Chemoselective and stereospecific iodination of alkynes using sulfonium iodate(i) salt

Article abstract of DOI:10.1039/c7ob03076b

An efficient and highly chemoselective iodination of alkynes using a sulfonium iodate(i) electrophilc reagent under metal-free conditions has been realized. The reactivity of sulfonium iodate(i) salt could be significantly diverse in the presence of water

Full text of DOI:10.1039/c7ob03076b

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DOI: 10.1039/C7OB03076B
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Chemoselective and Stereospecific Iodination of Alkynes using
Sulfonium Iodate(I) Salt
Dodla S. Rao,a Thurpu R. Reddy,a and Sudhir Kashyap*ab
Received 00th January 20xx,
Accepted 00th January 20xx
An efficient and highly chemoselective iodination of alkyne using Sulfonium Iodate (I) electrophilc
reagent under metal-free conditions has been developed. The reactivity of sulfonium Iodate (I)
salt could be significantly diverse in the presence of the water as the solvent, enabling the (E)-1,2-
diiodoalkenes stereospecifically. This stereodivergent approach is amenable to a wide range of
alkyne substrates and demonstrates diverse functional group tolerance resulting synthetically
valuable 1-iodoalkyne and (E)-vicinal-diiodoalkenes in good to excellent yields (up to 99%) with
100% selectivity at ambient condition.
DOI: 10.1039/x0xx00000x
www.rsc.org/
iodination of terminal alkynes in aqueous solvent albeit at high
temperature with limited substrate scope.9d
Introduction
Alternative classical methods to access desired 1-
The iodo-functionalized molecules have attracted considerable
attention due to their synthetic adaptability as key
intermediates and valuable synthons in organic chemistry.1 In
particular, 1-iodoalkynes represent important subclass which
have been extensively employed as useful precursors in
several fascinating chemical transformations.2 The presence of
iodo moiety in sp-hybridized acetylene led to development of
rapid and attractive stereocontrolled techniques viz Cadiot-
Chodkiewicz,3 Nozaki-Takai cross coupling,4 hetero-
functionalization via CuAAC "click reactions",5 total syntheses
of active natural products and biologically active molecules.6 In
addition to well appreciated role in material and polymer
research,7 iodoalkyne derivatives exhibit distinctive biological
activities hence served as promising chemical probes of
outmost pharmaceutical applications such as anti-HIV, anti-
microbial, and fungicidal agents.8
iodoalkynes in multistep or indirect process (Scheme 1)
includes (1) oxidative iodination of metal-acetylides via metal-
iodo exchange in the presence of a base;10 (2) NIS/Et3N-
mediated iodo-decarboxylation of propiolic acid intermediate
under Hundiesker reaction;11 (3) desilylation-iodination of
trialkylsilylacetylenes using NIS in the presence of metal-salt
such as AgNO3;12 (4) a two-steps Corey-Fuchs homologation-
iodination of aldehyde employing strong base such as BuLi or
13
°
LDA at -78 C; (5) one-pot homologation-double elimination
reaction of benzyl bromide using CHI3 and NaHMDS under
cryogenic reaction conditions.14
The conventional procedures for generating synthetically
useful 1-iodoalkynes involve direct oxidative iodination of
terminal alkyne with iodinating reagents.9 Most commonly,
addition of molecular iodine9a or hypervalent iodonium salts
on acetylenes applied to access corresponding 1-
iodoacetylenes.9b Indeed,
a combination of hypervalent
oxidant such as PhI(OAc)2, with KI as halide source in the
presence of metal catalyst and Et3N as additive also reported
for similar transformation.9c On the other hand, Bu4NI as iodo-
source with oxone as an oxidizing reagent promoted the
Scheme 1. Previous approaches for the synthesis of 1-iodoalkynes.
Likewise, 1,2-diiodovinyl substrates are considered
important synthetic building blocks and have been utilized
often as key intermediates in functional group manipulation
and valuable precursors in metal-catalyzed coupling
reactions.15 An approach to stereospecific synthesis of 1,2-
trans-diiodoalkenes is quite elusive and predominantly relies
a.Department of Chemistry, Malaviya National Institute of Technology (MNIT),
Jaipur-302 017, INDIA. E-mail: skashyap,chy@mnit.ac.in,
skr.kashyap@gmail.com.
b.INSPIRE Faculty, Department of Science and Technology (DST) and Assistant
Professor, Academy of Scientific and Innovative Research (AcSIR), INDIA.
