Synthesis, Characterization of Spirocyclic λ3-Iodanes and Their Application to Prepare 4,1-Benzoxazepine-2,5-diones and 1,3-Diynes

Article abstract of DOI:10.1002/chem.202005124

Herein, a [3+2] cycloaddition of aza-oxyallylic cations with ethynylbenziodoxolones for synthesis of new λ³-iodanes containing spirocyclic 4-oxazolidinone has been developed. This cyclic λ³-iodanes display stability in air and excellent solubility in organic solvent. Using them as substrate, both the 4,1-benzoxazepine-2,5-diones and symmetrical 1,3-diynes derivatives were afforded in high yield under copper(I)-catalyzed conditions.

Full text of DOI:10.1002/chem.202005124

Accepted Article
Accepted Article
Title: Synthesis, Characterization of Spirocyclic λ3-Iodanes and Their
Application to Prepare 4,1-Benzoxazepine-2,5-diones and 1,3-
Diynes
Authors: Tai-Ran Kang
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10.1002/chem.202005124
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Synthesis, Characterization of Spirocyclic 3-Iodanes and Their
Application to Prepare 4,1-Benzoxazepine-2,5-diones and 1,3-
Diynes
Xu Sun,[a,b] Xiao-Qiang Guo,[a] Lian-Mei Chen,*,[a] and Tai-Ran Kang*,[a,b]
Dedication ((optional))
Abstract: Herein, a [3+2] cycloaddition of aza-oxyallylic cations with
EBXs for synthesis of new3-iodanes containing spirocyclic 4-
oxazolidinone has been developed. This cyclic 3-iodanes display
stability in air and excellent solubility in organic solvent. Using them
as substrate, both the 4,1-benzoxazepine-2,5-diones and
symmetrical 1,3-diynes derivatives were afforded in high yield under
copper(I)-catalyzed conditions.
requirement of multistep procedure, Grignard reagents and
lithium acetylides.1a,1h,3,6 In 2019, the oxygen atom was replaced
by a nitrogen in the iodoheterocycle of EBXs was synthesized by
the group of Waser and coworkers.6h Very recently, the
EBX−acetonitrile complex was prepared by Tada and
coworkers.6i Inspired by these works, we were interested in
developing a modified EBXs, in which the carbonyl group was
replaced with a 4-oxazolidinone ring7 (Figure 1 B). We believed
that the modified EBXs would modulate their steric and
electronic environment, and have the potential to introduce
amide, ester or alkyl groups into an organic molecule under
proper reaction condition. Several examples of [3+2]
cycloaddition of azaoxyallyl cation8 with carbonyl compounds to
construct the 4-oxazolidinones motifs were reported in
literature.7 Accordingly, we envisioned that a [3+2] cycloaddition
of aza-oxyallylic cation with the carbonyl group of
Hypervalent iodine reagents including iodine (V) (called as
5-iodane), iodine(III) (called as3-iodane), iodonium salts and
iodonium ylide, show unique reactivity similar to transition metals,
and have been widely applied in organic synthesis.1 Non-cyclic
hypervalent iodines are usually unstable (Figure 1 A).1k Cyclic
hypervalent iodine reagents, such as, 1-hydroxy-1,2-
benziodoxol-3-(1H)-one (IBX), Dess–Martin periodinane (DMP),
benziodoxol(on)es (BXs) and ethynylbenziodoxolones (EBXs),
show higher stability than their acyclic analogs due to the
inclusion of the iodine atom into a heterocycles (Figure 1 B).1a, 1k
benziodazolone core would undergo to provide
a novel
spirocyclic 3-iodanes containing a spiro-4-oxazolidinones.
Therefore, the synthesis and application of cyclic iodanes have
1k
gained increasing attention during past decades.1a,
example, the cyclic iodine(III)
For
(called as 3-iodane)
containing acetate, halogens, trifluoromethyl, azides, cyanides,
aryl and alkyl groups,1h, 2 were reported by the pioneering groups,
such as, Waser, Zhdankin, Kita, Beringer, Koser, Valvoglis,
Moriarty, Ochiai, and Togni.1,2 More recently, two type of cyclic
3-iodanes containing a (diarylmethylene)amino and nitrooxy
groups were reported by the group of Kiyokawa, Minakata2f and
Katayev,2g respectively.
