doi.org/10.1002/ajoc.

202100296 Communication

Iridium-Catalyzed [4 + 3] Cyclization of ortho-Tosylaminophenyl-

Substituted para-Quinone Methides with Vinylic Oxiranes/Vinyl
Aziridines
Junwei Wang+,* Lin Zhao+, Caihong Li, Lei Zhao, Kun Zhao, Yang Hu, and Lihong Hu*[a]

Abstract: An Iridium-catalyzed [4 + 3] cyclization of ortho-

tosylaminophenyl-substituted para-quinone methides with
vinylic oxiranes or vinyl aziridines has been successfully
developed. In the presence of [Ir(cod)Cl]2 and a suitable
base, this unprecedented cascade reaction occurs readily in
good yield (up to 97%) and high diastereoselectivity (dr >
20 : 1), providing a highly efficient synthetic approach to
synthetically valuable seven-membered heterocyclic frame-
works.

para-quinone methides (p-QMs), as a class of versatile building

blocks, have been widely used in cyclization reactions for the
construction of heterocyclic frameworks.[1] Among them, ortho-
hydroxyphenyl-substituted p-QMs and ortho-tosylaminophenyl-
substituted p-QMs are two powerful four-atom synthons. Since
the seminal reports by Enders[2] and Hu,[3] respectively, a large
number of [4 + 1][4] and [4 + 2][5] cyclization reactions were well-
established based on these two substrates to construct oxygen-
and nitrogen-containing heterocyclic frameworks (Scheme 1a).
However, compared to [4 + 1] and [4 + 2] cyclizations for the
synthesis of five- and six-membered skeletons, [4 + 3] cycliza-
tion for the construction of seven-membered skeletons are
much more challenging due to unfavorable entropic factors
and transannular interactions.[6,7] Therefore, [4 + 3] cyclizations
based on p-QMs for the synthesis of seven-membered hetero-
cycles remain underdeveloped.
Recently, Shi and co-workers developed an iridium-cata-
lyzed [4 + 3] cyclization of vinyl aziridines with ortho-hydrox-
yphenyl-substituted p-QMs for the construction of seven-
membered benzoxazepine scaffold.[8] Li and co-workers estab-
lished an NHC-catalyzed enantioselective [4 + 3] cycloaddition
of ortho-hydroxyphenyl-substituted p-QMs with isatin-derived
Scheme 1. Reported Reactions based on p-QMs and Our Design.
enals for the asymmetric synthesis of spirobenzoxopinones.[9]
Despite these elegant approaches, [4 + 3] cyclizations of p-QMs
are still rather limited, and the [4 + 3] cyclizations based on
ortho-tosylaminophenyl-substituted p-QMs has not been estab- lished yet. Therefore, it is necessary to develop more cycliza-
tions for the construction of structurally diverse seven-mem-
bered heterocyclic frameworks. To fulfill this task, we decided to
[a] Prof. J. Wang,+ L. Zhao,+ C. Li, L. Zhao, Dr. K. Zhao, Dr. Y. Hu, Prof. L. Hu develop a highly efficient [4 + 3] cyclization reaction based on
Jiangsu Key Laboratory for Functional Substances of ortho-tosylaminophenyl-substituted p-QMs to construct seven-
Chinese Medicine School of Pharmacy
Nanjing University of Chinese Medicine membered nitrogen heterocyclic skeletons. Nevertheless, the
Nanjing (P. R. China) key to the success is to find a suitable three-atom reaction
E-mail: jwwang@njucm.edu.cn partner which can readily take part in this [4 + 3] cyclization
lhhu@njucm.edu.cn
[+] These authors contributed equally.
reaction with ortho-tosylaminophenyl-substituted p-QMs.
Supporting information for this article is available on the WWW under Vinyl three-membered heterocycles have successfully uti-
https://doi.org/10.1002/ajoc.202100296 lized as three-atom synthetic blocks in organic synthesis