Electronic Supplementary Information (ESI) available: [General synthesis
information, procedures, characterization data, spectral charts are provided]. See on direct addition of iodine or iodinating reagent on an
DOI: 10.1039/x0xx00000x
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acetylene triple bond.16 Though, some of oxidative operationally simple and applicable to wide substVraietweArstcicolepOen.linIet
diiodination methods often require additive such as CuI, H2O2, is pertinent to mention that a combiDnOatI:io10n.10o3f9/CM7Oe3BS0I30a7n6dB
Al2O3 and H2SO4 to realize stereoselective addition, thereby PhI(OAc)2 promoted mono-iodination of alkynes in the
restricting the substrate scope.17 Other reported methods presence of acetonitrile as the solvent, whereas, switching to
utilizing oxone as oxidant and halide salt such as KI and NaI, water as sole solvent and altering the amount of iodine source
effectively promoted the oxidative diiodination of a triple led to the formation of exclusive di-iodination product (E)-1,2-
bond.18 However, excessive use of oxidant involving hazardous diiodoalkene in complete stereospecific manner.
and toxic iodinating reagent, unconventional processes and
stereoselectively indiscriminate E/Z isomeric mixture of vicinal
diiodoalkenes or oxyhalogenataed α,α'-diidoketones18a as by-
products are some recognized challenges (Scheme 2).
Results and discussion
At the outset, phenyl acetylene (1a) was used as the model
substrate to examine oxidative iodination reaction by
employing sulfonium bis(acetoxy)iodate(I) Me3SI(OAc)2, active
electrophilic reagent system. Accordingly,
a preformed
solution of Me3SI (1.1 equiv) and PhI(OAc)2 (1.1 equiv) in
CH2Cl2, assumingly generate Me3SI(OAc)2 in situ, was treated
with 1a (1.0 equiv) at room temperature. Although, reaction
Scheme 2. Previous approaches towards 1,2-diiodoalkenes.
proceeded smoothly to
afford the
desired
1-
(iodoethynyl)benzene (2a) in moderate yield (88%) after 6 h
(Table 1, entry 1). To our delight, there was a significant
improvement in the yield (98%) as well rate of iodination
reaction when the reaction was performed in acetonitrile as
the solvent (Table 1, entry 2).
Owing to the prominence synthetic versatility and short of
commercial availability of iodo-functionalized derivatives,
development of stereoselective and efficient protocol utilizing
preferred reagent system is highly desirable. In this context,
we recently demonstrated the utility of sulfonium
bis(acetoxy)iodate(I) salt in stereoselective synthesis of 2-
deoxy glycoconjugates.19a The effectiveness and distinctive
adaptability of the present reagent system is further
demonstrated for regioselective vicinal bisfunctionalization of
a diverse range of olefins19b (Scheme 3).
Noteworthy, direct oxidative iodination of 1a employing
Me3SI(OAc)2 (1.1 equiv.) in acetonitrile works well to furnish 2a
in acceptable yield in 1 h (Table 1, entry 3). Further
optimization by using other organic solvents such as 1,2-
dichloroethane, toluene, AcOH, THF or DMF resulted no
improvement (Entries 4-8). Nevertheless, these results
highlighted the advantages of advanced protocol over
conventional oxidizing reagent systems.
Our previous work (Iodoglycosylation and vicinal bisfunctionalization)
I
I
Nu
O
O
Me3SI(OAc)2
Nu-H
or
or
Table 1. Synthesis of 1-iodoalkyne and comparative studies.