The EBXs and modified EBXs have been widely employed
as the substrates for the C–alkynyl, heteroatom–alkynyl bond,3
vinylbenziod-oxoles (VBXs)4 and heterocycles formation.5 In the
modified EBXs, the carbonyl group or oxygen atom were
changed for fine-tuning its reactivity.6 For example, the carbonyl
group of benziodazolone core are replaced by methyl or
trifluoromethyl group (Figure 1 B), which were synthesized and
applied by the groups of Ochiai,6a Zhdankin,6b Waser,6c-f,h and
Itoh.6i However, they are difficult to prepare due to the
Figure 1. Structure and bonding of hypervalent iodine reagents
[a]
[b]
Dr .X. Sun, Prof. Dr. X.-Q. Guo, Prof. Dr. L.-M. Chen, Prof. Dr. T.-
R. Kang
School of Food and Biological Engineering, Chengdu University,
Chengdu City 610106, China
E-mail: kangtairan@sina.com; lianmchen@sina.com
Dr Sun, Prof. Dr. T.-R.
Collaborative Innovation Center of Tissue Repair Material of
Sichuan Province, College of Chemistry & Chemical Engineering,
China West Normal University, Nanchong City, Sichuan 637002,
China
The cyclic 3-iodanes were applied as versatile electrophilic
group-transfer reagents in organic synthesis2 (Scheme 1 A). As
an alkynylated reagent, EBXs have been widely used in an
intermolecular alkynylation reaction.3 For example, EBXs
reacted with terminal alkynes to provide 1,3-diynes under gold-
catalyzed or nBuLi-promoted condition, which were reported by
the groups of Liu,10a Patil10b and Waser,10c respectively (Scheme
1 B). The major drawback of these methods is the formation of
Supporting information for this article is given via a link at the end
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one equivalent of “waste” 2-iodobenzoic acid or (2-
iodophenyl)methanol (Scheme 1 A and B).
entry
base
solvent
T (oC)/
time (h)
yield (%)
yield (%)
3aa[b]
3aa’[c]
1
2
3
4
5
6
7
8
9
Et3N
TFE
25/12
25/12
25/12
25/12
25/2
35
40
45
70
75
85
45
50
60
<10
<10
<10
15
Et3N
HFIP
HFIP
DCE
DCE
DCE
DCE
DCE
DCE
Na2CO3
Na2CO3
K2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
15
25/2
10
0/12
45b
45b
<10
-20/12
60/2
[a] Reaction conditions: 1a (0.1 mmol, 1.0 equiv), 2a (0.15 mmol, 1.5 equiv),
base (0.3 mmol, 3.0 equiv) in 0.5 mL solvent. [b] Isolated yield. [c] Determined
by 1H NMR analysis of the reaction crude reaction mixture.
At the outset of our studies, we chose EBX (1a) and N-
(benzyloxy)-2-bromo-2-methylpropanamide (2a) as
a model
system to optimize the reaction conditions, and the screening
results are summarized Table 1. Considering the stabilization of
azaoxyallyl cation in fluorinated solvents, the hexaflfluoro-2-
propanol (HFIP) and 2,2,2-trifuoroethanol (TFE) were employed
as solvent. NEt3 and Na2CO3 were employed as bases for the
reaction.7,8 However, 3aa was afforded only in low yields (35-
45%) for 12 h, and the byproduct nitrogen-substituted VBX 3aa’
(see SI for details) was trace (entries 1-3). When 1,2-
dichloroethane (DCE) was employed as solvent, the desired
product 3aa was afforded in 70% yield, and the byproduct 3aa’
was afforded in 15% yield (entry 4). Using K2CO3 and Cs2CO3 as
base, the yield of 3aa increased to 75% and 85% for 2 hours,
along with 15% and 10% yield of 3aa’, respectively (Table 1,
entries 4-6). Therefore, Cs2CO3 was the best choice (entry 6).
Lowing or raising the reaction temperature, the unsatisfactory
results were obtained (entries 7-9).
Scheme 1. Reaction of cyclic 3-iodanes.
