Two catalytic protocols for Achmatowicz rearrangement using cyclic diacyl peroxides as oxidants

Article abstract of DOI:10.1039/c8ob01382a

In situ generated bromonium-catalyzed and visible-light photocatalytic Achmatowicz rearrangements of furfuryl alcohols using cyclic diacyl peroxides as oxidants are described. Both protocols feature broad substrate scope, excellent functional group tolera

Full text of DOI:10.1039/c8ob01382a

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Takeharu Haino et al.
Solvent-induced emission of organogels based on tris(phenylisoxazolyl)
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DOI: 10.1039/C8OB01382A
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Two Catalytic Protocols for Achmatowicz Rearrangement by Using
Cyclic Diacyl Peroxides as Oxidants
Congyin Wei, a,b Rong Zhao, a,b Zhihong Shen, a,b Denghu Chang, a,b and Lei Shi*, a,b
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
In-situ generated bromonium-catalyzed and visible-light
photocatalytic Achmatowicz rearrangements of furfuryl alcohols by
using cyclic diacyl peroxides as oxidants are described. Both
protocols feature broad substrate scope, excellent functional group
tolerance, and mild reaction conditions, affording the synthetically
useful dihydropyranone derivatives in good yields.
Oxidation reactions are of fundamental significance in
nature and continue to play a key role in modern organic
synthesis and the industrial production of bulk and fine
chemicals.1 In this context, a large variety of oxidizing agents
such as hydrogen peroxide and other acyclic organic peroxides
have been and are being investigated extensively and
2
systematically for the challenging oxidative transformations.
In contrast, there have been few studies to date examining the
reactivity of cyclic diacyl peroxides,3 in spite of the fact that they
were found to exhibit the higher (or better) thermal stability
than their similarly atom-connected acyclic peroxides.4
Scheme 1 Representative transformations and applications of Achmatowicz
reaction products.
The Achmatowicz rearrangement5 6 over the past decades
has demonstrated its usefulness in the oxidative conversion of
substituted furylcarbinols into much more structurally complex
,-unsaturated dihydropyranone acetals containing multiple
functional handles for further synthetic transformations
(Scheme 1).7 Since its discovery,8 this oxidation reaction has
been considerably exploited as a highly efficient ring expansion
protocol for the synthesis of numerous pharmaceutically
relevant building blocks and natural products.9 Many kinds of
reagents have been employed for the rearrangement to date,
the most popular being N-bromosuccinimide (NBS)10 and
m-chloroperoxybenzoic acid (m-CPBA). Other conditions that
have also been reported include Br2/MeOH, in situ generated
dimethyldioxirane
(DMDO),
KBr/Oxone11
and
Oxone/photocatalysts.12 It is particularly noteworthy that
catalytic variants of Achmatowicz rearrangement are relatively
scarce.13 In the field of modern green and sustainable
chemistry,
catalytic
oxidative
transformations
as
environmentally friendly technologies with low waste
generation and energy consumption as well as high atom
economy and environmental friendliness are urgently required.
Furthermore, the direct utilization of water as a reaction
medium is an increasing trend to develop cleaner catalytic
14
processes.11-12,
In connection with our current research
interest in synthetic utility of cyclic diacyl peroxides.15 We now
reported herein two distinct catalytic protocols for
Achmatowicz rearrangement by employing cyclic diacyl
peroxides as efficient and mild oxidants, which follow different
reaction pathways according to the catalytic system and the
reaction conditions. To the best of our knowledge, cyclic diacyl
a.MIIT Key Laboratory of Critical Materials Technology for New Energy Conversion
and Storage, School of Chemistry and Chemical Engineering, Harbin Institute of
Technology, Harbin 150001, China
b.Shenzhen Graduate School, Harbin Institute of Technology, Shenzhen, People's
Republic of China
c. † Footnotes relating to the title and/or authors should appear here.
d.Electronic Supplementary Information (ESI) available: NMR spectra, CCDC
1580033-1580035. See DOI: 10.1039/x0xx00000x
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reaction efficiency (only 22% yield of 2a) was observed in the
Table 1 Optimization of the reaction conditions for in-situ generated bromonium-
catalyzed Achmatowicz rearrangement.a
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absence of the catalytic bromide (Table 1D, OenI:t1r0y.110139)./CF8inOaBl0ly1,3t8h2Ae
Table 2 Optimization of the reaction conditions for visible-light-induced photocatalytic
approach a
Entry
1
Oxidants
MPO
MPO
MPO
MPO
PPO
Solvent
THF
Yieldb(%)
40
2
DCM
65
Entry
1c
2d
3e
4
Oxidants
PPO
Solvent
Yieldb(%)
65
3
MeCN
46
THF/H2O=4/1
THF/H2O=4/1
THF/H2O=4/1
DCM/H2O=1/1
DMSO/H2O=1/1
MeCN/H2O=3/1
MeCN/H2O=3/1
MeCN/H2O=3/1
MeCN/H2O=3/1
MeCN/H2O=3/1
4
THF/H2O=4/1
THF/H2O=4/1
THF/H2O=4/1
THF/H2O=4/1
THF/H2O=4/1
THF/H2O=4/1
THF/H2O=4/1
THF/H2O=4/1
72
PPO
70
PPO
79
5
92
PPO
65
6
Cl-PPO
BPO
87
5
PPO
N.R
82
7
5
6
PPO
8c
9d
10e
11f
PPO
