Iodine promoted cascade cycloisomerization of 1-en-6,11-diynes

Article abstract of DOI:10.1039/c9cc08286g

An iodine promoted cascade cycloisomerization of 1-en-6,11-diynes is presented for the easy preparation of tetrahydrobenzo[f]isoquinolines. This developed reaction system is identified as having good functional-group applicability and can be scaled up to gram quantities. In this transformation, two new cyclic frameworks and one carbonyl group are formed with four new bonds constructed. Additionally, the resulting iodo-substituted compounds could be further derived through simple elimination reactions.

Full text of DOI:10.1039/c9cc08286g

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DOI: 10.1039/C9CC08286G
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Iodine Promoted Cascade Cycloisomerization of 1-En-6,11-diynes†
Yi-Feng Qiu,‡a Yue-Jie Niu,‡a Xian-Rong Song,b Xi Wei,a Hui Chen,a Shun-Xi Li,a Xi-Cun Wang,a
Congde Huo,*a Zheng-Jun Quan*a and Yong-Min Liangc
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
An iodine promoted cascade cycloisomerization of 1-en-6,11- be subsequently attacked by various nucleophilic groups.4
diynes is presented for the easy preparation of tetrahydroben- Consequently, cascade iodocyclization reaction has achieved
zo[f]isoquinolines. This developed reaction system is identified as remarkable applications in the construction of numerous cyclic
good functional-group applicability and can be scaled up to gram scaffolds due to its straightforward reaction system with easy
quantities. In this transformation, two new cyclic frameworks and operations and broad functional group compatibilities.5
one carbonyl group are formed with four new bonds constructed. Specifically, Larock,6 Yamamoto,7 Ma,5a,8 our group,9,10 and
Additionally, the resulting iodo-substituted compounds could be other groups.11–16 have made valuable constructive
further derived through simple elimination reactions.
contributions in this field by successful evolvements in diverse
basic cyclic systems, including furan,6a–6b,7d (iso)quinoline,7a–7c,12
functionalized benzene,9c,13 indole,14 and fused molecule15
(Scheme 1a). In particular, the Wang group presented an
efficient preparation of 4-iodomethyl substituted tetrahydro-β-
carbolines via cascade iodocyclization strategy in 2013 (Scheme
1b).16 Accordingly, in the last couple of years, we have favorably
explored a series of works on the construction of carbo- and/or
heterocyclic building blocks by cascade iodocyclization.10 Given
the demand and prospect of green chemistry as well as our
continued research interests on the preparation of cyclic
The synthesis of complex polycyclic molecules has always been
a
momentous research subject in synthetic chemistry,
especially for the preparation of multiple cyclic systems within
one step.1 Enynes have become the star starting materials for
efficient construction of such compounds.2 Still, reactions
involving these substrates typically depend on transition metal
catalysts or harsh conditions.2,3 In addition, some inherent
defects, such as poor product yields, troublesome operations,
and restricted substrate scope make reconsideration for further
applications in modern synthetic chemistry. Consequently, a
green synthetic strategy for potential industrial production with
straightforward conditions in low cost, is still fueled by the
increasing anticipations in organic synthetic chemistry.
(a) Larock, Yamamoto and et al.
R
E
E+
R
-LG
Y
Y
X
n
LG
X
n
As an eco-friendly and cost-effective accelerator, iodine
presents undisputed advantages in most cases, including being
easily operated and metal-free, as well as affording economies
of resource, time, and labor. As is well-known, the coordination
between the electrophile iodine cation and an unsaturated
bond could produce the corresponding onium ion, which would
R = aryl, alkyl
E+ = I+, Br+, Cl+
Y = N, O, S
n = 0, 1
X = C, N, O, S, Se
(b) Wang's work
I
N
Ts
I2 (1.2 equiv)
DEC, rt
NTs
N
N
(c) This work
OH
O
Meyer-Schuster
rearrangement
R
OH
a.
Path
A
1a
College of Chemistry and Chemical Engineering, Northwest Normal University,
I
I
NTs
Lanzhou, People’s Republic of China. E-mail: huocongde@nwnu.edu.cn,
quanzhengjun@hotmail.com
Jiangxi Key Laboratory of Organic Chemistry, Jiangxi Science Technology Normal
I+
NTs
2a
I
O
H2 or
I-
I
b.