(RO)n
X
X
(RO)n
Glycals
Nu
Alkenes
2-iodo-glycoside
β
-iodo
(X = O, CH2, Ar)
This work (Stereodivergent iodination)
Iodo source
Me3SI
Entry
1
Oxidant
Solvent
CH2Cl2
t[h]
Yield of 2a
CH3CN
R
I
I
R1
; H
Me S
I
3
PhI(OAc)2
6.0
88%
R1
R
PhI(OAc)2
H2O
R1
R1; H, Ar, Alk
1,2-trans
CH3CN
CH3CN
DCE
2
3
4
5
6
7
8
Me3SI
Me3SI(OAc)2
Me3SI
PhI(OAc)2
-
0.5
1.0
2.0
6.0
3.0
6.0
12
98%
92%
86%
NR
R
; Aryl, Naphthyl,
R
Aliphatic, Cyclic
I
Scheme 3. Selective iodo-functionalization using sulfonium iodate(I) reagent system.
PhI(OAc)2
PhI(OAc)2
PhI(OAc)2
PhI(OAc)2
PhI(OAc)2
Inspired by the recent success of unprecedented sulfonium
iodate reagent, we envisioned that the inherent ability of
electrophilc salt would offer facile iodination of an alkyne
moiety via direct oxidative addition on a triple bond. In
continuation of our efforts in search of novel and promising
alternative methods involving environmentally benign
Me3SI
Toluene
AcOH
THF
Me3SI
85%
NR
Me3SI
reagents,19 herein, we report
a
solvent controlled
DMF
Me3SI
78%
stereodivergent process to access 1-iodoalkyne and 1,2-trans-
diiodoalkene by employing Me3SI/PhI(OAc)2 under mild
reaction condition (Scheme 3). The present system provides
metal-free and molecular iodine free environment,
aReaction conditions: 1a (1.0 equiv.), Me3SI /PhI(OAc)2 (1.1 equiv. each) or
Me3SI(OAc)2 (1.1 equiv.), solvent (2 mL), rt., NR = No reaction.
2 | J. Name., 2012, 00, 1-3
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Having optimized protocol in hand, we next investigated iodoacetylene derivatives 2l-2m in 94% andView90Ar%ticle yOinelinlde
DOI: 10.1039/C7OB03076B
the scope and generality of high yielding and selective respectively. Notably, a heterocyclic bearing alkyne such as 3-
iodination for a wide range of electronically diverse alkynes ethynylpyridine
(1n), performed well under "oxidative-
(Table 2). The aryl alkynes containing different substituted iodination" process to generate synthetically useful 2n in 82%
halogens for instance 2-chloro (1b), 3-bromo (1c) and 4-flouro- yield.
phenylacetylene
(
1d) efficiently afforded the desired 1-
Encouraged by these findings, we next examined the scope
of unactivated acetylenes such as aliphatic and alicyclic alkyne
substrates. For this purpose, dec-1-yne (1o), a ten carbon
chain containing acetylene, was allowed to react under
optimized reaction condition to realize the selective iodination
furnishing 1-iododec-1-yne (2o) in 80% yield at ambient
temperature. Subsequently, acetylenes comprising alicyclic
iodoalkynes in excellent yields (2b-2d).
Table 2. Scope of Me3SI(OAc)2-mediated iodinationa
Br
F
moiety such as cyclopropyl
(1p), cyclopentyl (1q) and
cyclohexyl (1r) were iodinated successfully by using sulfonium
iodate(I) reagent to obtain the corresponding products in good
yields (2p-2r). On the other hand, the previous reported
method using Bu4NI/oxone for the oxidative iodination of
substrates comprising heterocyclic, aliphatic, naphthyl or aryl
acetylenes with methoxy substituent failed to deliver desired
product,9d further confirming the prominence of sulfonium
iodate(I) reagent system.