32
7
MPO
m-CPBA
BPO
65
PPO
22
8
72
PPO
35
9
N.R
92
PPO
22
10
Cl-PPO
a Reaction conditions: 1a (77 mg, 0.5 mmol), oxidant (0.6mmol), TBAB (8 mg, 2.5 μ
a Reaction conditions: 1a (77 mg, 0.5 mmol), oxidant (0.5 mmol), photocatalyst (0.5
c
·mol), solvent (5 mL), 25 °C, 12 h. b Isolated yield. Reaction temperature 80°C. d
b
c
mol % ), solvent (5 mL), 25 °C, 5 h. Isolated yield. Use fac-Ir(ppy)3 as
Use TBACl instead of TBAB. e Use TBAI instead of TBAB. f Not add catalyst.
d
e
photocatalyst.
Use Ru(bpy)3Cl2·6H2O as photocatalyst.
Use
Ir[dF(CF3)ppy]2(dtbbpy)PF6 as photocatalyst.
peroxides have never been explored as the external (or
terminal) oxidant for Achmatowicz oxidative rearrangement. 6
reaction conditions described in Table 1 entry 5, were selected
as the standard reaction conditions for our in-situ generated
bromonium-catalyzed Achmatowicz rearrangement.
The study commenced with an exploration of the reaction
of readily available 1-(furan-2-yl)pentan-1-ol (1a) shown in
Table 1, and various parameters such as reaction medium,
oxidants, catalysts and reaction temperature have been taken
into consideration to optimize the reaction conditions. To our
delight, 40% of desired product 2a was obtained using
cyclopentyl malonoyl peroxide (MPO) as the terminal oxidant
and 5 mol % of tetrabutylammonium bromide (TBAB) as the
ionic organocatalyst in detrahydrofuran (THF) at room
temperature for 12 h (Table 1, entry 1). Among a broad range
of reaction medium surveyed, namely dichloromethane (DCM),
dimethyl sulfoxide (DMSO), MeCN and a 4/1 mixture of THF and
H2O provided the expected product in superior yield (Table 1,
entry 2 and 3). Next, the effects of varying oxidants were also
investigated, and it was found that the efficiency of the desired
transformation increasing when phthaloyl peroxide (PPO) was
used as oxidant (Table 1, entry 5). Conversely, the act of
replacing PPO with acyclic peroxide (benzoyl peroxide, BPO) is
harmful (Table 1, entry 7). Interestingly, we observed that the
variation of the TBAB with tetrabutyl ammonium chloride
(TBACl) or tetrabutylammonium iodide (TBAI) has a significant
effect on the yield and reaction rate (Table 1, entries 8 and 9).
In addition, the yields of the transformation was obviously
reduced by increasing the reaction temperature room
temperature to 80oC (Table 1, entry 10), presumably due to the
instability of the subsequent intermediary halonium ion sources
at higher temperature. It should also be mentioned that the low
Visible-light-mediated photoredox catalysis has emerged
in recent years as a promising and enabling platform to access
important organic transformations due to its versatility and
environmental compatibility in green and sustainable
chemistry.16 Consequently, we decided to perform visible-light-
mediated photoredox catalysis as a viable alternative to
conventionally applied oxidation procedures of Achmatowicz
rearrangement. Examination of a range of photocatalysts and
oxidants in different solvents at room temperature revealed
that a combination of Ir[dF(CF3)ppy]2(dtbbpy)PF6 and 4,5-
dichlorophthaloyl deroxide (Cl-PPO) in a 3/1 mixture of MeCN
and H2O (Table 2, entry 10) reaction efficiency. As a comparison,
the us e o f o ther pho toca tal ys ts ( f ac - Ir(ppy) 3 o r
Ru(bpy)3 Cl2 ·6H2 O) under similar reaction molarities
0.5 mmol·L-1) resulted in diminished yields (Table 2, entries 1
and 2), which revealed that an adequately high oxidizing
capability f the excited photocatalyst to promote a SET process
is the crucial requirement. As anticipated, the choice of an
appropriate external oxidant was evidently most pivotal for
achieving an appreciable conversion to the desired product 2a
,
and the employment of BPO, MPO and m-CPBA all drastically
inhibited the reactivity (Table 2, entry 7, 8 and 9).
With two identified optimal reaction conditions in hand, we
then sought to explore the substrate scope of a variety of
furfuryl alcohols using both our in-situ generated bromonium-
2 | J. Name., 2012, 00, 1-3
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catalyzed protocol and visible-light-induced photocatalytic meta, para) on the aryl rings (1m
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,
1o
,
1q and 1r), seemed to
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approach. As shown in Table 3, the transformations using two
different methods generally proceed to afford the
Table 3 Substrate Scope of furfuryl alcohols a
have a
significant influence on theDOrIe: a10c.t1i0o3n9/Ce8fOfiBc0ie13n8c2yA.
Gratifyingly, both our methodologies for Achmatowicz
Scheme 2 Proposed Mechanism for the in-situ generated bromonium-catalyzed
protocol.
a Conditions: Meth A: The reaction was run in 0.5 mmol of furfuryl alcohol, PPO (98
mg), TBAB (8 mg), THF/H2O =4/1(5 mL), 25 °C, 12 h, isolated yield; Meth B:The
reaction was run in 0.5 mmol of furfuryl alcohol, Cl-PPO (115 mg),
Ir[dF(CF3)ppy]2(dtbbpy)PF6 (2.8 mg), MeCN/H2O=3/1 (5 mL), 25 °C, 12 h, isolated
yield.
rearrangement could be amenable to gram-scale synthesis
without any loss of reactivity and efficiency (2c). Following the
corresponding
good to excellent isolated yields (64%
reaction systems proved to be tolerant to several functional