University, Nanchang, People’s Republic of China
State Key Laboratory of Applied Organic Chemistry, Lanzhou University, Lanzhou,
People’s Republic of China. E-mail: liangym@lzu.edu.cn
† Electronic Supplementary Information (ESI) available: Detailed experimental
procedures; characterization data of products; copies 1H, 13C and 19F NMR spectra
of all compounds; crystallographic data of 2j (CCDC 1913985) and 2l (1935327) see
DOI: 10.1039/x0xx00000x
I-, then I+
R
I
c.
I
B
Path
Ts
R =
N
NTs
NTs
3a
Scheme 1 Previous Reports and Our New Design and
Anticipation
‡ These authors contributed equally to this work.
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3a isolated. p-TsOH·H2O (1.0 equiv) or K2CO3 (1.0 equiv)
frameworks,17 we designed an electrophilic iodocyclization of 1-
en-6,11-diyne substrate, which contained the 1,6-enyne and
propynol moieties within one combination. In this
transformation, two pathways would be foreseen including the
Meyer-Schuster rearrangement process and the nucleophilic
attack of iodide onto the allenic cation intermediate (Scheme
1c). In path A, with the generation of four new bonds, the high
step economy has drawn attention from successive cyclization
process. Whereas, the reaction is terminated after a classical
diiodization of propynols without further cyclization in path B.
Therefore, compound 2a was selected as the goal product in
this transformation. In addition, the resulting product
f
View Article Online
h Decomposed.
was added. g H2O (2 equiv) was addedD. OI: 10.1039/C9CC08286G
promotion to the yield of product 2a to 82% with less
decomposition (entry 13). By replacing iodine sources, iodine
still proved to have an advantage in this transformation (entries
14−17). Finally, the optimal reaction conditions for generation
2a were established as the addition of iodine (1 equiv) and H2O
(2 equiv) in 3-ethoxypropanenitrile (2 mL) under an air
atmosphere at 80 °C for 0.5 h.
Based on the optimal reaction conditions, the reaction scope
of this transformation was explored subsequently by employing
a series of 1-en-6,11-diynes (1a−1w) as the substrates. The
corresponding tetrahydrobenzo[f]isoquinolines (2a−2v) were
isolated in moderate to good yields smoothly (Scheme 2). The
structures of product 2j and 2l were further identified by X-ray
crystal structure analysis (see the Supporting Information). In
general, substituent groups R1 for both electron-rich (1b−1g)
and -insufficient (1h−1l) ones on the para-position all showed
good compatibilities in this transformation. Due to the
electronic effect of the substituent groups, the products
contained an electron-withdraw group (EDG) would generate
higher yields than the electron-rich ones (2h−2j vs 2b−2g). It
was noteworthy that the substrate with an acetyl (1k) or cyan
(1l) group worked well and gave the corresponding product in a
satisfactory yield. Similar to the case of para-substituents
groups, the starting materials with meta- and ortho-substituent
tetrahydrobenzo[f]isoquinoline was
numerous natural products and pharmaceutically active
molecules.18
a core structure of
Compound 1a (0.2 mmol) was settled as the model starting
material in the initial exploration for our anticipation.
Gratifyingly, the cyclic product 2a was isolated in 38% yield in
the presence of iodine (1.2 equiv) in MeCN (2 mL) under an air
atmosphere at 80 °C for 0.5 h (Table 1, entry 1). This
transformation showed exclusive compatibility in nitrile
solvents, in which 3-ethoxypropanenitrile proved to be the
most efficient one (entries 2−9). Afterwards, the adjustment on
the amount of iodine to 1 equiv gave a high yield of 73% and
reduced the amount of by-product 3a observed by TLC analysis
(entry 10). Lowing the reaction temperature or adding
additional base/acid promoter would be beneficial to the side
reactions (entries 11−12). The addition of H2O (2 equiv) gave a
further
OH
O
I
2 (1 equiv)
R2
H2O (2 equiv)
R1
R2
R1
3-ethoxypropanenitrile
80 oC, 0.5 h