Cl
I
I
I
2b; >99%
2c; >99%
2d; 90%
2i; 92%
Et
I
MeO
Me
I
I
2e; 3-OMe; >99%
2f
2g; 3-Me; 94%
Next, it was of interest to explore the possibility of
sulfonium iodate(I) reagent system for di-iodination of sp-
hybridized alkyne moiety to generate synthetically useful
vicinal diiodoalkenes. Initially, treatment of a preformed
solution of Me3SI and PhI(OAc)2 (1.1 equiv each) in CH3OH with
phenylacetylene 1a (1.0 equiv) at room temperature resulted
the mixture of di-iodo product 3a along with mono-iodo 2a in
a ratio 70:30, as observed by 1H NMR spectrum of crude
reaction mixture (Scheme 4). We anticipated that the
activation of alkyne by Me3SI(OAc)2 electrophilic salt
generated in situ from Me3SI/PhI(OAc)2 following addition of
Me3SI as a second iodine source (nucleophilic iodide) would
provide effective and selective di-iodination. However,
increasing the relative molar amount of Me3SI (2-3 equiv) with
PhI(OAc)2 (1.1 equiv) did not offer the requisite selectivity
even after prolonged reaction time or by varying the
temperature.
2h
; 4-OMe; 86%
; 4-Me; 88%
tBu
MeO
CF3
2k
I
I
2j
; 96%
; 92%
2l
; 94%
I
I
N
5
I
I
2m; 90%
2n; 82%
2q; 89%
2o; 80%
Interestingly, by switching the solvent system to water and
altering the equivalents of Me3SI (2.2 equiv), di-iodination
reaction proceeded efficiently and complete conversion of 1a
was realized in at most 30 min affording the exclusive (E)-(1,2-
I
I
I
2p; 87%
2r; 86%
diiodovinyl)benzene
(3a) in 95% yield (Scheme 4). The
aReaction conditions: Substrate 1 (1.0 equiv), Me3SI (1.1 equiv.), PhI(OAc)2 (1.1
stereochemistry of compound 3a was precisely correlated by
proton and proton-decoupled carbon spectrum, also found
consistent and with conformity that of literature data.9d
equiv.), acetonitrile (2 mL), rt, 30 min.
As summarized in Table 2, we next probed the feasibility of
electron-donating substituent such as methoxy (1e-1f), methyl
(1g-1h), ethyl (1i) and tert-butyl (1j) on phenyl ring. Of note, all
the reactions proceeded smoothly, affording the
corresponding iodinated products 2e-2j in 86-99% yields.
Indeed, trifluoromethyl substrate 1k found to be compatible
under present conditions, underwent oxidative iodination
reaction resulting the desired product 2k in 92% yield.
Subsequently, the selective iodination of polycyclic aryls such
as naphthyl 1l and pyrene 1m containing acetylene moiety are
accomplished successfully to obtain the venerable
Scheme 4. Stereospecific vicinal di-iodination of alkyne.
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Gratifying, changing to water "green" solvent system could
Journal Name
Aromatic alkynes with halogen at differeVinewt ArpticolesOitniolinne
led to entirely different product with absolute stereo including 2-chloro, 4-bromo, 4-flouro (1bD-O1dI:)10a.n10d39e/lCe7cOtrBo0n30r7ic6hB
chemistry. Noteworthy, the divergent synthesis of a choice of substituents for instance 3-methoxy, 4-methoxy, 3-methyl, 4-
product from same substrate by employing equivalent reagent methyl, 4-ethyl, 4-tert-butyl (1e-1j) were evaluating under
under solvent controlled conditions is quite attractive with a stabilized conditions to obtain the desired di-iodinated
purpose of expanding the utility. With the optimized reaction products 3b-3h in good to excellent yields. Also, the aryl
conditions, we investigated the scope and generality of the acetylene containing CF3 moiety 1k, a naphthyl 1l or a pyrene
stereospecific trans-diiodination protocol, results are 1m were all performed well affording the desired 1,2-
summarized in Table 3.
diiodovinyl compounds 3k-3n in good yields. In contrast, 1n
apparently gave a mixture of diiodo/iodo product 3n/2n under
standard conditions in 91% overall yield; 3n (64%) and 2n
(27%), approximately 3:1 ratio, determine by relative
integration of separable proton in 1H NMR spectrum.
Table 3. Substrate scope for Me3SI/PhI(OAc)2-mediated di-iodination of alkynesa
We further extended the scope for unactivated substrates,
aliphatic and alicyclic acetylenes under eco-friendly protocol
(Table 3). We observed that dec-1-yne (1o), and cyclic
acetylenes 1p-1r effectively participated in present oxidative-
diiodination resulting the desired products 3o-3r in 100%
stereospecific manner. Given this success, validity of
Me3SI/PhI(OAc)2/H2O system is further investigated for the
stereoselective transformation of internal acetylenes into 1,2-
trans-diiodoalkenes. Thus, 1-phenyl-1-propyne (1s) reacted
well and afforded the (E)-1,2-diiodo-1-phenylpropene 3s in
80% yield, confirming the anti-addition. Subsequently, 1-
phenyl-1-butyne
(1t) and 1,2-diphenylethyne (1u) were
iodinated in good yields leading to (E)-1,2-diiodoolefins (3t-3u
)
with controlled stereoselectivity. Nevertheless, the oxidative
di-iodination reaction was applicable to an aliphatic internal
acetylene for instance 3-hexyne
(1v), affording (E)-3,4-
diiodohex-3-ene (3v) in 90% yield.
To further established the synthetic potential of
representative protocol, the gram-scale selective iodination of
acetylene was successfully conducted. (Scheme 5). Employing
Me3SI and PhI(OAc)2 (1.1 equiv each) in a large scale iodination
of 1-fluoro-4-ethynylbenzene 1d (1.2 g, 10 mmol) in
acetonitrile at room temperature afforded the product 2d
(2.09 g) in 85% yield, slightly lower as compared to 1.0 mmol
scale (90%). In addition, 1-decyne 1o (1.38 g) under standard
di-iodination conditions resulted the corresponding (E)-1,2-
diiododec-1-ene 3o (3.06 g) in 78% isolated yield albeit in a
longer reaction time. Nevertheless, the results are consistent
in support with aforementioned selective iodination,
highlighting the efficiency and feasibility on large scale.
Scheme 5. Scale-up reactions for selective iodination.
aReaction conditions: Substrate 1 (1.0 equiv), Me3SI (2.2 equiv.), PhI(OAc)2 (1.1
equiv.), water (2 mL), rt, 30 min.
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To gain the insight into the mechanism of di-iodination
ARTICLE
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DOI: 10.1039/C7OB03076B
reaction, a series of control experiments were performed
(Scheme 6). The reaction of 1a with excess of Me3SI (2.2 equiv)
and oxidant PhI(OAc)2 (1.1 equiv) in acetonitrile failed to
produced any di-iodinated product 3a
, instead 2a was
obtained as a sole product in quantitative yield (Scheme 6, eq.
i). Similar results were obtained when 1a was activated with
2.2 equivalence of electrophilic salt, Me3SI(OAc)2 in
acetonitrile (Eq. ii). Next, submitting 1-iodoalkyne 2a to our
standard di-iodination conditions also found to be ineffective,
resulting complete recovery of starting material (Eq. iii). The
reaction was re-examined by iodate reagent Me3SI(OAc)2 in
the presence of 1.1 equivalence Me3SI as iodosource in water,
providing un-reacted 2a (Eq. iv). These experiments indicate
distinct activation of acetylene moiety by electrophilic salt in
the presence of H2O and possibility of enhanced nucleophilicity
of iodide salt in more polar solvent. Illustrating the crucial role
of water for the oxidative di-iodination, these results also ruled
out the involvement of 2a as an intermediate in this
transformation.
Scheme 7. A plausible mechanism for Me3SI(OAc)2-mediated selective iodination of
alkynes.
In case of acetonitrile solvent, the reactive
π
complex could produce mono-iodo product
-coordinated
via
B
E
intramolecular deprotonation of terminal alkyne by acetate
ion to release acetic acid (pathway b). To further support the
mechanism, a positive starch solution test observing by a
colour changes from red to intense blue, confirming the
existence of the electrophilc iodate (I) species and formation
of molecular iodine intermediate. Moreover, the presence of
TEMPO, a radical scavenger under the standard oxidative
iodination processes, does not influences the outcome of the
reactions, supporting the postulated ionic mechanistic
scenario and consistent with the experimental results and
literature precedent.
Conclusions
In conclusion, we have developed a metal-free, molecular
iodine free protocol for stereodivergent iodination of alkynes
under solvent-controlled process. The intrinsic reactivity of
sulfonium iodate(I) salt in two different solvents resulting in
selective iodination to access 1-iodoalkynes and vicinal (E)-
diiodoalkenes. This protocol successfully applied to a wide
range of substrates affording diverse functionalized and
synthetically useful iodinated molecules at ambient
temperature. This new system not only provide an efficient
and operationally simple process, but also utilizing readily
available and environmentally benign reagents. The present
results open new dimensions of sulfonium iodate reagent for
other nucleophilic version to introduce nitrogen, carbon,
oxygen, and sulphur functionality on C-C multiple bond.
Mechanistic studies and further investigating synthetic
application of sulfonium iodate(I) salt in modern organic
chemistry are currently ongoing in our laboratory.
Scheme 6. Control experiments and effect of solvent on selective iodination of alkyne.
Although a detailed mechanism for sulfonium iodate
mediated di-iodination remains unclear at this moment, we
proposed a plausible pathway based on literature analogy and
supported by aforementioned control experiments. As shown
in scheme 7, it is hypothesized that the electrophilic iodate (I+)
salt Me3SI(OAc)2 (an equivalent to IOAC) generated via
oxidative transfer of acetyl groups from PhI(OAc)2 to Me3SI
would trap an alkyne (
A
) to form the
π
Thereafter, generation of iodonium species
-coordinated species
B.
C
and AcO- ion,
which could trapped under present solvent system (pathway
a). Subsequent attack of nucleophilic iodide (I-) on iodonium
ion intermediate
C
from opposite side finally leading to di-
with absolute anti-
iodination adduct 1,2-trans-diiodoalkene
D
addition selectivity. Alternatively, molecular iodine could be
generated by the combination of an iodide ion (Me3S+I-) and
electrophilc iodate (I) salt (acetyl hypoiodite, AcO-I+), which
then undergoes electrophilic addition on a triple bond to
produce 1,2-(E)-diiodoalkene stereospecifically.
Experimental
General Synthesis Information: Unless otherwise noted,
materials were obtained from commercial suppliers and used
without purification. Anhydrous solvents were purchased for
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the reactions and used without further desiccation. All CDCl3) δ 136.64, 134.12, 129.71, 129.16, 126.31, 1V2ie3w.1A7rti,cl9e0O.n8li3ne,
reactions were performed in flame-dried round bottom flasks, 12.27; the overall spectroscopic datDaOI:a10re.103i9n/C7cOoBm03p0le76tBe
fitted with rubber septa or glass gas adapters, under a positive agreement with assigned structures and consistent with
pressure of nitrogen or argon. Analytical thin-layer literature.14
chromatography (TLC) was performed using aluminum backed 1-Bromo-4-(iodoethynyl)benzene (2c): Following general
UV F254 pre-coated silica gel flexible plates. Removal of procedure
A using 4-bromo-2-ethynylbenzene (1c, 100 mg,
solvent under reduced pressure refers to distillation with a 0.552 mmol) and purified by silica gel column chromatography,
rotary evaporator attached to a vacuum pump (~3 mmHg). eluting with hexanes afforded the title compound as pale
Melting points were obtained in open capillary tubes using a yellow solid (168 mg, 0.546 mmol, 99%). Mp. 88-89 °C;
1
micro melting point apparatus and were uncorrected. Optical (literature: 89-91 °C). H NMR (500 MHz, CDCl3) δ 7.44 (d, J =
rotations were recorded with a digital polarimeter at 589 nm 8.4 Hz, 2H), 7.29( d, J = 8.4 Hz, 2H); 13C NMR (126 MHz, CDCl3)
(sodium D-line). NMR were recorded on 300, 400 or 500 MHz δ 133.68, 131.48, 123.13, 122.25, 93.01, 8.02; the overall
nuclear magnetic resonance spectrometers. The proton spectroscopic data are in complete agreement with assigned
resonances are annotated as: chemical shift (δ) relative to structures and consistent with literature.9d
tetramethylsilane (δ 0.0) using the residual solvent signal as an 1-Fluoro-4-(iodoethynyl)benzene (2d): Following general
internal standard or tetramethylsilane itself: chloroform-d (δ procedure
A using 4-fluoro-2-ethynylbenzene (1d, 105 mg,
7.26, singlet), multiplicity (s, singlet; d, doublet; t, triplet; q, 0.873 mmol) and purified by silica gel column chromatography,
quartet; m, multiplet; br, broad), coupling constant (J, Hz), and eluting with hexanes afforded the title compound as pale
1
number of protons for a given resonance is indicated by nH. yellow oil (193 mg, 0.786 mmol, 90%). H NMR (400 MHz,
The chemical shifts of 13C NMR are reported in ppm relative to CDCl3) δ 7.44-7.37 (m, 2H), 7.03-6.97 (m, 2H); 13C NMR (101
the central line of the triplet at 77.0 ppm for CDCl3. IR spectra MHz, CDCl3) δ 163.99, 161.51, 134.28, 134.20, 115.64, 115.42,
were recorded on an FT-IR spectrometer and wave numbers of 92.97, 5.94; the overall spectroscopic data are in complete
maximum absorption peaks are presented in cm-1. High agreement with assigned structures and consistent with
resolution mass analyses (HRMS) were performed on a mass literature.9d
spectrometer using ESI-TOF techniques.
