Direct oxidative lactonization of alkenoic acids mediated solely by NaIO4: Beyond a simple oxidant

Article abstract of DOI:10.1039/c6cc02246d

Triflic acid-catalyzed direct oxidative lactonization of alkenoic acids mediated solely by NaIO₄ without halogen salts is described. Sodium periodate works not only as an oxidant, but also as an active reagent and directly mediates the lactonization. A new cheap, green, and practical oxidative lactonization approach has been developed using NaIO₄ as the sole reagent.

Full text of DOI:10.1039/c6cc02246d

View Article Online
View Journal
ChemComm
Accepted Manuscript
This article can be cited before page numbers have been issued, to do this please use: Y. Kang, X. Chen,
C. Yao and X. Ning, Chem. Commun., 2016, DOI: 10.1039/C6CC02246D.
This is an Accepted Manuscript, which has been through the
Royal Society of Chemistry peer review process and has been
accepted for publication.
Accepted Manuscripts are published online shortly after
acceptance, before technical editing, formatting and proof reading.
Using this free service, authors can make their results available
to the community, in citable form, before we publish the edited
article. We will replace this Accepted Manuscript with the edited
and formatted Advance Article as soon as it is available.
You can find more information about Accepted Manuscripts in the
Information for Authors.
Please note that technical editing may introduce minor changes
to the text and/or graphics, which may alter content. The journal’s
standard Terms & Conditions and the Ethical guidelines still
apply. In no event shall the Royal Society of Chemistry be held
responsible for any errors or omissions in this Accepted Manuscript
or any consequences arising from the use of any information it
contains.
www.rsc.org/chemcomm

Please do not adjust margins
ChemComm
Page 1 of 4
View Article Online
DOI: 10.1039/C6CC02246D
Journal Name
COMMUNICATION
Direct oxidative lactonization of alkenoic acids mediated solely by
NaIO4: beyond oxidant
Yan-Biao Kang,* Xian-Min Chen, Chuan-Zhi Yao, and Xiao-Shan Ning
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
A triflic acid–catalyzed direct oxidative lactonization of alkenioc
acids mediated solely by NaIO4 without halogen salts is described.
Sodium periodate works not only as an oxidant, but also an active
reagent directly mediates the lactonization. A new cheap, green,
and practical oxidative lactonization approach has been developed
using NaIO4 as the solely reagent.
Scheme 1. Effect of KI.
Oxidative lactonization1 is useful organic transformation for
synthesis of lactones from alkenoic acids. As an intramolecular
version of diacyloxylation2 reaction, lactonization is an
approach for five- or six-membered lactone rings.
Prévost−Woodward reaction3 and Upjohn reaction conditions4
can sometimes be applied for oxidative lactonization, but
stoichiometric silver carboxylates or toxic osmium is involved.
Stoichiometric NaIO4 and LiBr has been established as a
modification for Prévost−Woodward reaction, however a two-
step procedure is still necessary.5 In the transition-metal free
Next, the reaction conditions were investigated. Various
Brønsted acids were screened and triflic acid proved to be the
optimized catalyst (Table 1, Entries 2
necessary acetyl reagent for high conversions, which works also
as a co-solvent (Entries 2, 7 8). In the absence of Ac2O, 68% of
6). Acetic ahydride is a

1a was recovered (Entry 7). Finally, a standard condition is
established and used to investigate the reaction scope (Entry 9).
Table 1. Reaction conditions.
6
conditions, PhI(OAc)2 and peracids have been developed as
highly efficient methods for diacetoxylation or lactonization of
alkenes.7,8 In the hypervalent iodine mediated dihydroxylation
or diacetoxylation of alkenes, stoichiometric or sometimes
substoichiometric additives such as LiBr, KI or PhI were used as
reagent for in situ generate of halogen anion of PhI(OAc)2 which
work as active reagents. On the basis of our research on the
discovery of new reactions,9 we developed a NaIO4–mediated
transition-metal-free oxidative lactonization of alkenoic acids
without halogen additives where NaIO4 works beyond oxidant.
Initially, substoihiometric KI was used as catalyst for the
oxidative lcatonization of 1a to 2a. Surprisingly, the control
reaction without of KI could also give the same conversion
(Scheme 1). KI has been believed to be a necessary additive to
generate iodium to form intermediate 3a. However, 2a was
supposed to be coverted from 3a in typical Prévost–Woodward
reaction conditions.
entrya
1
2
3
4
5
6
7
8
cat.
—
TfOH
TsOH
CF3CO2H
HCl
HCO2H
TfOH
TfOH
TfOH
TfOH
TfOH
TfOH
TfOH
TfOH
NaIO4 (equiv)
1.2
solvent
AcOH−Ac2O
AcOH−Ac2O
AcOH−Ac2O
AcOH−Ac2O
AcOH−Ac2O
AcOH−Ac2O
AcOH
2a (%)b
26
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.25
0.25
0.50
1.2
1.2
1.2
74 (64c)
64
62
42
62
15d
Ac2O
0
9
AcOH−Ac2O
AcOH−Ac2O
AcOH−Ac2O
other
AcOH−Ac2O
AcOH−Ac2O
76
10
11
12g
13h
14i
29e
52f
trace
59 (63)
69
a Conditions: 1a (1 mmol), acid (5 mol%), NaIO4, AcOH−Ac2O (2/1, v/v, 2 mL),
70 °C. b By 1H NMR (400 MHz) using ethyl 3-phenylpropionate as the internal
c
d
e
standard. Using 10 mol% of TfOH. With 5% of 3a and 68% of 1a. With
23% of 3a and 35% of 1a. f With 39% of 3a. g When THF, DMF, DMSO or CH3CN
was used as solvent 1a was recovered. h At 60 oC (80 oC). i For 10 hours.
Center of Advanced Nanocatalysis, Department of Chemistry, University of
Science and Technology of China, Hefei, Anhui 230026, China
* E-mail: ybkang@ustc.edu.cn
Electronic Supplementary Information (ESI) available: [Experimental procedure,
spectra]. See DOI: 10.1039/x0xx00000x
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 1
Please do not adjust margins