Table 1 Optimization of the Reaction Conditionsa
I
NTs
NTs
Entry Iodine source Solvent
(equiv)
Yield
2a (%)b
38
63
54
1
2
2a
2b
2c
2d
2e
2g
, R = H, 82%
, R = Ph, 71%
, R = F, 80%
, R = Cl, 79%
, R = Br, 84%
1
2
3
4
5
6
7c
8d
9d
10
11e
12f
13g
14g
15g
16g
I2 (1.2)
I2 (1.2)
I2 (1.2)
I2 (1.2)
I2 (1.2)
I2 (1.2)
I2 (1.2)
I2 (1.2)
I2 (1.2)
I2 (1.0)
I2 (1.0)
I2 (1.0)
I2 (1.0)
NIS (1.0)
ICl (1.0)
IBr (1.0)
IPy2Bf4 (1.0)
MeCN
EtCN
n-PrCN
i-PrCN
O
2h
, R = Me, 75%
, R = Et, 71%
2i
2j
, R = t-Bu, 77%
, R = n-pentyl, 58%
, R = OMe, 62%
R
R
2k
, R = Ac, 62%
2l
, R = CN, 55%
I
NTs
O
2f
51
3-ethoxypropanenitrile 67
DCE
toluene
THF
isopropanol
3-ethoxypropanenitrile 73
3-ethoxypropanenitrile trace
3-ethoxypropanenitrile trace
3-ethoxypropanenitrile 82
3-ethoxypropanenitrile traceh
3-ethoxypropanenitrile 42
3-ethoxypropanenitrile 54
3-ethoxypropanenitrile trace
O
OMe
O
R
21
trace
trace
trace
I
I
I
NTs
NTs NO2
NTs
R
2m
2p
2q
, R = Me, 68%
, R = Me, 66%
, R = Cl, 75%
2n
2o, 47%
, R = Cl, 74%
O
O
O
R
Cl
I
I
I
NTs
NTs
NTs
2r
, R = Me, 78%
2s
2t
2u
, R = Cl, 85%
, 88%
, 62%
O
O
O
R
17
a
Unless otherwise noted, all reactions were conducted
with 1a (0.2 mmol) and iodinated reagent (1 equiv) in
solvent (2 mL) under an air atmosphere at 80 °C for 0.5 h.
b Isolated products yields are given. c 64% of by-product 3a
I
Br
NTs
NTs
NTs
I
2w
2x
, R = n-pentyl, trace
b
c
2v
2a'
, trace
, 77%
, R = 2-thienyl, trace
Scheme 2 Substrate Scope.a Unless otherwise noted, the
reactions were conducted with 1 (0.2 mmol), I2 (1 equiv), and
H2O (2 equiv) in 3-ethoxypropanenitrile (2 mL) under an air
atmosphere at 80 °C for 0.5 h. Isolated products yields are
a
d
e
was isolated. 1a was decomposed. This reaction was
conducted at room temperature with 85% of by-product
2 | J. Name., 2012, 00, 1-3
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given.b Only diiodo-product was observed. c Br2 or NBS was used into the corresponding benzo[f]isoquinolines 4a−4c, 4i and 4j in
View Article Online
DOI: 10.1039/C9CC08286G
instead of I2.
the presence of KOH in ethyl alcohol (Scheme 5).
O
O
groups (1m−1o) also exhibited good tolerance. The
transformation
KOH (3 equiv)
proceeded
smoothly
for
various
EtOH, reflux, 3 h
R
R
multisubstituted substrates, the corresponding products were
isolated in moderate to good yields (1o−1s). Notably, the nitro
group survived in the transformation with the corresponding
product 2o isolated smoothly under the optimal conditions.
Additionally, the yields of substrates with representative R2
substituents seemed to be good as well, including electron-rich
(methyl-substituted, 2t and 2v) and electron-deficient (chloro-
substituted, 2u) groups. The substrate contained an aliphatic
chain 1w or a heterocyclic group (2-thienyl, 1x) failed to give the
corresponding products due to an unstable intermediate B (see
Scheme 7). And the replacement of electrophilic reagent to
bromine, more by-products were observed without the
generation of product 2a’.
Encouraged by the above results, the substrate contained a
non-terminal olefin was then applied (Scheme 3). Due to the
high activity of tertiary iodoalkane, product 2y with an
isopropenyl group was isolated in 70% yield by the elimination
of HI. Subsequently, the reactions of carbon-tethered 1,6-enyne
moiety was further explored under the optimal conditions. As
depict in Scheme 3, the substrate with a carbon linker 1z could
I
NTs
N
4b
4c
4i, R = Cl, 99%
4j
, R = Me, 88%
2
4a
4
, R = H, 95%
, R = Et, 90%
, R = Br, 97%
Scheme 5 Synthetic Transformations
plausible mechanism that is consistent with the
A
experimental results and the precedent literature4b,9 is
proposed in Scheme 6. In fact, iodine cation activates the
hydroxy group of the substrate 1 and propagates propargylic
cation A, which would undergo a subsequent tautomerism to
generate the allenic cation B.10 The attack of water onto
intermediate B affords intermediate C followed by the
coordination of iodine cation with acetylenic moiety.