,

-unsaturated dihydropyranone products in
95%). Importantly, both
Scheme 3 Proposed Mechanism for the Photoredox mediated Achmatowicz
−
Rearrangement.
groups, including ether (2d, 88% and 87%), ketone (2i, 72% and
above-mentioned procedures, Achmatowicz rearrangement of
1c proceeded smoothly to give rise to piperidine 2c in 85% and
88% yields.
According to the above experimental results and previous
relevant reports,11 a plausible mechanism is proposed for both
transformations in Scheme 2 and Scheme 3. For our in-situ
generated bromonium-catalyzed Achmatowicz rearrangement,
the in-situ generated brominating agent originating from PPO
and TBAB led to the formation of a bromonium intermediate
85%), alkene (2s, 81% and 79% ) and halogens (2m and 2o
,
82−95% yield), thereby significantly expanding the substrate
scope and synthetic usefulness. No noticeable and competing
side reactions such as arene bromination, ketone
-
bromination, alkene difunctionalition, and alcohol oxidation
occur simultaneously in both pathways to achieve Achmatowicz
rearrangement products. Moreover, neither electron-donating
and withdrawing properties, or the substitution patterns (ortho,
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Kennedy and N. C. Tomkinson, Org. Lett., 2015, 17, 5132-
(
1
), which can undergo a SN2-like nucleophilic addition of H2O
(or bromonium ring-opening reaction) to give brominated
hemiacetal (2)
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5135.
DOI: 10.1039/C8OB01382A
3. R. Zhao, D. Chang and L. Shi, Synthesis, 2017, 49, 3357-
3365.
.
For our visible-light promoted photocatalytic Achmatowicz
rearrangement, it is thought to proceed through the reduction
of cyclic diacyl peroxide by the excited-state (Ir(III) */Ir(IV)= -
0.98V), yielding radical cation and Ir(IV), which is same with the
previous visible-light-mediated Achmatowicz rearrangement by
the use of Ru(bpy)3Cl2·6H2O and sodium persulfate. The Ir(IV)
species (E1/2 III/II =1.68 V vs SCE) effects second single electron
transfer (SET) to furfuryl alcohol, giving the distonic radical
anion, which can further oxidize the radical cation to
furanoxonium ions. Eventually, the hydrolysis of brominated
hemiacetal or oxocarbenium furnishes the corresponding
hydropyranone.
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Conclusions
In summary, by the combination of cyclic diacyl peroxide as
oxidant with TBAB or Ir[dF(CF3)ppy]2(dtbbpy)PF6 as catalyst,
we have demonstrated two catalytic protocols for Achmatowicz
rearrangement. These two approaches are characterized by
their good functional group tolerance, mild reaction condition
(room temperature and atmospheric pressure), and utilization
of easily available cyclic diacyl peroxides, thus making them an
attractive feature in the practical preparation of Achmatowicz
rearrangement products.
Conflicts of interest
There are no conflicts to declare.
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This work was financially supported by the “Fundamental
Research
Funds
for
the
Central
University”
(HIT.BRETIV.201502), and the Open Project Program of Hubei
Key Laboratory of Drug Synthesis and Optimization, Jingchu
University of Technology (no. opp2015ZD01).
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DOI: 10.1039/C8OB01382A
Development of two new catalytic protocols for Achmatowicz rearrangement using
cyclic diacyl peroxides as the terminal oxidant.