C.-J. Wang, Org. Lett. 14 (2012) 6230–6233;
(d) H. Qian, W. Zhao, H.H.Y. Sung, I.D. Williams, J. Sun, Chem. Commun. 49
(2013) 4361–4363;
(e) S. Fustero, L. Herrera, R. Lázaro, E. Rodríguez, M.A. Maestro, N. Mateu, P.
Barrio, Chem. Eur. J. 19 (2013) 11776–11785;
(f) G. Pandey, R. Varkhedkar, D. Tiwari, Org. Biomol. Chem. 13 (2015) 4438–
4448;
(g) R. Achary, I.-A. Jung, H.-K. Lee, J. Org. Chem. 83 (2018) 3864–3878;
(h) S. Xing, H. Cui, J. Qin, N. Gu, B. Zhang, K. Wang, Y. Wang, L. Xia, Y. Wang,
Org. Chem. Front. 5 (2018) 1950–1956;
(i) Z. Feng, Z. Yuan, X. Zhao, Y. Huang, H. Yao, Org. Chem. Front. 6 (2019) 3535–
3539;
(j) Z.-R. Guan, Q. Wan, M.-W. Ding, Tetrahedron 75 (2019) 4626–4631.
[8] Indoles (ref. 6a), Ruppert–Prakash reagents (ref. 6b), enolates from electron-
deficient alkenes (ref. 6c), enolates from activated methyne compounds (ref
6d), phenols (ref. 6e), and Cu-acetylides from aryl acetylenes (ref. 6f) as carbon
nucleophiles have been utilized in the cascade reactions.
[9] (a) A. Alexakis, P. Mangeney, Advanced Asymmetric Synthesis, G. R.
Stephenson Springer, London, 1996, pp. 93–110;
(b) C. Ko, Synthesis Methods Using Cyclic Acetals and Aminals, ProQuest, Ann
Arbor, 2011;
(c) M.D. Fletcher, M.M. Campbell, Chem. Rev. 98 (1998) 763–796;
(d) A. Rouchaud, J.-C. Braekman, Eur. J. Org. Chem. (2009) 2666–2674;
(e) I. Bosque, J.C. Gonzalez-Gomez, M.I. Loza, J. Brea, J. Org. Chem. 79 (2014)
3982–3991;
(f) C.-E. Nge, C.-Y. Gan, K.-H. Lim, K.-N. Ting, Y.-Y. Low, T.-S. Kam, Org. Lett. 16
(2014) 6330–6333;
(g) Y. Ochi, S. Yokoshima, T. Fukuyama, Org. Lett. 18 (2016) 1494–1496;
(h) B.M. Williams, D. Trauner, Angew. Chem. Int. Ed. 55 (2016) 2191–2194.
[10] Recent reports on asymmetric synthesis of aminals: (a) G.B. Rowland, H.
Zhang, E.B. Rowland, S. Chennamadhavuni, Y. Wang, J.C. Antilla J. Am. Chem.
Soc. 127 (2005) 15696–15697;
(b) Y. Liang, E.B. Rowland, G.B. Rowland, J.A. Perman, J.C. Antilla, Chem.
Commun. (2007) 4477–4479;
(c) X. Cheng, S. Vellalath, R. Goddard, B. List, J. Am. Chem. Soc. 130 (2008)
15786–15787;
(d) M. Hatano, T. Ozaki, Y. Sugiura, K. Ishihara, Chem. Commun. 48 (2012)
4986–4988;
(e) T. Kurihara, S. Satake, M. Hatano, K. Ishihara, T. Yoshino, S. Matsunaga,
Chem. Asian J. 13 (2018) 2378–2381;
(f) S.Y. Park, Y. Liu, J.S. Oh, Y.K. Kweon, Y.B. Jeong, M. Duan, Y. Tan, J.-W. Lee, H.
Yan, C.E. Song, Chem. Eur. J. 24 (2018) 1020–1025.
[11] Recent reports on synthesis of cyclic aminals: (a) K. Ohmatsu, S. Kawai, N.
Imagawa, T. Ooi ACS Catal. 4 (2014) 4304–4306;
(b) J. Hu, B. Kong, Y. Liu, B. Xu, Y. Zhao, P. Gong, ChemCatChem 9 (2017) 403–
406;
(c) S. Mukhopadhyay, S.C. Pan, Chem. Commun. 54 (2018) 964–967;
(d) W. Shi, L. Zhou, B. Mao, Q. Wang, C. Wang, C. Zhang, X. Li, Y. Xiao, H. Guo, J.
Org. Chem. 84 (2019) 679–686.
[12] 1,3-Disubstituted isoindoline derivatives, such as 3, have been proposed as
reaction intermediates in a Cu-catalyzed aerobic domino process for the
synthesis of isoindolin-1-ylidene derivatives. H. Chen, Q. Wang, Y. Huang
Tetrahedron 71 (2015) 3632–3636.
[13] Trost et al. have reported one example of the stepwise synthesis of isoindoline
derivative such as 3 as the synthetic application of their asymmetric reaction
product. B.M. Trost, E. Gnanamani, C.-I. Hung Angew. Chem. Int. Ed. 56 (2017)
10451–10456.
[14] Complete crystallographic data for the structure analysis in this paper have
been deposited with the Cambridge Crystallographic Data Centre, CCDC No.
1996138 (3aa). Copies of the data can be obtained, free of charge, on
application to CCDC, 12 Union Road, Cambridge CB2 1EZ, UK, (fax: +44-(0)
1223-336033 or e-mail: deposit@ccdc.cam.ac.uk).
[15] When the cascade process was conducted using (Z)-1e instead of (E)-1e under
otherwise identical conditions, the same product cis-3ea was obtained in 95%
yield. See the supplementary data for details.
[16] For the plausible reaction mechanisms of aminal exchange, see the
supplementary data (Scheme S1).
[17] Transformation of aminals via the formation of an N-sulfonyliminium cations:
A. Armstrong, G.R. Cumming, K. Pike Chem. Commun. (2004) 812–813.