We initially envisioned that
a
copper(I)-catalyzed
intramolecular rearrangement reaction of the spirocyclic3-
iodanes would happen to provide the expected 1-
((benzyloxy)(phenylethynyl)-amino)-2-methyl-1-oxopropan-2-yl-
2-iodobenzoate (Scheme 1 C). However, the expected product
was not obtained, but both the unexpected 4,1-benzoxazepine-
2,5-diones and 1,3-diynes were obtained through a sequence
bond formation involving C=O, Csp2−N and Csp−Csp, together
with a sequence bond cleavage involving I-O, Csp2−I and
Csp3−N (Scheme
benzoxazepine-2,5-diones12 were very valuable compounds. To
our knowledge, strategy for synthesis of both 4,1-
1
C). Both the 1,3-diynes11 and 4,1-
a
With the optimal reaction conditions established, we next
explored the substrate scope. A wide range of cyclic 3-iodanes
containing spiro-4-oxazolidinones were prepared, as shown in
Scheme 2. When R1 was phenyl group, the substituents at the
para, meta, or ortho positions of phenyl ring, and the substrates
containing a variety of functional groups including methyl (1b,
1d), halogens (1c, 1e), phenyl (1f) and ester (1g) exhibited
good results, affording the cyclic3-iodanes 3aa−3ga in
moderate to good yields (66%−85%). However, when R1 was
alkyl group (Et or cyclohexyl), the desired product did not obtain
benzoxazepine-2,5-diones and 1,3-diynes in one-pot has not
been reported so far. Herein, we report that the spirocyclic 3-
iodanes containing a 4-oxazolidinone ring were synthesized
through a [3+2] cycloaddition of aza-oxyallylic cation with EBXs.
Both the 4,1-benzoxazepine-2,5-dione and 1,3-diyne derivatives
were afforded by copper-catalyzed the spirocyclic 3-iodanes.
Table 1. Optimization of reaction conditions.[a]
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due to the mess of reaction. When R2 was Cl group, the product
3ha was afforded in 68% yield. To our gratification, when R1 was
TIPS, various substituents at the benziodazolone core (R2 = H,
Me, F, NO2 and R3 = Cl) (1i-m) were tried, providing the 3-
iodanes (3ia, 3ja, 3ka, 3la, 3ma) in excellent yields (90-96%).
Scheme 2. Scope of ethynylbenziodoxol(on)es.[a,b]
[a] Reaction conditions: 1a or 1i (0.1 mmol, 1.0 equiv), 2b-h (0.15 mmol, 1.5
equiv), Cs2CO3 (0.3 mmol, 3.0 equiv) in 0.5 mL 1,2-dichloroethane for 2-6 h at
room temperature. [b] Isolated yield.
Table 2. Optimization of reaction conditions[a]
[a] Reaction conditions: 1a-m (0.1 mmol, 1 equiv), 2a (0.15 mmol, 1.5 equiv),
Cs2CO3 (0.3 mmol, 3.0 equiv) in 0.5 mL 1,2-dichloroethane for 2-6 h at room
temperature. [b] Isolated yield.
The scope of α-halohydroxamates was also examined
(Scheme 3, 2b-h). Replacing the benzyl group with isopropyl
(3ab, 3ib), tert-butyl (3ic), methyl (3id), allyl (3ie) and halogen
substiuted benzyl (3if, 3ig) groups worked well. It was found that
the reactivity of the silyl substituents was better than that of
phenyl group on the cyclic 3-iodanes. For example, 3ab (R1 =
Ph) was obtained in 60% yield, and 3ib−ig (R1 = TIPS) were
obtained in excellent yields (92-96%). When R1 was triethyl silyl
group, the desired product 3ih was afforded in 96% yield.
However, the monomethyl, monoethyl, and monophenyl-
substituent on α-halohydroxamates failed to provide the desired
products, and only the corresponding byproducts (VBXs) were
obtained in almost quantitative yields.
entry
catalyst
-
base
T (oC)/t (h)
135/12
135/12
135/12
135/12
135/12
90/12
4a yield (%)[b]
5a yield (%)[c]
1
2
3
4
5
6
-
-
-
CuCl
CuBr
CuI
K3PO4
K3PO4
K3PO4
K2CO3
K3PO4
85
90
92
40
60
95
98
99
90
95
It should be noted that all these cyclic3-iodanes (3aa-ma,
3ab, and 3ib-ih) display stable in air and have excellent
solubility in common organic solvents, such as DMF, methanol,
chloroform, dichloromethane, and acetonitrile. The structure of
3ab was confirmed by single crystal X-ray analysis (see SI for
details).
CuI
CuI
[a] Reaction conditions: 3aa (0.1 mmol, 1.0 equiv), catalyst (10 mol%), base
(0.1 mmol, 1.0 equiv) in 0.5 mL DMF. [b] Isolated yield. [c] Isolated yield.