Please do not adjust margins
ChemComm
Page 2 of 4
COMMUNICATION
The scope of this reaction was investigated and the desired
Journal Name
The reaction of 1a to 2a was monitored byVie1wHArNticMle ORnlitnoe
products were generally obtained in moderate to good yields determine whether 3a is the intermediatDeO. AI: s10s.h10o3w9/nC6inCCSc0h22e4m6De
(Scheme 2). For example, pent-4-enoic acid 1a was subjected 3, the disappearance of 1a in a straight line until it disappears.
the reactions to produce 2a in 71% isolated yield. Similarly, 2,2- Intermediate 3a increases at the early phase of the reaction and
substituted pent-4-enioc acids such as 1b1d gave the desired decreases after about 8 hours. On the contrary, product 2a
products 2b 2d in good yields. 4-Phenylpent-4-enoic acid 1e is keeps increasing until the disappearance of intermediate 3a

,
a special example because the reaction passed through a 1,2- despite the starting material 1a disappears after about 10
phenium shift and an abnormal product 2e was afforded. Ring hours. This monitoring experiment directly suggests that 3a is
system 1g and 1h resulted in the spiro lactones 2g and 2h. Hept- an essential intermediate for this oxidative lactonization of 1a
.
5-enoic acid 1j was subjected to the oxidative lactonization and
the target product 2j was obtained in 67%. 2-Allylbenzoic acid
1k gave the six-membered lactone 2k in 91% yield. Aliphatic
terminal alkene such as 1-octene 1l gave the corresponding
diacetoxyl product in moderate yield.
1a
100
3a
80
2a
60
40
20
0
0
200
400
600
800 1000
Time (min)
Scheme 3. Monitoring reaction by 1H NMR.
In Prévost−Woodward conditions, silver carboxylate
(RCO2Ag) is used to promote the substitution step to convert
iodides to acetoxylation products. In current conditions, there
is no silver carboxylate and the substitution of iodo-group to
OAc-group seems under question. Control experiments in the
presence or absence of NaIO4 proves that the conversion of 3a
to 2a should not be a simple SN2 reaction (Scheme 4, Eq 1). No
3a is converted to 2a without NaIO4. This means NaIO4 is not just
an oxidant for iodolactonization of 1a to 3a, it is also necessary
for the substitution step.
Scheme 4.
The relationship between the amount of NaIO4 and the
conversion of 2a and 3a was investigated (Scheme 4, Eq 2). The
increase of the amount NaIO4 gives rise to the increase of
Scheme 2. Reaction scope. Conditions:
mmol), 70 °C, 14 h, isolated yield. a TfOH (10 mol%), 80 °C . b At 60 °C . c NaIO4 (0.5
mmol), 80 oC.
1 (1 mmol), TfOH (5 mol%), NaIO4 (1.25
conversion of 2a as well as the ratio of 2a/3a. Despite there is
2 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 3 of 4
ChemComm
Please do not adjust margins
Journal Name
COMMUNICATION
no trace iodide containing in the NaIO4, large amount of 3a is
still produced in 39% when 0.5 equiv of NaIO4 is used. This
suggests that large amount of [I+] forms during the reaction
process.
View Article Online
DOI: 10.1039/C6CC02246D
To confirm if trace amount of KI or other low oxidation state
iodines contributes to this reaction, NaIO4 has been examined
by XPS analysis. As shown in Figure 1, the elements binding
energy range from 615 to 640 eV, NaIO4 was confirmed as the
major component with NaIO3. Either NaI or I2 was observed
from 618 to 620 eV (Table 2).
Scheme 5. Working model: beyond SN2.
Figure 1. XPS spectra of NaIO4.
Table 2. Elements binding energy (eV) of XPS.
Conclusions
NaIO4
(I3d5/2
623.8
NaIO4
(O1s)
NaIO3
(I3d5/2
NaI
I2
)
)
(I3d5/2
)
(I3d5/2
)
In conclusion, we have developed an oxidative lactonization
mediated solely by NaIO4, which is beyond a simple oxidant to
oxidized and regenerate the reactive halogen anions or
hypervalent iodanes in previous reports. This is the first time
discovery of the multiple role of NaIO4 in lactonization. Other
oxidation reactions including diacetoxylation of alkenes and
iodination of esters solely using NaIO4 as a multiple-role reagent
is undergoing in our laboratory.
531.8
623.3
618.3a
619.7a
Major
Minor
None
None
a NaI and I2 were not observed in NaIO4.
On the basis of control experiments, a plausible reaction
working model is proposed in Scheme 5. Intermediate
generated from the acetylation of [IO4 ], followed by
B
–
protonation to form
captured by C C bond to give onium intermediate
converted to 2a via intermediate and
C with a cationic iodine center which is
═
D
.
D
is
Notes and references
–
E
F
with releasing of [IO3
We thank the National Natural Science Foundation of China (NSFC
21404096, U1463202), the Fundamental Research Funds for the Central
Universities of China (WK2060190026, WK3430000001), Anhui
Provincial Natural Science Foundation (1608085MB24) for financial
support.
] which repeats this process to generate another 2a and iodite
–
anion [IO2 ] (Scheme 4, Eq 2). Iodite is exceeding unstable and
–
transformed to [IO4 ] and [I+] by disproportionation. Iodine
cation is captured by 1a to afford 3a, which is further converted
to 2a via
H or B'. Iodo lactone 3a could not directly transform to
2a through a SN2 process (Scheme 5, Eq 1), thus an oxidation-
reductive elimination process is proposed. In this working
model, the generation of iodine cation as well as the formation
of 2a through two simultaneous pathways. Here NaIO4 works as
a direct lactonization reagent and the source of iodine cation,
where it is beyond a simple oxidizing reagent.
1
(a) M. Hudlicky, Oxidations in Organic Chemistry; ACS Monograph
Series 186; American Chemical Society: Washington, DC, 1990; pp
174. (b) R. A. Johnson, K. B. Sharpless, In Catalytic Asymmetric
Synthesis, 2nd ed.; Ojima, I., Ed.; Wiley-VCH: New York, WeinHein,
2000; p 357. (c) A. H. Haines, Comprehensive Organic Synthesis, 1st
ed; B. M. Trost, I. Fleming, Eds.; Pergamon: Oxford, 1991; Vol. 7, p
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 3
Please do not adjust margins

