Alkene Oxyalkylation Enabled by Merging Rhenium Catalysis with Hypervalent Iodine(III) Reagents via Decarboxylation

Article abstract of DOI:10.1021/ja410195j

Rhenium-catalyzed oxyalkylation of alkenes is described, where hypervalent iodine(III) reagents derived from widely occurring aliphatic carboxylic acids were used as, for the first time, not only an oxygenation source but also an alkylation source via decarboxylation. The reaction also features a wide substrate scope, totally regiospecific difunctionalization, mild reaction conditions, and ready availability of both substrates. Mechanistic studies revealed a decarboxylation/radical-addition/cation-trapping cascade operating in the reaction.

Full text of DOI:10.1021/ja410195j

Communication
pubs.acs.org/JACS
Alkene Oxyalkylation Enabled by Merging Rhenium Catalysis with
Hypervalent Iodine(III) Reagents via Decarboxylation
Yin Wang,†,‡ Lei Zhang,†,§ Yunhui Yang,† Ping Zhang,§ Zhenting Du,*,‡ and Congyang Wang*,†
†Beijing National Laboratory of Molecular Sciences, CAS Key Laboratory of Molecular Recognition and Function, Institute of
Chemistry, Chinese Academy of Sciences, Beijing 100190, China
‡College of Science, Northwest A&F University, Yangling, Shaanxi 712100, China
§College of Chemistry and Materials Science, Hebei Normal University, Shijiazhuang 050024, China
S
* Supporting Information
Scheme 1. Transition-Metal-Catalyzed Alkene
Difunctionalizations with HIRs
ABSTRACT: Rhenium-catalyzed oxyalkylation of alkenes
is described, where hypervalent iodine(III) reagents
derived from widely occurring aliphatic carboxylic acids
were used as, for the first time, not only an oxygenation
source but also an alkylation source via decarboxylation.
The reaction also features a wide substrate scope, totally
regiospecific difunctionalization, mild reaction conditions,
and ready availability of both substrates. Mechanistic
studies revealed a decarboxylation/radical-addition/cation-
trapping cascade operating in the reaction.
lkene difunctionalizations are, among organic transforma-
A
tions, of the most prominent importance for efficient
buildup of molecular complexity. They are highlighted by the
Sharpless osmium-catalyzed dihydroxylations1a and amino-
hydroxylations.1b However, because the Os catalysts are
expensive and highly toxic, alternative methods are needed to
complement the Sharpless protocols and, more importantly,
achieve greater reaction diversity.2 Along this line, the use of
hypervalent iodine(III) reagents (HIRs) in difunctionalization of
alkenes has recently garnered significant attention owing to their
ready accessibility, ease of handling, low cost, and environ-
mentally benign character.3,4 In these events, HIRs react
commonly as electrophiles with olefins, leading to three-
membered iodonium ions, and further act as excellent leaving
groups to be replaced by other nucleophiles. The resulting
reaction categories rely heavily on the limited types of key
intermediates such as iodiranium and aziridinium ions.4 Clearly,
there is still a high demand for achieving the sought-after reaction
diversity as well as regio- and stereocontrol on alkene
difunctionalization with HIRs.
described the diacetoxylation and aminooxygenation of olefins
by employing the binary system of copper catalysts and HIRs.
Mechanistically, these transformations rely on the oxidation of
low oxidation state metal species to high oxidation states (PdII/
PdIV, AuI/AuIII, and CuI/CuIII) by hypervalent iodines to
facilitate the formation of C−X bonds. Most recently, Zhu et
al. disclosed an intramolecular alkylarylation of olefins by visible-
light-promoted Ir-catalyzed decarboxylation of HIRs, though the
reaction substrates were limited to 1,1-disubstituted N-
arylacrylamides (Scheme 1B).8 As part of our ongoing interest
in rhenium catalysis and decarboxylation reactions,9,10 here we
report an unprecedented intermolecular decarboxylative oxy-
alkylation of alkenes enabled by the combination of Re catalysis
with HIRs (Scheme 1C).11 Remarkably, this reaction displays a
mechanistically distinct manifold between HIRs and Re catalysts
which is in contrast to those of other transition metals (e.g., Pd,
Au, Cu, and Ir). It also represents the first example wherein HIRs
act as both oxygenation and alkylation sources in the
difunctionalizations of alkenes.
To meet this demand, the merging of transition-metal catalysis
and HIRs has evolved as a powerful strategy to develop varied
alkene difunctionalization reactions in the past few years.5−8 For
instance, Sorensen, Muniz, Stahl, Sanford, and others elegantly
̃
At the outset, we selected 4-tert-butylstyrene 1c and
iodosobenzene diacetate 2a as model substrates (Table 1).