Scheme 3. Scope of of α-halohydroxamates.[a,b]
We switched our focus toward exploring their application, as
shown in Table 2. We chose 3aa as model substrate to optimize
the reaction conditions. Without copper catalyst and base,
heating 3aa in DMF at 135 oC, no new product was observed on
the thin layer chromatography (TLC) for 12 h (Table 2, entry 1).
This observation suggests that 3aa is stable in DMF at high
temperature. When 3aa was treated in the presence of CuCl and
K3PO4 as the catalytic system in DMF at 135 oC, 4a and 5a were
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afforded in 85% and 95% yield, respectively (entry 2). The
expected copper(I)-catalyzed an intramolecular rearrangement
reaction didn’t happen. Therefore, the expected product 1-
((benzyloxy)(phenylethynyl)-amino)-2-methyl-1-oxopropan-2-yl-
2-iodobenzoate compound wasn’t obtained (See SI for details).
And then, various copper(I) and bases were examined (entries
3-5). The best result was obtained with CuI and K3PO4 as
catalytic system, giving 4,1-Benzoxazepine-2,5-dione 4a in 92%
yield and 1,3-diyne 5a in 99% yield (entry 4). The lower yield of
4a was afforded if K2CO3 is used as base (entry 5). Lowering the
using various groups on the aryl ring (R1), the corresponding
1,3-diynes, including methyl (5b, 5d), ester (5c), bromine (5e),
phenyl (5f) and 1-napthyl (5g) group were obtained in
quantitative yields, and the 4,1-benzoxazepine-2,5-dione 4a
was also obtained in excellent yields (90-93%). When R1 were
alkyl group, the corresponding 1,3-diyne and the 4,1-
benzoxazepine-2,5-diones were not obtained. The structure of
4a was confirmed by single crystal X-ray analysis (see SI for
details).
o
o
temperature from 130 C to 90 C, the yield of 4a reduced to
60% (entry 6).
Scheme 4. Scope of cyclic 3-iodanes.[a,b]
Scheme 5. Proposed speculative mechanism.
We propose a possible reaction mechanism in Scheme 5.
The copper(I) catalyst activates cyclic3-iodane 3aa1a,13 to form
the iodonium salt A or the copper(III) complex B by a ring
opening.1a,13 Both A and B would transform directly to copper(I)
complex C, iodine radical and alkyne radical intermediate. The
symmetrical 1,3-diyne 5a can be formed via a homocoupling of
alkyne radical.14 The copper(I) complex C undergoes a ring
opening to form copper(I) complex D, which followed to produce
copper(III) complex E via an oxidative addition process. The
desired product 4a and the initial copper (I) catalyst were
obtained from the copper (III) complex E by a reductive
elimination process.
In summary, we have developed a (3+2)-cycloaddition
reaction between EBXs and azaoxyallyl cations to afford a
spirocyclic 3-iodines bearing a 4-oxazolidinone ring. The cyclic
3-iodines is structurally characterized by X-ray analysis and
displays satisfactory solubility and stability in solution as well as
in the solid state. Using them as precursors, both the 4,1-
benzoxazepine-2,5-diones and symmetrical 1,3-diynes were
obtained under a copper(I)-catalyzed condition. The potential
applied research on the spirocyclic 3-Iodines and the 4,1-
benzoxazepine-2,5-diones are ongoing in our group.
[a] Reaction conditions: 3 (0.1 mmol, 1 equiv), CuI (10 mmol%), K3PO4 (0.1
mmol, 1.0 equiv) in 0.5 mL DMF for 12h at 135oC. [b] Isolated yield.
We next explored the substrate scope under the optimized
reaction conditions.
A
wide range of both the 4,1-
benzoxazepine-2,5-diones 4a-h and 1,3-diynes 5a-g were
shown in Scheme 4. When R3 were chlorine group substituted
benzyl (4b), methyl (4c), isopropyl (4d) and allyl (4e), it led to
give the corresponding 4,1-benzoxazepine-2,5-diones in 88-93%
yields and 1,3-diyne 5a in almost quantitative yields. When R2
was CF3 and Me group, it gave the similar results. Pleasingly,
Acknowledgements
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2018, 20, 7694-7698; d) Li, Ming, J. H. Wang, W. Li, C. D. Lin, L. B.