Please do not adjust margins
ChemComm
Page 4 of 4
COMMUNICATION
Journal Name
437. d) R. M. Romero, T. H. Wöste, K. Muñiz, Chem-Asian J. 2014,
, 972.
View Article Online
DOI: 10.1039/C6CC02246D
9
2
Recent references for dihydroxylation/diacetoxylation reaction: (a) Z.
K. Wickens, P. E. Guzmán, R. H. Grubbs, Angew. Chem. Int. Ed. 2015,
54, 236. (b) C. Alamillo-Ferrer, S. C. Davidson, M. J. Rawling, N. H.
Theodoulou, M. Campbell, P. G. Humphreys, A. R. Kennedy, N. C. O.
Tomkinson, Org. Lett. 2015, 17, 5132. (c) J. H. Park, C. Y. Park, H. S.
Song, Y. S. Huh, G. H. Kim, C. P. Park, Org. Lett., 2013, 15, 752. (d)
M. Bekkaye Y. Su, G. Masson, Eur. J. Org. Chem. 2013, 3978. (e) B.
C. Giglio, V. A. Schmidt,E. J. Alexanian, J. Am. Chem. Soc. 2011, 133
,
13320. (f) P. D. Oldenburg, Y. Feng, I. Pryjomska-Ray, D. Ness, L.
Que, J. Am. Chem. Soc. 2010, 132, 17713. (g) T. W. S. Chow, E. L.
M. Wong, Z. Guo, Y. G. Liu, J. S. Huang, C.-M. Che, J. Am. Chem.
Soc. 2010, 132, 13229. (h) K. Suzuki, P. Oldenburg, L. Que, Angew.
Chem. Int. Ed. 2008, 47, 1887. (i) J. W. de Boer, J. Brinksma, W. R.
Browne, A. Meetsma, P. L. Alsters, R. Hage, B. L. Feringa, J. Am.
Chem. Soc. 2005, 127, 7990.
3
4
(a) C. Prévost, Compt. Rend. 1933, 196, 1129. (b) R. B. Woodward, F.
V. Brutcher, J. Am. Chem. Soc. 1958, 80, 209.
(a) V. VanRheenen, R. C. Kelly, D. Y. Cha, Tetrahedron Lett. 1976,
23, 1973. (b) E. N. Jacobsen; I. Marko, W. S. Mungall, G. Schroeder,
K. B. Sharpless, J. Am. Chem. Soc. 1988, 110, 1968.
5
6
L. Emmanuvel, T. M. A. Shaikh, A. Sudalai, Org. Lett. 2005, 7, 5071.
(a) R. N. Reddi, P. K. Prasad, A. Sudalai, Org. Lett. 2014, 16, 5674.
(b) C. Röben, J. A. Souto, E. C. Escudero-Adán, K. Muñiz, Org. Lett.
2013, 15, 1008. (c) C. Röben, J. A. Souto, Y. González, A.
Lishchynskyi, K. Muñiz, Angew. Chem. Int. Ed. 2011, 50, 9478. (d)
M. Uyanik, T. Yasui, K. Ishihara, Angew. Chem. Int. Ed. 2010, 49
,
