Copper-Catalyzed Acyloxycyanation of Alkynes with Acetonitrile: Regioselective Construction of Cyclic Acrylonitriles by 6-endo or 5-exo Cyclization

Article abstract of DOI:10.1002/adsc.201700577

An efficient difunctionalization of alkynes by tandem iodolactonization and copper-catalyzed cyanation using acetonitrile as a cyanating reagent is reported for the first time. This approach can afford cyano-containing isocoumarin or phthalide derivatives

Full text of DOI:10.1002/adsc.201700577

Title: Copper-Catalyzed Acyloxycyanation of Alkynes with Acetonitrile:
Regioselective Construction of Cyclic Acrylonitriles by 6-endo or
5-exo Cyclization
Authors: Yamin Zhu and Zengming Shen
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To be cited as: Adv. Synth. Catal. 10.1002/adsc.201700577
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10.1002/adsc.201700577
Advanced Synthesis & Catalysis
COMMUNICATION
DOI: 10.1002/adsc.201((will be filled in by the editorial staff))
Copper-Catalyzed Acyloxycyanation of Alkynes with Acetonitrile: Regioselective
Construction of Cyclic Acrylonitriles by 6-endo or 5-exo Cyclization
Yamin Zhu,a Zengming Shena,*
a
School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai,
200240, China
Fax: 86-21-54748325; e-mail: shenzengming@sjtu.edu.cn
Received: ((will be filled in by the editorial staff))
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201######.
cyanating reagent. This reaction also offers a new
way to synthesize a series of cyano-containing
isocoumarin and phthalide derivatives that have not
been accessed so far.
Abstract: An efficient difunctionalization of alkynes
by tandem iodolactonization and copper-catalyzed
cyanation using acetonitrile as a cyanating reagent is
reported for the first time. This approach can afford
cyano-containing
isocoumarin
or
phthalide
Isocoumarin and phthalide derivatives are known to
have a wide occurrence in natural products and
pharmaceutical compounds.[10] Due to the potential
functionalities of isocoumarin and phthalide
derivatives, we decided to focus our initial study on
the construction of cyclic acrylonitrile structures by
using methyl 2-(phenylethynyl)benzoate 1a as a
model substrate. We propose the intramolecular
acyloxycyanation of alkynes may undergo two
competing cyclization pathways to provide the 6-endo
isocoumarin products 2 or 5-exo phthalide products 5
(Scheme 1c).[11]
derivatives in good yields by careful choice of the
carboxylate nucleophiles and electrophilic iodine
sources. Thus, an acyloxycyanation strategy can be
achieved in good yields and high regioselectivity of
either 6-endo or 5-exo cyclization products.
Keywords: acyloxycyanation, acetonitrile, isocoumari-
ns, phthalides, iodolactonization
Difunctionalization has emerged as an efficient
method for the transformation of alkynes by
introducing two functional groups in one pot.[1]
Although transition metal-catalyzed cyanofunctional-
ization of alkynes have been reported to build vinyl
C‒CN bonds (i.e. X‒C=C‒CN where X = C, O, S, Si,
B, Br, Ge, Sn) (Scheme 1a).[2,3] To date, only one
example of intermolecular cyanotriflation using
aryl(cyano)iodonium triflates as the cyano-source has
been documented (Scheme 1b).[3k] Therefore, the
available methodologies for oxycyanation of alkynes
remains limited. Nitriles are versatile precursors to
build other useful functional groups, but are also
important motifs found in drugs, dyes, pesticides,
electronic materials.[4] Due to the toxicity of many
cyanating
reagents,
developing
user-friendly
protocols and green cyano-sources has been an
ongoing effort.[5,6] Considering the challenge of
alkyne oxycyanation, we were interested in
developing an acyloxycyanation with acetonitrile as a
cyano source (Scheme 1c). Acetonitrile is an
attractive cyano source, featuring several advantages:
1) it is abundant, affordable, and commonly used as a
solvent; 2) it is a safe and atom-economic “CN”
source; 3) it can avoid the generation of high
concentration of “CN” during cyanation processes.[7,8]
As highlighted by Takagi,[9] the high concentration of
cyanide may reduce catalytic efficiency of transition
metal-catalysts due to catalyst poisoning. Herein, we
describe the first Cu-catalyzed regioselective
acyloxycyanation of alkynes with acetonitrile as the
Scheme 1. Strategies for alkyne cyanofunctionalization
With this hypothesis in mind, we chose to test the
acyloxycyanation with
a
Cu/TEMPO/(Me3Si)2
protocol, which was first reported by our group as an
efficient method for acetonitrile C‒CN bond cleavage
(Table 1).[8d-f] However, under these conditions, no
desired cyclic acyloxycyanated products 2a or 5a
were observed. Instead, lactonization led to 3-phenyl-
1H-isochromen-1-one 3a in quantitative yield (Table
1, entry 1).[12]
We hypothesized that
a
sequential one-pot
1
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10.1002/adsc.201700577
Advanced Synthesis & Catalysis
iodolactonization/cyanation protocol could avoid rings were subjected to the standard conditions. These
forming of unexpected lactonizated byproduct 3a. reactions underwent 6-endo acyloxycyanation to
Additionally, it opens a new avenue to achieve provide the corresponding products in moderate to
selective
formation
of
6-endo
vs
5-exo
acyloxycyanation products.[13] Gratifyingly, a 6% Table 2. Scope of 6-endo acyloxycyanation.[a,b]
yield of 6-endo acyloxycyanation product 2a was
detected without the formation of 5-exo isomer 5a
when using iodine monochloride (ICl, 1.1 equiv) as
an
iodinating
reagent.