After an extensive survey of reaction parameters,12 to our delight,
the decarboxylative oxyalkylation product 3ca was detected in
85% NMR yield after reaction with Re2(CO)10 as catalyst and
demonstrated that palladium catalysis coupled with HIRs enables
a wide range of alkene difunctionalizations, including amino-
oxygenation,5a−e diamination,5f−h dioxygenation,5i−k amino-
fluorination,5l and aryloxygenation,5m−p among others5q−s
(Scheme 1A). Meanwhile, Muniz6a and Nevado6b et al.
̃
successfully combined gold catalysis with HIRs, allowing for
efficient alkene diamination, aminooxygenation, and arylamina-
tion. The groups of Seeyad and Chai,7a Blakey,7b and Chiba7c
Received: October 4, 2013
© XXXX American Chemical Society
A
dx.doi.org/10.1021/ja410195j | J. Am. Chem. Soc. XXXX, XXX, XXX−XXX

Journal of the American Chemical Society
Communication
a
a b
,
Table 1. Screening of Reaction Parameters
Scheme 2. Scope of Alkenes
b
yields (%)
temp
entry
cat. (5 mol%)
Re2(CO)10
solvent
(°C)
3ca 4ca 5ca
1
2
3
4
5
6
7
Et2O
Et2O
Et2O
Et2O
Et2O
Et2O
Et2O
Et2O
Et2O
Et2O
Et2O
80
80
80
80
80
80
80
80
80
80
50
85
0
6
0
4
0
3
3
3
0
0
0
0
2
5
c
−
ReCl(CO)5
ReBr(CO)5
[Re(CO)3Br(thf)]2
MnBr(CO)5
Mn2(CO)10
Sc(OTf)3
72
60
77
0
13
13
7
0
0
0
d
8
d
0
0
9
In(OTf)3
0
0
e
10
Re2(CO)10
Re2(CO)10
83
8
f
g
11
83 (82)
2
a
Reaction conditions unless otherwise noted: 1c (0.2 mmol), 2a (0.4
b
a
mmol), catalyst (0.01 mmol), solvent (1.0 mL), 12 h. Determined by
Reaction conditions: 1 (0.5 mmol), 2a (1.0 mmol), Re2(CO)10
c
1H NMR analysis with an internal standard. No catalyst.
b
(0.0125 mmol), Et2O (1.25 mL), 50 °C, 12 h. Isolated yields of
product 3 are shown. 2.5 mol% ReCl(CO)5. Visible light (15-W
household bulb). 5.0 mol% Re2(CO)10, 80 °C. Dioxygenation
byproduct 6ma was detected in 25% NMR yield (d.r. = 2:1). Two
c
d
d
e
f
Diacetoxylation product 6ca was formed. In dark. 2.5 mol%
e
f
g
Re2(CO)10, 0.5 mL Et2O. Isolated yield on 0.5 mmol scale.
g
h
diastereoisomers (threo:erythro = 3.4:1). d.r. = 1.7:1.
diethyl ether as solvent at 80 °C (entry 1). The concomitant
formation of small amounts of oxidative Heck product 4ca and
alkene oxydimethylation product 5ca was also observed in the
reaction. Importantly, no products were formed in the absence of
Re2(CO)10 (entry 2). Other Re catalysts gave inferior results,
while manganese congeners showed no effectiveness at all
(entries 3−7). Interestingly, traditional Lewis acids such as
Sc(OTf)3 and In(OTf)3 merely formed the vicinal diacetox-
ylation product 6ca (entries 8 and 9). Varying the solvents
proved Et2O to be optimal.12 Notably, the reaction proceeded
equally well when conducted in the dark, in contrast to the
previous Ir system (entry 10).8 Further optimizations demon-
strated that the catalyst loading can be lowered to 2.5 mol% and
the reaction temperature can be decreased to 50 °C at a higher
concentration with no influence on the reaction outcome (entry
11).12 Hence, 3ca was obtained in 82% isolated yield with
excellent chemo- and regioselectivity. Control experiments
showed that byproducts 4ca and 5ca could not be generated
from 3ca nor 6ca under the reaction conditions, which gave a
hint on the possible reaction mechanism.12
Next, a range of HIRs were tested as shown in Table 2.