2175. (e) M. Ochiai, K. Miyamoto, M. Shiro, T. Ozawa, K.
Yamaguchi, J. Am. Chem. Soc. 2003, 125, 13006. (f) U. H. Hirt, M. F.
H. Schuster, A. N. French, O. G. Wiest, T. Wirth, Eur. J. Org. Chem.
2001, 1569. (g) U. H. Hirt, B. Spingler, T. Wirth, J. Org. Chem. 1998,
63, 7674. (h) T. Wirth, U. H. Hirt, Tetrahedron: Asymmetry 1997, 8,
23. (i) V. V. Zhdankin, R. Tykwinski, B. Berglund, M. Mullikin, R.
Caple, N. S. Zefirov, A. S. Kozmin, J. Org. Chem. 1989, 54, 2609. (j)
V. V. Zhdankin, M. Mullikin, R. Tykwinski, B. Berglund, R. Caple,
N. S. Zefirov, A. S. Kozmin, J. Org. Chem. 1989, 54, 2605.
7
8
(a) Y.-B. Kang, L. H. Gade, J. Am. Chem. Soc. 2011, 133, 3658. (b)
Y.-B. Kang, L. H. Gade, J. Org. Chem. 2012, 77, 1610.
(a) S. Haubenreisser, T. H. Wöste, C. Martínez, K. Ishihara, K., K.
Muñiz, Angew. Chem. Int. Ed. 2016, 55, 413. (b) M. Fujita, M. Wakita,
T. Sugimura, Chem. Commun. 2011, 47, 3983.
9
(a) J. Liu, H.-X. Zheng, C.-Z. Yao, B.-F. Sun, Y.-B. Kang, J. Am.
Chem. Soc. 2016, 136, 3294−3297. (b) J.-J. Ge, C.-Z. Yao, M.-M.
Wang, H.-X. Zheng, Y.-B. Kang, Y.-D. Li, Org. Lett. 2016, 18, 228.
(c) C.-Z. Yao, Q.-Q. Li, M.-M. Wang, X.-S. Ning, Y.-B. Kang, Chem.
Commun. 2015, 51, 7729. (d) Q.-Q. Li, Z.-F. Xiao, C.-Z. Yao, H.-X.
Zheng, Y.-B. Kang, Org. Lett. 2015, 17, 5328. (e) H.-X. Zheng, Z.-F.
Xiao, C.-Z. Yao, Q.-Q. Li, X.-S. Ning, Y.-B. Kang, Y. Tang, Org. Lett.
2015, 17, 6102. (f) X.-S. Ning, X.-J. Dong, Z.-F. Xiao, C.-Z. Yao, Y.-
B. Kang, Asian J. Org. Chem. 2015, 4, 333. (g) R. Deng, Y. Huang, X.
Ma, G. Li, R. Zhu, B. Wang, Y.-B. Kang, Z. Gu, J. Am. Chem. Soc.
2014, 136, 4472. (h) C.-Z. Yao, Z.-F. Xiao, J. Liu, X.-S. Ning, Y.-B.
Kang, Org. Lett. 2014, 16, 2498. (i) C.-Z. Yao, Z.-F. Xiao, X.-S. Ning,
J. Liu, X.-W. Zhang, Y.-B. Kang, Org. Lett. 2014, 16, 5824. (j) Z.-F.
Xiao, C.-Z. Yao, Y.-B. Kang, Org. Lett. 2014, 16, 6512.
4 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins