Visible light-promoted ring-opening functionalization of unstrained cycloalkanols via inert C-C bond scission

Article abstract of DOI:10.1039/C8SC01763H

Described herein is a novel, useful, visible light-promoted ring-opening functionalization of unstrained cycloalkanols. Upon scission of an inert cyclic C-C σ-bond, a set of medium- and large-sized rings are readily brominated under mild reaction conditio

Full text of DOI:10.1039/C8SC01763H

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Visible light-Promoted Ring-Opening Functionalization of
Unstrained Cycloalkanols via Inert C-C Bond Scission
Dongping Wang,a Jincheng Maoc and Chen Zhu*,a,b
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
Described herein is a novel, useful, visible light-promoted ring-opening functionalization of unstrained cycloalkanols. Upon
scission of the inert cyclic C-C σ-bond, a set of medium- and large-sized rings are readily brominated under mild reaction
conditions to afford the corresponding distal bromo-substituted alkyl ketones that are hard to make otherwise. The
products are versatile building blocks, which are easily converted to other valuable molecules in one-step operation. The
protocol is also applicable to the unprecedented ring-opening cyanation and alkynylation of unstrained cycloalkanols.
www.rsc.org/
A. Ring strain energy
Introduction
Ring Size
3
4
5
6
7
8
9
10
11
12 .... 15
4.1 1.9
C-C bond activation is always a challenging issue in synthetic
chemistry. Over the past few decades, this area has received
great attention relying on the cleavage of cyclic C-C bonds.1
The strained cycloalkanols such as cyclopropanols and
cyclobutanols have emerged as privileged precursors for the
Strain energy
(kcal/mol)
27.5 26.3 6.2 0.1 6.2 9.7 12.6 12.4 11.3
accomplished in this work
B. Intramolecular PCET-enabled ring opening (Knowles, ref. 7)
Ir cat.
B:
collidine
e-
O
OH
O
preparation of β- and γ-substituted ketones through the
2,3
radical-mediated ring-opening functionalization.
H
thiophenol
O
R
R
R
Recently,
DCM
hv
R
we have consecutively reported the ring-opening
functionalization of cyclobutanols to construct various
chemical bonds, e.g., C-F, C-Cl, C-N, C-S, C-C, etc., based on the
silver or manganese catalysis.4 However, the opening of
unstrained rings (in particular, 5-7 and 12-15 membered rings)
are always confronted with a formidable challenge. It is mainly
attributed to the significantly decreased ring-strain energy
(Scheme 1A).5 During our research, it was also found that the
intramolecular dehydration took place in competition with
ring-opening pathway to suppress reaction outcome.
Therefore, an efficient catalytic protocol should be sought for
the ring opening of unstrained cycloalkanols.
H
R = electron-rich arene
C. CeCl3-enabled ring-opening amination (Zuo, ref. 8)
CeCl3
CeIII
CeIV
O
R
OH
nBu4NCl
R
O
R
O
R
DBAD
- e-
n
CH3CN
hv
N
Boc
NHBoc
n
n
n
D. Ring-opening bromination of unstrained cycloalkanols (this work)
Ir cat.
O
R
OH
O
one-step
conversion
PIDA
NBS
R
R
n
n
hv
X
Br
n
X = O, N, B, I, C...
up to 15-membered ring
n = 0, 1, 2, 7, 10
Advantages:
Photoredox catalysis has proven to be a powerful tool for
the mild generation of alkyloxy radical that triggers the
subsequent ring-opening reactions or other transformations.6
Recently, Knowles et al. applied the intramolecular proton-
1. Opening of medium/ large-sized rings
2. Mild reaction conditions
3. Broad functionality tolerance
4. Useful and versatile products
coupled electron transfer (PCET) to the photocatalytic ring Scheme 1 Ring-opening functionalization of unstrained cycloalkanols.