Although
6-endo
iodolactonization intermediate 6a was isolated in 92%
yield (entry 2). Further screening of silver-salt
oxidants led to substantial improvement in yields of
2a (entries 3–5).[8b-c,8g,14] Interestingly, we noted that
two equivalents of AgOAc are necessary since one
equivalent of AgOAc only gave 17% yield (entry 6).
By switching TMEDA to PPh3, 2a was obtained in
the excellent yield of 94% within 18 h (entry 14).
Other types of ligands, such as DMEDA, 1,10-phen,
bpy, dppe, dppf and PPh3O, furnished 2a in moderate
yields (67–83%, entries 8–13). Changing the oxygen
atmosphere to air resulted in slight decrease in yield
(71% yield, entry 15). Additionally, the use of
nitrogen atmosphere displayed very low reactivity (15%
yield, entry 16). Reducing temperature resulted in a
lower yield of 2a (63% yield, entry 17).
Table 1. Reaction conditions screening for 6-endo
acyloxycyanation.[a]
]
[a
Conditions: substrate 1 (0.2 mmol), CH3CN (1.5 mL), ICl (1.1 equiv),
Cu(OAc)2 (20 mol%), PPh3 (20 mol%), (Me3Si)2 (2 equiv), AgOAc (2
[b]
[c]
[d]
o
equiv), O2, 150 C, 18–48 h.
Isolated yield. R1 = Me.
The first
step: substrate 1 (0.2 mmol), CH3CN (1.5 mL), ICl (1.1 equiv), 1 h; the
second step: Cu(OAc)2 (20 mol%), PPh3 (20 mol%), (Me3Si)2 (2 equiv),
AgOAc (2 equiv), O2, 150 oC, 18–48 h.
good yields of 54–92% (2f–2i). Notably, we
discovered that two 4-cyano-α-pyrone structures
could be accessed through our procedure in 51% and
57% yield, respectively (2j and 2k). Additionally,
heteroaromatic nitriles were formed under our
procedure demonstrating the generality of our
method. For example, aryl ethers (-OMe), phenols (-
OH), aryl thioethers (-SMe), and anilines (-NMe2)
could replace the ester (-COOR) group (2l–2n) (see
the supporting information, Scheme S1).
[a]
Conditions: 1a (0.2 mmol), ICl (1.1 equiv), CH3CN (1.5 mL),
We hypothesized we could control the
regioselectivity of the iodolactonization prior to Cu-
o
[b]
Cu(OAc)2 (20 mol%), ligand, (Me3Si)2 (2 equiv), oxidant, O2, 150 C.
1
Determined by H NMR using 1,3,5-trimethoxybenzene as the internal catalyzed cyanation to afford 5-exo acyloxycyanation
standard. [c] Without ICl. [d] Isolated yield. [e] Under air. [f] Under N2. [g] The by careful choice of the nucleophilic carboxylate and
reaction was run at 130 oC.
iodinating reagent. To reach this goal, we examined
potassium benzoate or carboxylic acid substrates with
different I+ electrophiles such as iodine monochloride
(ICl), N-iodosuccinimide (NIS), and iodine (I2). We
found that the identity of the nucleophile plays a
With this protocol for 6-endo acyloxycyanation in
hand, we next examined the substrate scope with a
variety of 2-(alkynyl)benzoate esters, as shown in
Table 2. Other ester groups (R1 = Et, i-Pr, t-Bu) could
also furnish the corresponding 3-phenyl-4-
cyanoisocoumarin product 2a smoothly in 61–86%
yields. Alkyne moieties bearing different aryl, alkyl
and heteroaryl groups were well tolerated with up to
99% yields (2b–2e). Substrates with electron-
donating or electron-withdrawing groups on aromatic
major
role
on
the
regioselectivity
of
iodolactonization. For example, the use of benzoate
ester or benzoic acid predominantly afforded 6-endo
cyclization products. In contrast, when using
potassium benzoate, 5-exo cyclization became the
major product (see the supporting information, Table
S1).[12a,15] To our delight, 5-exo iodolactonization was
achieved in good yield and selectivity (85% yield,
2
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10.1002/adsc.201700577
Advanced Synthesis & Catalysis
>20:1 selectivity) when using potassium 2- Aromatic and heteroaromatic rings also provided the
(phenylethynyl)benzoate 4a with NIS in acetonitrile desired 5-exo cyclization products (5b–5d) albeit with
for 5 minutes at room temperature (see the supporting lower yields. Different substituents on the aryl ring
information, Table S1). In case of potassium have been evaluated with our protocol. For example,
benzoate, I+ sources with
both 5-methyl- (4g) and 4,5-dimethoxy- (4h)
substituted potassium benzoates gave the desired
products in 42% and 65% yields, respectively. In
addition, heterocycle substrate 4i with quinoline
structure underwent cyclization, albeit in low yield
(27%).