Zhang, L. R. Wen. J. Org. Chem. 2019, 84, 8523-8530; e) M. Li, W. Li,
C. D. Lin, J. H. Wang, L. R. Wen, J. Org. Chem. 2019, 84, 6904-6915.
a) M. Ochiai, Y. Masaki, M. Shiro J. Org. Chem. 1991, 56, 5511−5513;
b) V. V. Zhdankin, C. J. Kuehl, A. P. Krasutsky, J. T. Bolz, A. Simonsen.
J. Org. Chem. 1996, 61, 6547−6551; c) J. P. Brand, J. Charpentier, J.
Waser, Angew. Chem., Int. Ed. 2009, 48, 9346−9349; d) J. P. Brand, C.
Chevalley, R.Scopelliti, J. Waser. Chem. -Eur. J. 2012, 18, 5655−5666.
e) J. P. Brand, J. Waser. Chem. Soc. Rev. 2012, 41, 4165−4179; f) D.
F.González, J. P. Brand, J. Waser, Chem.- Eur. J. 2010, 16, 9457−9461
g) J. Kaschel, D. B. Werz. Angew. Chem., Int. Ed. 2015, 54, 8876−8878.
h) D. P. Hari, L. Schouwey, V. Barber, R. Scopelliti, F. Fadaei-Tirani, J.
Waser, Chem.- Eur. J. 2019, 25,9522-9528. i) M. Yudasaka, D. Shimbo,
T. Maruyama, N. Tada, A. Itoh. Org. Lett. 2019, 21, 1098-1102.
a) A. Acharya, K.Montes, C. S. Jeffrey. Org. Lett. 2016, 18, 6082−6085;
b) K. Zhang, C.Yang, H.Yao, A. Lin. Org. Lett. 2016, 18, 4618−4621; c)
Q. Jia,; Z. Du, K. Zhang, J. Wang. Org. Chem. Front. 2017, 4, 91−94; d)
S.Jiang, K. Li, J. Yan, K. Shi, C.Zhao, L.Yang, G. Zhong. J. Org. Chem.
2017, 82, 9779-9785; e) P.-L. Shao, Z.-R. Li, Z.-P. Wang, M.-H. Zhou,
Q. Wu, P. Hu, Y. He. J. Org. Chem. 2017, 82, 10680-10686.
We are grateful for financial support from the National Natural
Science Foundation of China (NO. 21672172), and the project of
Youth Science and Technology Innovation Team of Sichuan
Province, China (NO. 2017TD0008).
[6]
Keywords: hypervalent iodine reagents • azaoxyallyl cations •
benzoxazepinediones • 1,3-diynes • copper
[1]
For reviews: a) D. P. Hari, P. Caramenti, J. Waser. Acc. Chem. Res.
2018, 51, 3212−3225; b) J. Charpentier, N. Frueh, A. Togni. Chem. Rev.
2015, 115, 650−682; c) V. V. Zhdankin, P. J. Stang. Chem. Rev. 2008,
108, 5299−5358; d) A. N. French, S Bissmire, T. Wirth. Chem. Soc.
Rev. 2004, 33, 354−362; e) T. Wirth. Angew. Chem., Int. Ed. 2005, 44,
3656−3665; f) V. V. Zhdankin, P. J.Stang. Chem. Rev. 2002, 102,
2523−2584; g) J. P. Brand, D. F. González, S. Nicolai, J. Waser. Chem.
Commun., 2011, 47, 102–115; h) Y. Li, D. P. Hari, M. V. Vita, J. Waser,
Angew. Chem. Int. Ed. 2016, 55, 4436-4454; i) J. Waser, Synlett 2016,
27, 2761-2773; j) A. Yoshimura, V. V. Zhdankin, Chem. Rev. 2016, 116,
3328-3435; k) X. Wang, A. Studer. Acc. Chem. Res. 2017, 50, 1712-
1724; l) J. Kaschel, D. B. Werz. Angew. Chem., Int. Ed. 2015, 54, 8876-
8878.
[7]
[8]
a) A. Acharya, D. Anumandla, C. S. Jeffrey, J. Am. Chem. Soc. 2015,
137, 14858-14860; b) M. C. DiPoto, R. P. Hughes, J. Wu, J. Am. Chem.
Soc. 2015, 137, 14861-14864; (c) W. Ji, L. Yao, X. Liao. Org. Lett.
2016, 18, 628-630; d) M. C. DiPoto, J. Wu, Org. Lett. 2018, 20, 499-501;
e) D. Ji, J. Sun, Org. Lett. 2018, 20, 2745-2748; f) S. Sun, R. Chen, G.