opening of unstrained cycloalkanols.7 In this remarkable
progress, however, the electron-rich tertiary alcohols were
required to generate the arene radical cation, key
a
intermediate for the intramolecular PCET process. It somewhat
limited the practicality of protocol (Scheme 1B). Later, Zuo et
al. disclosed an elegant photocatalytic ring-opening amination
of unstrained cycloalkanols by cerium chloride complex
(Scheme 1C).8 Beyond that, other types of ring-opening
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Table 1 Reaction parameters surveya
Results and discussion
At the outset, we implemented the reaction parameters
survey with the less strained 1-phenylcyclopentanol 1a as
model substrate and NBS as bromine source (Table 1). It was
found that the use of biphasic solvents was crucial to the
reaction. In the presence of photoredox catalyst (PC) and
hypervalent iodine reagent, the ring-opening bromination
readily proceeded under visible-light irradiation, affording the
desired δ-bromo alkyl ketone 2a. A brief evaluation of solvents
indicated that CCl4/H2O delivered the best yield (entry 4),
while the use of PhCF3/H2O also resulted in the comparable
yield (entry 9). The yield was slightly improved to 76% by using
PC 2 instead of PC 1 (entry 13). Other than PIDA, hypervalent
iodine reagents such as BI-OH, IBX, and DMP were also
suitable to the reaction, but leading to lower yields (entries 16-
18). The amount of H2O was important to the reaction
outcome. Raising the volume of H2O in biphasic solvents
decreased the yield (entry 19), whereas using anhydrous CCl4
only led to trace amounts of product 2a (entry 20). Both PC
and PIDA were not indispensable; removing either one could
still afforded the product in modest yields (entries 21 and 22).
It might suggested that the overall ring-opening process was
appeared as an overlying outcome of two different pathways.
The reaction did not proceed in the absence of both PC and
PIDA or in dark (entries 23 and 24). Finally, the yield of 2a was
further improved to 78% with the use of PhCF3/H2O as the
mixed solvent (entry 25).
Entry
Solvent
(v/v 20/1)
DCM/H2O
DCE/H2O
CHCl3/H2O
CCl4/H2O
DMF/H2O
DMSO/H2O
acetone/H2O
toluene/H2O
PhCF3/H2O
CH3CN/H2O
THF/H2O
MeOH/H2O
CCl4/H2O
CCl4/H2O
CCl4/H2O
CCl4/H2O
CCl4/H2O
CCl4/H2O
CCl4/H2O
CCl4
Photoredox
catalyst
PC 1
PC 1
PC 1
PC 1
PC 1
PC 1
PC 1
PC 1
PC 1
PC 1
PC 1
PC 1
PC 2
PC 3
PC 4
PC 2
PC 2
PC 2
PC 2
PC 2
PC 2
-
Hypervalent
iodine
PIDA
PIDA
PIDA
PIDA
PIDA
PIDA
PIDA
PIDA
PIDA
PIDA
PIDA
PIDA
PIDA
PIDA
PIDA
BI-OH
IBX
Yield
(%)b
22
21
15
74
0
1
2
3
4
5
6
0
7
<5
<5
68
35
0
8
9
10
11
12
13
14
15
16
17
18
19c
20
21
22
23
24d
25
0
76
59
24
70
55
65
70
<5
53
45
0
DMP
PIDA
PIDA
-
With the optimized reaction conditions in hand, we set
about investigating the generality of protocol (Scheme 2).
Firstly, a variety of cyclopentanols were tested. Generally,
electron-deficient aryl substituents were preferred in the
reaction, leading to the δ-bromo alkyl ketones in synthetically
CCl4/H2O
CCl4/H2O
CCl4/H2O
CCl4/H2O
PhCF3/H2O
PIDA
-
-
PC 2
PC 2
PIDA
PIDA
0
78
useful yields. Halides (2b-2d), in particular bromide (2d), were
a1a (0.2 mmol), NBS (0.3 mmol, 1.5 equiv.), hypervalent iodine (0.4 mmol, 2.0
well tolerated, providing a platform for the late-stage product
equiv.), and PC (0.006 mmol, 3 mol %) in mixed solvents (2.0 mL/ 0.1 mL) at rt, 14
manipulation. Positional change (para-, meta-, and ortho-) of
b
c
W blue LEDs irradiation. Yields of isolated products. CCl4/H2O (2.0 mL/ 0.2 mL).
dIn dark.
substituents did not impede the transformation
(2g-2i).