Specifically, HIRs derived from primary, secondary, and tertiary
aliphatic carboxylic acids were all well compatible with the alkene
oxyalkylation protocol, affording the corresponding products
3fb−ff smoothly. Note that visible light illumination by a
a
Table 2. Scope of HIRs
With the optimized conditions in hand, we then examined the
reactivity of various alkenes with PhI(OAc)2 2a as the reaction
partner (Scheme 2). It was shown that neither electron-donating
nor -withdrawing groups on the benzene moieties had an obvious
effect on the reaction outcome (3aa−ha). Among them, a range
of functionalities including benzylic C−H bonds, ether, ester,
and halogens were well tolerated in the reaction. Ortho- and
meta-substituted aromatic alkenes also reacted smoothly with 2a,
leading to the expected products 3ia and ja. Similarly, 2-
vinylnaphthalene delivered the corresponding product 3ka in
good yield. Of note, no noticeable products were detected when
aliphatic alkenes were used. Internal alkenes demonstrated a
relatively sluggish reactivity; however, the expected products
3la−oa could be obtained in synthetically valuable yields with
slight modifications of reaction conditions. Remarkably, 1-
phenyl-1,3-butadiene underwent a vicinal oxyalkylation on the
terminal double bond, affording solely product 3pa in a
completely regioselective manner.
a
Reaction conditions: 1f (0.5 mmol), 2 (1.0 mmol), Re2(CO)10
b
(0.025 mmol), Et2O (1.0 mL), 80 °C, 12 h. Isolated yields of
product 3. 2.5 mol% Re2(CO)10, Et2O (1.25 mL), 50 °C. Visible
light (15-W household bulb). 6fg: 9% NMR yield. 6fh: 11% NMR
c
d
e
f
g
yield. 6ai: 42% NMR yield.
B
dx.doi.org/10.1021/ja410195j | J. Am. Chem. Soc. XXXX, XXX, XXX−XXX

Journal of the American Chemical Society
Communication
a
common household bulb was needed to enhance the reaction
efficiency in some cases, which provides an additional handle to
tune the reaction outcome. It should be pointed out that fatty
acids are the key components in natural oils and fats, which
represent the most important renewable raw materials for the
chemical industry.13 Hence, we subjected the HIRs 2g and 2h,
derived from lauric acid and palmitic acid, respectively, to our
reaction conditions. Gratifyingly, the long-chain oxyalkylation
products 3fg and 3fh were successfully obtained in synthetically
useful yields. In addition, when HIR resulting from benzoic acid
was employed, the oxyarylation product 3ai was obtained in low
yield, with concurrent formation of alkene dioxygenation
byproduct 6ai, suggesting a likely radical decarboxylation
mechanism.
Scheme 3. Mechanistic Experiments
To delve into the possible reaction mechanism, a series of
experiments were conducted. Initially, the crossover experiments
between two different HIRs were examined to ascertain whether
the alkylation and oxygenation moieties originate from the same
HIR molecule (Scheme 3A). It turned out that four hybrid
products were obtained when equimolar amounts of HIRs 2a
and 2b were treated with olefin 1a, which implied a separate
intermolecular alkylation/oxygenation might occur in the
reaction. Interestingly, when HIRs 2a and 2j were subjected to
the reaction conditions, only two products, 3aa and 3aj, arising
from the decarboxylation of 2a were formed, which showed that
2j could participate in the oxygenation step despite its
ineffectiveness in the decarboxylation step.12 To differentiate
the roles of two carboxylate groups in symmetrical HIRs (such as
2a), the reaction of unsymmetrical substrate 2k was then
explored and failed to yield any oxyalkylation products (Scheme
3B). We speculated that heterolytic rather than homolytic
breaking of the I−O bond of 2k might take place first, resulting in
the formation of acetate anion and cyclic iodonium cation, which
are unable to decarboxylate in the reaction. In addition, Dess−
Martin periodinane 7 exhibited no expected reactivity at all,
which underlines the essential role of iodine(III) cores in
substrates 2.
To probe the nature of the decarboxylation step, the radical-
trapping reagent TEMPO was added into the reaction of 1a and
2a (Scheme 3C). It was shown that the formation of product 3aa
was completely prohibited, and product 8 was obtained in 21%
NMR yield, suggesting again a radical decarboxylation
mechanism. Furthermore, the methyl radical could also be
trapped by TEMPO in the absence of alkene 1a. Considering
that lauroyl peroxide can easily generate acyloxy radical and
subsequent alkyl radical via decarboxylation,14 we examined the
crossover reaction of 2a and lauroyl peroxide with alkene 1a to
gain insight into the nature of the ensuing oxygenation step after
the alkyl radical addition to the alkene (Scheme 3D). It turned
out that only two acetated products, 3aa and 3ag′, originating
from decarboxylation of 2a and lauroyl peroxide, respectively,
were detected. No acyloxy radical-trapped products were formed,
suggesting that the oxygenation step might occur through attack
of a cationic intermediate 9 by the nucleophilic acetate anion
(AcO−). Importantly, formation of ester 10 instead of 3aa and
3ag′ was detected in the absence of Re catalyst, indicating that Re
is indispensable in generating cationic species 9.12,14 To further
confirm the ionic character of the oxygenation step, an equimolar
amount of methanol was added to the reaction of 1f and 2a
(Scheme 3E). To our delight, product 3fa′, arising from
nucleophilic trapping of intermediate 9 by methanol, was
obtained in 21% isolated yield, supporting our hypothesis.12
a
Yields determined by 1H NMR analysis unless otherwise noted.