Wang, J. Wang. Org. Biomol. Chem. 2018, 16, 8011-8014; g) Y. An, H.
Xia, J. Wu. Chem. Commun. 2016, 52, 10415-10418; h) H.-W. Zhao,
Y.-D. Zhao, Y.-Y. Liu, L.-J. Zhao, N.-N. Feng, H.-L.Pang, X.-Q. Chen,
X.-Q. Song, J. Du. RSC Adv. 2017, 7, 12916-12922; i) W. Lin, G. Zhan,
M. Shi, W. Du, Y. Chen, Chin. J. Chem. 2017, 35, 857-860; j) K. Zhang,
Xu, X.; J. Zheng, H. Yao, Y. Huang, A. Lin, Org. Lett. 2017, 19, 2596-
2599; k) X. Cheng, X.Cao, J. Xuan, W.-J. Xiao. Org. Lett. 2018, 20, 52-
55; l) J. Xuan, X. Cao, X. Cheng, Chem. Commun. 2018, 54, 5154-
5163.
[2]
For selected examples for synthesis and application of cyclic3-iodanes:
a) V. V. Zhdankin, Curr. Org. Synth. 2005, 2, 121−145; b) V. V.
Zhdankin, A. P. Krasutsky, C. J. Kuehl, A. J. Simonsen, J. K.
Woodward, B. Mismash, J. T.Bolz. J. Am. Chem. Soc. 1996, 118,
5192−5197; c) M. Ochiai, T.Sueda, K. Miyamoto, P. Kiprof, V. V.
Zhdankin. Angew. Chem., Int. Ed. 2006, 45, 8203−8206; d) P.
Eisenberger, S. Gischig. A.Togni. Chem.- Eur. J. 2006, 12, 2579−2586;
e) J. Kaschel, D. B.Werz. Angew. Chem., Int. Ed. 2015, 54, 8876−8878;
f) K. Kiyokawa, D. Okumatsu, S. Minakata. Angew. Chem. Int. Ed. 2019,
58, 8907–8911; g) R. Calvo, A. L. Tellier, T. Nauser, D. Rombach, D.
Nater, D. Katayev. Angew. Chem., Int. Ed, 2020, 59, 17162-17168.
For selected examples: a) S. Banerjee, N. T. Patil, Chem. Commun.
2017, 53, 7937-7940; b) L. D. Caspers, P. Finkbeiner, B. J. Nachtsheim,
Chem.- Eur. J. 2017, 23, 2748-2752; (c) Z.-M. Chen, C. S. Nervig, R. J.
DeLuca, M. S. Sigman, Angew. Chem. Int. Ed. 2017, 56, 6651-6654; d)
B. V. M. Teodoro, L. F. Silva, J. Org. Chem. 2017, 82, 11787-11791; e)
S.-B. Wang, Q. Gu, S.-L. You, J. Org. Chem. 2017, 82, 11829-11835; f)
S. Peng, Z. Wang, L. Zhang, X. Zhang, Y. Huang, Nat. Commun. 2018,
9, 375; g) H. Jiang, A. Studer, Chem.- Eur. J. 2019, 25, 516-520; h) R.
Frei, M. D. Wodrich, D. P. Hari, P. A. Borin, C. Chauvier, J. Waser, J.
Am. Chem. Soc. 2014, 136, 16563; i) J. P. Brand, J. Charpentier, J.
Waser. Angew. Chem., Int. Ed. 2009, 48, 9346; j) C. Feng, T.-P. Loh.
Angew. Chem., Int. Ed. 2014, 53, 2722; k) F. Xie, Z. Qi, S. Yu, X. Li, J.
Am. Chem. Soc. 2014, 136, 4780. l) T. Aubineau, J. Cossy, Chem.
Commun., 2013, 49, 3303-3305.
[3]
[9]
For selected examples, a) J. P. Brand, J. Charpentier, J. Waser, Angew.
Chem., Int. Ed. 2009, 48, 9346-9349; b) S. Nicolai, S. Erard, D. F.
González, J. Waser, Org. Lett. 2010, 12, 384-387; c) D. F. González, J.
P. Brand, J. Waser, Chem.- Eur. J. 2010, 16, 9457-9461; d) R. Frei, J.
Waser, J. Am. Chem. Soc. 2013, 135, 9620-9623; e) F. Le Vaillant, T.