Asian J. Org. Chem. 2021, 10, 2152 – 2156 2152 © 2021 Wiley-VCH GmbH

because of their inherent ability to generate highly reactive
zwitterionic π-allyl metal intermediates under metal-catalysis.
Since Yamamoto’s pioneering work on the [3 + 2] cycloaddition
reaction of electron-deficient alkenes with vinylic oxiranes and
vinyl aziridines in 1998 and 2002, respectively,[10,11] a large
number of cyclization reactions based on vinylic oxiranes and
vinyl aziridines have been established by Zhang,[12] Zhao[13] and
Studer,[14] as well as many other groups (Scheme 1b).[15]
However, most vinylic oxiranes and vinyl aziridines involved
reactions are [3 + 2] cyclizations with electron-deficient alkenes
and [3 + 3] cyclizations with 1,3-dipoles, while the examples of
[4 + 3] cyclizations with four-atom synthons are very limited. In
particular, [4 + 3] cyclizations of vinylic oxiranes have not yet
been disclosed. Therefore, the development of [4 + 3] cycliza-
tions of vinylic oxiranes and vinyl aziridines is highly needed. To
achieve the above-mentioned goals and as part of our ongoing
efforts to construct nitrogen heterocyclic skeletons, we were
attracted to the possibility of [4 + 3] cyclization of vinylic
oxiranes or vinyl aziridines with ortho-tosylaminophenyl-sub-
stituted p-QMs (Scheme 1c). Herein, we report the investiga-
tions on this [4 + 3] cyclization reaction.
To verify our hypothesis, we chose ortho-tosylaminophenyl-
substituted p-QM 1 a and vinylic oxiranes 2 as model substrates
to test the feasibility of this designed [4 + 3] cyclization reaction
(Table 1). Initially, in the presence of Pd2(dba)3·CHCl3 catalyst
and BINAP ligand, the expected [4 + 3] cyclization occurred and
expected product 3 a was afforded. Albeit with low yield (27%),
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Communication
this initial result illustrated that our design was feasible.
Encouraged by this promising result, a series of phosphine
ligands were screened (entries 1–8). However, these phosphine
ligands failed to improve the yield, indicating that a suitable
catalyst was crucial for the success of this reaction. Therefore,
several other metal catalysts were examined (entries 9–13). We
were pleased to find that [Ir(cod)Cl]2 could promote this
transformation and increase the yield to 80% (entry 13). With
[Ir(cod)Cl]2 as the optimal catalyst, different bases were
examined subsequently (entries 14–18) and we found that
organic base Et3N performed best (entry 13). After establishing
the optimal catalyst and base, the influence of solvent was
examined, however, other solvents such as CHCl2, CHCl3,
acetonitrile and dioxane failed to improve the efficiency
(entries 19–22). Finally, the optimal reaction conditions were
selected as those shown in entry 13.
After establishing the optimized conditions, the generality
of this catalytic system was explored. We were pleased to find
that a wide range of p-QMs 1 could be easily reacted with
vinylic oxiranes 2 to afford the corresponding seven-membered
heterocyclic products 3 a–3 l in 76–90% yields with high
diastereoselectivity (dr > 20 : 1) (Scheme 2). In detail, p-QMs
bearing electron-neutral (R = H), electron-donating (R = Me) or
electron-withdrawing (R = F, Cl, Br) groups on the benzene ring
could easily undergo this reaction to deliver products 3 a–3 e in
good yields (76-87%). Changing the position of substituents has
little effect on the yield, the corresponding products 3 f–3 i were

Table 1. Reaction Condition Optimization Studies.[a]

entry catalyst ligand base solvent yield [%][b]

1 Pd2(dba)3·CHCl3 BINAP Et3N toluene 27

2 Pd2(dba)3·CHCl3 Xantphos Et3N toluene 0
3 Pd2(dba)3·CHCl3 DPEphos Et3N toluene 0
4 Pd2(dba)3·CHCl3 dppf Et3N toluene 21
5 Pd2(dba)3·CHCl3 dppbz Et3N toluene 10
6 Pd2(dba)3·CHCl3 dppe Et3N toluene 32
7 Pd2(dba)3·CHCl3 dppp Et3N toluene 7
8 Pd2(dba)3·CHCl3 dppb Et3N toluene 10
9 Pd(PPh3)4 Et3N toluene 0
10 [Cp*RhCl2]2 Et3N toluene 0
11 [RuCl2(p-cymene)]2 Et3N toluene 0
12 Co(C5H7O2)3 Et3N toluene 0
13 [Ir(cod)Cl]2 Et3N toluene 80
14 [Ir(cod)Cl]2 DBU toluene 27
15 [Ir(cod)Cl]2 DMAP toluene 30
16 [Ir(cod)Cl]2 Cs2CO3 toluene 70
17 [Ir(cod)Cl]2 K2CO3 toluene 26
18 [Ir(cod)Cl]2 KOH toluene 65
19 [Ir(cod)Cl]2 – Et3N CH2Cl2 34
20 [Ir(cod)Cl]2 – Et3N CHCl3 27
21 [Ir(cod)Cl]2 – Et3N CH3CN 40
22 [Ir(cod)Cl]2 – Et3N dioxane 55

[a] All reactions were carried out with 0.1 mmol of 1 a (1 equiv), 0.15 mmol of 2 (1.5 equiv) and 0.2 mmol of base (2.0 equiv) in solvent (1.5 mL) at room
temperature for 3 h. [b] Determined by 1H NMR using 1,3,5-trimethoxybenzene as an internal standard, all dr > 20 : 1.