Although the highly electron-rich aryl such as anisole was not
suitable due to the electrophilic bromination of aryl, it could
be overcame by mounting an additional electron-withdrawing
group (2h). This method also allowed for the preparation of
secondary bromide (2j). The ring opening of unsymmetric
cycloalkanols proceeded in a regioselective manner. However,
the synthesis of tertiary bromide was failed under the current
reaction conditions. The scope of cyclohexanols was
investigated more extensively than cyclopentanols. Besides
the functional groups already examined, other groups such as
cyano (2q and 2t) and ester (2z) were also compatible to the
reaction conditions. In addition to the aryl-substituted
cyclohexanols, the alkyl-substituted cyclohexanols were apt to
furnish the elusive distal-bromo dialkyl ketones (2w and 2x).
Various substituents could be incorporated to the alkyl chain
functionalization of unstrained cycloalkanols are still
anticipated.
Alkyl bromides are versatile building blocks in synthetic
chemistry, which can be easily converted to other valuable
molecules through nucleophilic substitution or cross couplings.
We considered that the ring-opening bromination of
unstrained cycloalkanols would give rise to the distally bromo-
substituted alkyl ketones which are synthetically valuable but
hard to make otherwise. Herein, we provide support for this
hypothesis (Scheme 1D). A set of medium- and large-sized
rings are readily brominated through the mild cleavage of inert
cyclic C-C σ-bond with the assistance of visible-light irradiation.
The newly formed C-Br bonds can function as the privileged
precursors for many other useful chemical bonds. Moreover,
the protocol is also applicable to the unprecedented ring-
opening cyanation and alkynylation of unstrained
cycloalkanols.
by using the functionalized cycloalkanol precursors (2y-2ab). In
the presence of excess NBS, the threefold bromination took
place on the toluene-substituted cycloalkanol to give product
2ac which was brominated at both benzylic and distal
positions. The reaction with the cyclohexanol derived from
2 | J. Name., 2012, 00, 1-3
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Scheme 3 Transformation of products to other useful molecules.
1,4-cyclohexandione afforded the unsaturated 1,4-diketone
via dehydrobromination (2ad). Likewise, the ring-opening
bromination of cycloheptanols bearing various functional
groups also readily proceeded, affording the corresponding
distal-bromo alkyl ketones in useful yields
(2ae-2ak).
Unfortunately, the ring opening of eight- and ten-membered
cycloalkanols failed, leading to complex mixtures. The reason is
unclear so far. Remarkably, the opening of large-sized rings
such as cyclododecanols and cyclopentadecanols occurred
efficiently, yielding a variety of distally brominated alkyl
ketones that are hard to make otherwise (2al-2ar).
To manifest the utility of protocol, the products were
converted to other valuable molecules via nucleophilic
substitution or cross-coupling in one or two steps (Scheme 3).
Firstly, the bromide in 2a was easily replaced by azide and
iodide, forming new C-N3 and C-I bonds in good yields (
).9 Then, the ketone in 2a was reduced to alcohol that
intramolecularly attacked the alkyl bromide, leading to
tetrahydropyran
in two steps with high yield.10 Alternatively,
3 and
4
5
the C-Br bond was readily converted to C-B and C-C bonds via
transition-metal catalyzed cross-coupling reactions, affording
synthetically useful building blocks or molecules (6 and 7
).11
Scheme 2 Scope of unstrained cycloalkanols.
Reaction conditions: 1 (0.2 mmol), NBS (0.3 mmol, 1.5 equiv.), PIDA (0.4 mmol,
2.0 equiv.), and PC (0.006 mmol, 3 mol %) in mixed solvents (2.0 mL/ 0.1 mL) at
rt, 14 W blue LEDs irradiation. Yields of isolated products are given. aWith
Condition b. b[Ir(dF(CF3)ppy)2(dtbbpy)]PF6 as PC. cNBS (0.8 mmol, 4.0 equiv.).
Scheme 4 Production of haloperidol analogues.