Courant, J. Waser, Angew. Chem., Int. Ed. 2015, 54, 11200-11204; f) Y.
Li, J. Waser, Angew. Chem., Int. Ed. 2015, 54, 5438-5442; g) K. D.
Collins, F. Lied, F. Glorius, Chem. Commun. 2014, 50, 4459-4461; h) D.
P. Hari, J. Waser, J. Am. Chem. Soc. 2017, 139, 8420-8423. i) S. G.
Modha, M. F. Greaney, J. Am. Chem. Soc. 2015, 137, 1416-1419; j) J.
Buendia, B. Darses, P. Dauban, Angew. Chem., Int. Ed. 2015, 54,
5697-5701; k) A. Boelke, P. Finkbeiner, B. J. Nachtsheim, Beilstein J.
Org. Chem. 2018, 14, 1263-1280.
[10] a) X. Li, X. Xie, N. Sun, Y. Liu. Angew. Chem., Int. Ed.,2017, 56, 6994–
6998; b) S. Banerjee, N. T. Patil, Chem.Commun., 2017, 53, 7937–
7940; c) J. Schörgenhumer, M. Waser, Org. Biomol. Chem., 2018, 16,
7561-7563.
[4]
For selected examples: a) B. Lu, J. Wu, N. Yoshikai. J. Am. Chem. Soc.
2014, 136, 11598-11601; b) J. Wu, N. Yoshikai. Angew. Chem. Int. Ed.
2015, 54, 11107-11111; c) D. P. Hari, J. Waser. J. Am. Chem. Soc.
2016, 138, 2190-2193; d) D. P. Hari, J. Waser. J. Am. Chem. Soc. 2017,
139, 8420-8423; e) S. Banerjee, B. Senthilkumar, N. T. Patil. Org. Lett.
2019, 21, 180-184. f) J. Wu, X. Deng, H. Hirao, N. Yoshikai. J. Am.
Chem. Soc. 2016, 138, 9105-9108. g) J. Wu, K. Xu, H. Hirao, N.
Yoshikai. Chem.- Eur. J. 2017, 23, 1521-1525; h) J. Wu, X. Deng, N.
Yoshikai. Chem. - Eur. J. 2019, 25, 7839-7842; i) B. Liu, C.-H. Lim, G.
M. Miyake, J. Am. Chem. Soc. 2018, 140, 12829-12835.
[11] a) S. L. Rubab, B. Nisar, A. R. Raza, N. Ullah, M. N. Tahir, Molecules
2013, 19, 139-148. b) B. Nisar, A. R. Raza, D. S. Black, N. Kumar, M. N.
Tahir, Chirality, 2013, 25, 865-870.
[12] For reviews: a) J. M. Tour, Chem. Rev. 1996, 96, 537–553; b) R. E.
Martin, F. Diederich, Angew. Chem., Int. Ed. 1999, 38, 1350–1377.
[13] J. Borrel, G. Pisella, J. Waser. Org. Lett. 2020, 22, 422-427.
[14] Z. W. Chen, H. F. Jiang, A. Z. Wang, S. R. Yang. J. Org. Chem. 2010,
75, 6700-6703.
[5]
For selected examples: a) B. Lu, J. Yoshikai. J. Am. Chem. Soc. 2014,
136, 11598-11601; b) J. L. Wu, N. Yoshikai. Angew. Chem. Int. Ed.
2015, 54, 11107-11111. c) M. Li, J. H. Wang, W.Li, L. R. Wen, Org. Lett.
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10.1002/chem.202005124
Chemistry - A European Journal
COMMUNICATION
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COMMUNICATION
The spirocyclic hypervalent iodine
reagents containing 4-oxazolidinone
ring are prepared via a (3+2)-
Xu Sun,[a,b] Xiao-Qiang Guo, [a] Lian-Mei
Chen,* [a] and Tai-Ran Kang*,[a,b]
Page No. – Page No.
cycloaddition of azaoxyallyl cations
with EBXs. They display satisfactory
stability and solubility in organic
solvents. Using them as precursors,
both 4,1-benzoxazepine-2,5-diones
and 1,3-diynes derivatives were
afforded in one-pot under copper (I)-
catalyzed conditions.
Synthesis, Characterization of
Spirocyclic 3-Iodanes and Their
Application to Prepare 4,1-
Benzoxazepine-2,5-diones and 1,3-
Diynes
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