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Communication
several attempts, we found that organic base DMAP performed
best, delivering 5 a in 91% yield.
With the optimal reaction conditions in hand, we continued
to explore the substrate scope of the [4 + 3] cyclization between
p-QMs and vinyl aziridines. As shown in Scheme 3, p-QMs 1
bearing different substituents on the benzene ring could
smoothly participate in the reaction and afford the expected
products 5 a–5 h in excellent yields (90–97%). The position and
electronic properties of substituents on the benzene ring have
little effect on the reaction efficiency. Moreover, the change of
N-protecting group also does not affect the efficiency of this
reaction, and the corresponding products 5 i–5 k were obtained
in 67–93% yields. The structure and relative configuration of

Scheme 2. Generality of the [4 + 3] Cyclization between p-QMs and Vinylic

Oxiranes. All reactions were carried out with 0.1 mmol of 1, 0.15 mmol of 2,
0.005 mmol of [Ir(cod)Cl]2 and 0.2 mmol of Et3N in toluene (1.5 mL) at room
temperature for 3 h. Yields reported were isolated yields. All dr > 20 : 1 and
all products are racemic.

obtained in 80–86% yields. Moreover, the reaction efficiency

was less affected by the N-protecting group, and the corre-
sponding products 3 j–3 l were obtained in high yields (80–
90%). The structure and relative configuration of this series of
products was determined by the single-crystal X-ray diffraction
analysis of 3 a.[16]
Subsequently, to investigate whether this [4 + 3] cyclization
is suitable for vinyl aziridines. The reaction of p-QM 1 a and vinyl
aziridines 4 was carried out under above standard conditions.
To our delight, the expected reaction occurred and the [4 + 3]
adduct 5 a was obtained in 83% yield with high diastereose- Scheme 3. Generality of the [4 + 3] Cyclization between p-QMs and Vinyl
Aziridines. All reactions were carried out with 0.1 mmol of 1, 0.15 mmol of 4,
lectivity (dr > 20 : 1). Based on this promising result, we inves- 0.005 mmol of [Ir(cod)Cl]2 and 0.2 mmol of DMAP in toluene (1.5 mL) at
tigated different bases because the appropriate base is room temperature for 5 h. Yields reported were isolated yields. All dr > 20 : 1
beneficial to improve the reaction efficiency (not shown). After and all products are racemic.

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Communication
this series of products was unambiguously assigned by the
single-crystal X-ray diffraction analysis of 5a.[16]
After completing the research on the generality of the
[4 + 3] cyclization, we turned to evaluate the robustness and
practicality of this protocol. First, scale-up reactions were carried
out under standard conditions. As depicted in Scheme 4, when
the [4 + 3] cyclizations between p-QMs and vinylic oxiranes or
vinyl aziridines were carried out in 1 mmol scale, the corre-
sponding products 3 a and 5 a were isolated in 80% and 90%
yields, respectively. Then, the synthetic transformations of 3 a
were performed to evaluate the practicality of the cyclization
product. The catalytic hydrogenation of 3 a in the presence of
Pd/C afforded the hydrogenated product 3 aa in 60% yield
(Scheme 5a). In addition, 3 a could undergo olefin metathesis in
the presence of Grubbs II catalyst, offering product 3 ab in an
acceptable yield (41%) (Scheme 5b).
Scheme 6. The Plausible Mechanism.
Finally, a plausible mechanism was suggested as shown in
Scheme 6. We proposed that the amino group of the ortho-

tosylaminophenyl-substituted p-QMs could form a highly

nucleophilic nitrogen anion in the promotion of a base, which
would attack the zwitterionic π-allyl metal intermediate I to
generate transient intermediate II. Then, an intramolecular oxa/
aza-1,6-addition would result in a [4 + 3] cyclization to give the
corresponding seven-membered scaffold.

Conclusions

In conclusion, we developed an unprecedented Iridium-cata-

lyzed [4 + 3] cyclizations of ortho-tosylaminophenyl-substituted
p-QMs with vinylic oxiranes or vinyl aziridines. This protocol not
only fulfilled the task of developing new cyclization reactions of
ortho-tosylaminophenyl-p-QMs but also provided a highly
efficient synthetic method to construct structurally diverse
seven-membered heterocyclic frameworks.
Scheme 4. Large-scale Synthesis.

Acknowledgements

This work was supported by the National Natural Science

Foundation of China (grant: 81803342), the Natural Science
Foundation of Jiangsu Province (grant: BK20180826), the Gradu-
ate Research and Innovation Projects of Jiangsu Province
(SJCX20_0531).

Conflict of Interest

The authors declare no conflict of interest.

Keywords: [4 + 3] Cyclization · para-Quinone Methides · Vinylic

Oxiranes/Vinyl Aziridines

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[16] CCDC 2046766 (3 a), 2059801 (5 a) contain the supplementary crystallo-
graphic data for this paper.
Manuscript received: April 26, 2021
Revised manuscript received: June 18, 2021
Version of record online: June 26, 2021
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