1-(iodoethynyl)-3-methoxybenzene (2e): Following general
using 1-ethynyl-3-methoxybenzene (1e, 104 mg,
Representative procedure for the synthesis of 1-iodoalkyne procedure
A
(A); A preformed solution of Me3SI (242 mg, 1.1 mmol, 1.1 0.787 mmol) and purified by silica gel column chromatography,
equiv.) and PhI(OAc)2 (354 mg, 1.1 mmol, 1.1 equiv.) in eluting with hexanes afforded the title compound as pale
acetonitrile (2 mL) was treated with alkyne
1 (1a, 102 mg, 110 yellow solid (201 mg, 0.780 mmol, 99%). Mp. 43-44 °C;
1
uL, 1.0 mmol, 1.0 equiv.) at room temperature. After the (literature: 41-42 °C). H NMR (500 MHz, CDCl3) δ 7.24-7.17
completion of reaction, the reaction was diluted with EtOAc (m, 1H), 7.06-6.99 (m, 1H), 6.96 (dd, J = 2.5, 1.4 Hz, 1H), 6.91-
(10 mL), quenched with saturated NaHCO3 (5 mL), saturated 6.84 (m, 1H), 3.79 (s, 3H); 13C NMR (101 MHz, CDCl3) δ 159.04,
aqueous sodium thiosulfate (2 mL) and extracted with EtOAc 129.21, 124.74, 124.18, 116.98, 115.44, 93.98, 55.17, 6.48; the
(3 X 30 mL). The combined organic layers were washed with overall spectroscopic data are in complete agreement with
brine solution, dried over anhydrous Na2SO4, concentrated in assigned structures and consistent with literature.14
vacuo and purified by silica gel column chromatography to 1-(iodoethynyl)-4-methoxybenzene (2f): Following general
obtain the desired 1-iodoalkynes (2a-2r). All the products were procedure A using 1-ethynyl-4-methoxybenzene (1f, 102 mg,
fully characterised by 1H and 13C spectroscopy and MS 0.771 mmol) and purified by silica gel column chromatography,
spectrometry and were in complete agreement with the eluting with hexanes afforded the title compound as pale
assigned structure and correlated with literature data.