Table 3. Scope of 5-exo acyloxycyanation.[a,b]
Although the detailed reaction mechanism
warrants further study, a proposed mechanism for the
Cu-catalyzed acyloxycyanation of alkynes with
acetonitrile is depicted in Scheme 2 on the basis of
literature[12a,15] and our observations. The alkyne in 1a
or 4a is first activated by coordination to the
electrophilic iodine source (I+). Two competing
pathways can then be involved in the following
nucleophilic attack. When using methyl 2-
(phenylethynyl)benzoate 1a and iodine monochloride
(ICl), 6-endo-dig cyclization is preferred to form
product 6a (path A). Conversely, when using
potassium benzoate 4a and N-iodosuccinimide (NIS),
5-exo-dig cyclization is preferred to form product 7a
(path B). The cyanation of 6a is described in cycle C.
Intermediate 6a may undergo oxidative addition with
LnCuIOAc to produce LnCuIII species I with assistance
of AgOAc to precipitate AgI. Ligand exchange with
cyanide, which is generated in situ by the cleavage of
acetonitrile, gives CuIII–cyanide species II. Finally,
reductive elimination of the intermediate II provides
the desired acyloxycyanation product 2a. The Cu-
catalyzed cyanation proceeds in the same fashion for
the 5-exo acyloxycyanation product 5a. Notably, the
selective performance of 6-endo versus 5-exo
acyloxycyanation depends on careful choice of the
nucleophilic partner and iodinating reagent. Thus, the
iodolactonization step is responsible for the
regioselectivity of 6-endo or 5-exo acyloxycyanation.
The reason for the regioselectivtiy is not fully
understood at this stage.
[
a
] Conditions: the first step:
3 (0.2 mmol), ICl (1.1 equiv), CH3CN (1.5
mL), r.t., air, 0.5 h. After extraction, the residue was washed by
acetonitrile into oven-dried Schlenk tube. Then other compounds were
added into it for the second step: Cu(OAc)2 (20 mol%), pyridine-2-ol
(40 mol%), (Me3Si)2 (2 equiv), AgOAc (2 equiv), CH3CN (1.5 mL),
air, 150 oC, 18
–
48 h. [b] Isolated yield.
lower
electrophilicity
prefer
5-exo
iodolactonization.[12] With these results in hand, we
optimized the following cyanation conditions and
determined that a stepwise protocol gave the desired
5-exo acyloxycyanation product (77% isolation yield,
see the supporting information, Table S2).
We further explored the generalization and
limitation of 5-exo acyloxycyanation (Table 3).
Alkyne moieties attached with alkyl groups, such as t-
Bu (4e) and n-Pr (4f) gave good yields (62–64%).
In conclusion, we report a novel approach for
3
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10.1002/adsc.201700577
Advanced Synthesis & Catalysis
Scheme 2. Proposed mechanism
Cu-catalyzed acyloxycyanation of alkynes by
using acetonitrile as a green and affordable
cyanating reagent. This transformation displays a
new avenue for selective construction of 6-endo
or 5-exo cyclic acrylonitriles, which may possess
Acknowledgements
This work was supported by the National Natural Science
Foundation of China (21672144, 21272001), Shanghai Education
Committee (13ZZ014). We are grateful to the Instrumental
Analysis Center of SJTU for compound analysis.
synthetic
applications
in
pharmaceutical
molecules. Careful choice of the carboxylate
nucleophiles and iodinating reagents allows for
selective iodolactonization to furnish various 6-
and 5-membered rings. By using benzoate esters
or potassium benzoates bearing alkynyls, cyano-
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5
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10.1002/adsc.201700577
Advanced Synthesis & Catalysis
COMMUNICATION
Copper-Catalyzed Acyloxycyanation of Alkynes
with Acetonitrile: Regioselective Construction of
Cyclic Acrylonitriles by 6-endo or 5-exo
Cyclization
Adv. Synth. Catal. Year, Volume, Page – Page
Yamin Zhu,a Zengming Shena,*
6
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