Determined by GC-MS. Isolated yields.
b
c
Based on the above mechanistic studies, a possible reaction
mechanism is depicted in Scheme 4. HIR 2 first undergoes a
heterolytic cleavage of one I−O bond, giving cationic species 11,
which is reduced by ReI catalyst, affording radical iodine
intermediate 12. Homolytic breaking of the remaining I−O
bond in 12 could form PhI and an acyloxy radical, which suffers a
decarboxylation process to generate alkyl radical 13 and release
CO2 simultaneously.15 It is proposed that visible light might
accelerate this decarboxylation step. Addition of alkyl radical 13
to alkene 1 would lead to radical intermediate 14, which is
oxidized by ReII species to give cation 9 and regenerate ReI
species. Nucleophilic attack of 9 by a carboxylic anion would
eventually result in the formation of product 3, while elimination
of a proton from 9 would afford the oxidative Heck byproduct 4
and the ensuing oxydialkylation byproduct 5.
Scheme 4. Tentative Reaction Mechanism
In summary, we have developed an efficient process for
oxyalkylation of simple alkenes by merging rhenium catalysts
with HIRs derived from aliphatic carboxylic acids. It is the first
time that HIRs are adopted as both alkylation and oxygenation
sources in alkene difunctionalizations.16 The wide substrate
scope, excellent regioselectivity, mild reaction conditions, ease of
C
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Journal of the American Chemical Society
Communication
Stahl, S. S. J. Am. Chem. Soc. 2006, 128, 7179. (c) Desai, L. V.; Sanford,
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importance of fatty acids in sustainable chemistry,13 implemen-
tation of this strategy of merging Re catalysts with HIRs for
functionalization of unsaturated hydrocarbons holds promise in
organic synthesis and is currently underway in our laboratory.
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ASSOCIATED CONTENT
* Supporting Information
Experimental details and spectroscopic data. This material is
available free of charge via the Internet at http://pubs.acs.org.
■
S
AUTHOR INFORMATION
Corresponding Author
wangcy@iccas.ac.cn
■
Notes
(6) For Au catalysis with HIRs: (a) Iglesias, A.; Muniz, K. Chem.Eur.
̃
The authors declare no competing financial interest.
J. 2009, 15, 10563. (b) de Haro, T.; Nevado, C. Angew. Chem., Int. Ed.
2011, 50, 906.
ACKNOWLEDGMENTS
■
(7) For Cu catalysis with HIRs: (a) Seayad, J.; Seayad, A. M.; Chai, C.
L. L. Org. Lett. 2010, 12, 1412. (b) Mancheno, D. E.; Thornton, A. R.;
Stoll, A. H.; Kong, A.; Blakey, S. B. Org. Lett. 2010, 12, 4110. (c) Sanjaya,
S.; Chiba, S. Org. Lett. 2012, 14, 5342.
(8) For Ir catalysis with HIRs: Xie, J.; Xu, P.; Li, H.; Xue, Q.; Jin, H.;
Cheng, Y.; Zhu, C. Chem. Commun. 2013, 49, 5672.
Generous financial support from the National Natural Science
Foundation of China (21002103, 21272238) and the National
Basic Research Program of China (973 Program) (No.
2011CB808600) is gratefully acknowledged.
(9) For a leading review on Re catalysis: (a) Kuninobu, Y.; Takai, K.
Chem. Rev. 2011, 111, 1938. For a leading review on decarboxylation:
(b) Rodríguez, N.; Goossen, L. J. Chem. Soc. Rev. 2011, 40, 5030.
(10) (a) Xia, D.; Wang, Y.; Du, Z.; Zheng, Q.-Y.; Wang, C. Org. Lett.
2012, 14, 588. (b) Tang, Q.; Xia, D.; Jin, X.; Zhang, Q.; Sun, X.-Q.;
Wang, C. J. Am. Chem. Soc. 2013, 135, 4628. (c) Wang, C.; Piel, I.;
Glorius, F. J. Am. Chem. Soc. 2009, 131, 4194. (d) Wang, C.; Rakshit, S.;
Glorius, F. J. Am. Chem. Soc. 2010, 132, 14006.
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