Subsequently, the tautomerism and intramolecular attack onto
iodonium cation of intermediate C generates intermediate D,
which was coordinated by another iodine cation. Finally,
product 2 could be obtained by the exo attack of naphthalene
moiety onto the new iodonium cation by release of a molar
amount of iodine cation.15a,15h,16
OH
H2O
I+
be
smoothly
converted
into
the
desired
tetrahydrophenanthrene product 2z in 76% yield.
NTs
NTs
I
OH
NTs
1a
2a
A
B
OH
O
I
2 (1 equiv)
optimal
conditions
I+
H2O (2 equiv)
3-ethoxypropanenitrile
80 oC, 0.5 h
O
O
NTs
NTs
1y
I-
I+
O
2y
, 70%
O
H
I
I
I
I2
NTs
I
NTs
OH
NTs
I
E
D
C
I
2 (1 equiv)
Cl
Cl
H2O (2 equiv)
Scheme 6 Proposed Reaction Mechanism
3-ethoxypropanenitrile
80 oC, 0.5 h
I
COOMe
COOMe
In summary, we have presented an iodine promoted cascade
cyclization of 1-en-6,11-diynes to synthesize a series of iodo-
tetrahydrobenzo[f]isoquinoline or tetrahydrophenanthrene
derivatives. This reaction system is proven to have good
functional group compatibility in satisfactory yields within a
short reaction time. Specifically, some particular functional
groups (acetyl, nitro, and cyan groups) were tolerated in this
transformation. Notably, the use of a simple and green
promoter iodine avoids the addition of toxic and expensive
transition metal catalyst or oxidant. From the point view of
synthetic strategy, two cyclic systems were established with
one carbon−oxygen, carbon−iodine, and two carton−carton
bonds constructed in a single step, which might provide a
feasible experience to the follow-up analogous cascade
reaction design. In addition, the generated iodo-products could
be further derived through the subsequent elimination
reaction.
COOMe
COOMe
1z
2z
, 76%
Scheme 3 Synthesis of 2y (2z) from 1y (1z).a aThe reactions were
conducted with 1y (1z) (0.2 mmol), I2 (1 equiv), and H2O (2
equiv) in 3-ethoxypropanenitrile (2 mL) under an air
atmosphere at 80 °C for 0.5 h. Isolated products yields are given.
A notable feature of this transformation was that the reaction
system could be scaled up to gram quantities (Scheme 4).
Product 2a was isolated in 67% yield on the gram scale under
the standard conditions. This might afford potential value for
this approach in synthetic industry.
OH
O
I
2 (1 equiv)
H2O (2 equiv)
3-ethoxypropanenitrile
80 oC, 0.5 h
I
NTs
NTs
, 1.0 g
1a
67%
2a
, 0.86 g
Financial support was received from the National Natural
Science Foundation of China (NSF21562036), China
Scheme 4 Scale-up Experiment
Another lightspot was that the generated iodo-products
could be identified as significant synthetic intermediates. For
instance, iodo-products 2a−2c,2i and 2j could be transformed
Postdoctoral
Science
Foundation
Funded
Project
(2018M631218), Gansu Province Science Foundation for Youths
(18JR3RA099), and Northwest Normal University Young
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 3
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T. Zhu, S. Chen, C. Luan, Y. Xia, Y. Shen, Y.-X. Li, Y. Hua and Y.-
Scholars Research Capacity Improvement Program (NWNU-
LKQN-18-6). Also, we are grateful to Dr. Ming Li (Lanzhou
University) for the high-resolution mass spectrum analysis.
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DOI: 10.1039/C9CC08286G
Table of contents entry
Iodine Promoted Cascade Cycloisomerization of 1-En-6,11-diynes
Yi-Feng Qiu, Yue-Jie Niu, Xian-Rong Song, Xi Wei, Hui Chen, Shun-Xi Li, Xi-Cun Wang, Congde
Huo, Zheng-Jun Quan and Yong-Min Liang
Page No. – Page No.
Cascade Iodocyclization: An iodine promoted cascade cycloisomerization of 1-en-6,11-
diynes is presented for the easy preparation of tetrahydrobenzo[f]isoquinolines. In this
transformation, two new cyclic frameworks and one carbonyl group are formed with four new
bonds constructed.