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Journal Name
cyanation
A. Ring-opening
of large-sized cycloalkanol
Ph
OH
[Ir(ppy)2(dtbbpy)]PF6
O
CN
Ts , PIDA
12
Ph
CH3CN
7
5
CN
9
14 W blue LEDs
1
40%, 22 h
B. Ring-opening alkynylation of large-sized cycloalkanol
SO2Ph
O
TBS
Ph
Ph
OH
[Ir(ppy)2(dtbbpy)]PF6
PIDA
7
12
CH3CN
5
14 W blue LEDs
TBS
10
1
44%, 22 h
Scheme 6 Ring-opening cyanation and alkynylation of unstrained cycloalkanols.
cyano- or alkynyl-substituted alkyl ketones in synthetically
useful yields (9 and 10), providing a non-trivial approach to
construct the remote C-C bonds (Scheme 6).
Scheme 5 Plausible pathways of ring-opening bromination.
Haloperidol is a marketed antipsychotic drug extensively
used to treat schizophrenia and Tourette's syndrome. After
gaining
precursors, we accomplished the preparation of haloperidol
analogues in high yields (8a
8d, Scheme 4).12 The test for their
a portfolio of distal-bromo alkyl bromides as
Conclusions
We have described a novel and efficient visible light-enabled
ring-opening functionalization of unstrained cycloalkanols via
-
biological activities is now ongoing.
the mild cleavage of cyclic C-C σ-bonds.
cyclopentanols, cyclohexanols,
A
variety of
According to the experimental results, the plausible
mechanism is depicted (Scheme 5, top). Although the detailed
cycloheptanols,
cyclododecanols, and cyclopentadecanols are readily
proceeded to furnish the distally brominated alkyl ketones that
often function as the precursors of complex molecules in
organic and medicinal synthesis. As shown above, this method
provides the important feedstocks for the production of
haloperidol analogues. The newly formed C-Br bonds in
products are easily transformed into other valuable chemical
bonds, thus illustrating the utility of method. The protocol is
also applicable to the elusive ring-opening cyanation and
alkynylation of unstrained cycloalkanols, providing an unusual
strategy for construction of the remote C-C bonds.
process for the generation of cycloalkoxy radical
I is not fully
understood, the radical I might be delivered via two pathways.
Firstly, Stern-Volmer studies disclose that the excited state of
IrIII catalyst PC 2 could be oxidatively quenched by NBS to
generate the IrIV complex (see the Supporting Information).
However, the oxidation potential of this IrIV complex (E1/2
=
IV/III
1.21 V in MeCN vs. SCE) is unable to oxidize cycloalkanol
> 2.0 V in MeCN vs. SCE) to alkoxy radicals
1
(Ep/2
I
via SET process (for
the cyclic voltammetry studies, see the Supporting
Information). Thus, we postulate an intramolecular proton-
coupled electron transfer (PCET) process for the generation of
alkoxy radical
I
in the presence of an IrIV complex and weak
base such as succinimide anion (path a).13 Alternatively,
Conflicts of interest
homolysis of the O-I bond in situ formed by the reaction of
cycloalkanol
(path b).14 In either way, the visible-light irradiation is
indispensable. The subsequent β-C scission of leads to the
ring-opened alkyl radical II, which is intercepted by NBS to give Acknowledgements
the final product . Notably, CBr4 is also a competent bromine
1 with PIDA might also lead to the alkoxy radical I
There are no conflicts to declare.
I
2
C.Z. is grateful for the financial support from Soochow
University, the National Natural Science Foundation of China
(Grant no. 21722205), the Project of Scientific and Technologic
Infrastructure of Suzhou (SZS201708), and the Priority
Academic Program Development of Jiangsu Higher Education
Institutions (PAPD).
source in lieu of NBS to afford the same brominated product,
suggesting the formation of intermediate II during the reaction
(Scheme 5, bottom).
This protocol is also applicable to the challenging ring-
opening cyanation and alkynylation of unstrained
cycloalkanols.15 Under the similar reaction conditions, 1-
phenyl cyclododecanol was readily converted to the distally
Notes and references
4 | J. Name., 2012, 00, 1-3
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‡ Dedicated to Professor Takahiko Akiyama on the occasion of 11 (a) Z.-L. Shen, K. K. K. Goh, C. H. A. Wong, Y.-S. Yang, Y.-C. Lai,
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Reported herein is a novel, useful, visible light-promoted ring-opening functionalization of
unstrained cycloalkanols.