yellow solid (171 mg, 0.663 mmol, 86%). Mp. 63-64 °C;
1
using (literature 61-62 °C). H NMR (500 MHz, CDCl3) δ 7.37 (d, J =
Iodoethynylbenzene (2a): Following general procedure
A
ethynylbenzene (1a, 93 mg, 0.912 mmol) and purified by silica 8.9 Hz, 2H), 6.83 (d, J = 8.9 Hz, 2H), 3.81 (s, 3H); 13C NMR (101
gel column chromatography, eluting with hexanes afforded the MHz, CDCl3) δ 159.78, 133.65, 115.37, 113.73, 93.90, 55.16,
title compound as pale yellow oil (204 mg, 0.893 mmol, 98%). 4.23; the overall spectroscopic data are in complete
1H NMR (500 MHz, CDCl3) δ 7.44 (d, J = 1.9 Hz, 1H), 7.43- 7.42 agreement with assigned structures and consistent with
(m, 1H), 7.33-7.30 (m, 3H); 13C NMR (101 MHz, CDCl3) δ literature.9d
132.30, 128.78, 128.21, 123.36, 94.11, 6.10; the overall 1-(iodoethynyl)-3-methylbenzene (2g): Following general
spectroscopic data are in complete agreement with assigned procedure
structures and consistent with literature.9d
0.775 mmol) and purified by silica gel column chromatography,
1-Chloro-2-(iodoethynyl)benzene (2b): Following general eluting with hexanes afforded the title compound as pale
procedure using 1-chloro-2-ethynylbenzene (1b, 125 mg, yellow solid (176 mg, 0.729 mmol, 94%). Mp. 47-49 °C;
A using 1-ethynyl-3-methylbenzene (1g, 90 mg,
A
0.919 mmol) and purified by silica gel column chromatography, (literature 49-51 °C). 1H NMR (400 MHz, CDCl3) δ 7.27-7.19 (m,
eluting with hexanes afforded the title compound as pale 3H), 7.15 (d, J = 6.9 Hz, 1H), 2.33 (s, 3H); 13C NMR (101 MHz,
yellow solid (238 mg, 0.909 mmol, 99%). Mp. 101-102 °C; CDCl3) δ 137.84, 132.79, 129.65, 129.29, 128.05, 123.05, 94.24,
1
(literature: 100-102 °C). H NMR (400 MHz, CDCl3) δ 7.49-7.45 21.15, 5.81; the overall spectroscopic data are in complete
(m, 1H), 7.38 (dd, J = 8.0, 1.3 Hz, 1H), 7.28-7.24 (m, 1H), 7.23 agreement with assigned structures and consistent with
(dd, J = 4.7, 1.8 Hz, 1H), 7.21-7.18 (m, 1H); 13C NMR (101 MHz, literature.9e
6 | J. Name., 2012, 00, 1-3
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1-(iodoethynyl)-4-methylbenzene (2h): Following general agreement with assigned structures and consistent with
View Article Online
A
using 1-ethynyl-4-methylbenzene (1h, 92 mg, literature.12a
DOI: 10.1039/C7OB03076B
procedure
0.789 mmol) and purified by silica gel column chromatography, 4-(iodoethynyl)pyrene (2m): Following general procedure
A
eluting with hexanes afforded the title compound as pale using 4-ethynylpyrene (1m, 100 mg, 0.438 mmol) and purified
1
yellow solid (168 mg, 0.694 mmol, 88%). H NMR (500 MHz, by silica gel column chromatography, eluting with hexanes
CDCl3) δ 7.32 (d, J = 7.3 Hz, 2H), 7.11 (d, J = 7.5 Hz, 2H), 2.34 (s, afforded the title compound as pale yellow solid (139 mg,
1
3H); 13C NMR (126 MHz, CDCl3) δ 138.98, 132.16, 128.95, 0.394 mmol, 90%). Mp. 125-127 °C; H NMR (500 MHz, CDCl3)
120.32, 94.21, 21.50, 4.90; the overall spectroscopic data are δ 8.50 (d, J = 9.1 Hz, 1H), 8.20 (d, J = 7.6 Hz, 1H), 8.17 (d, J = 7.6
in complete agreement with assigned structures and Hz, 1H), 8.13 (d, J = 9.1 Hz, 1H), 8.09 -8.04 (m, 3H), 8.00 (dd, J =
consistent with literature.14
12.2, 4.6 Hz, 2H); 13C NMR (101 MHz, CDCl3) δ 132.90, 131.50,
1-ethyl-4-(iodoethynyl)benzene (2i): Following general 131.11, 130.92, 130.32, 128.60, 128.42, 127.09, 126.24,
procedure using 1-ethynyl-4-ethylbenzene (1i, 93 mg, 0.715 125.74, 125.69, 125.15, 124.24, 124.20, 124.14, 117.72, 93.44,
mmol) and purified by silica gel column chromatography, 10.94; IR (CHCl3, cm-1): 3050, 2125, 1690, 1500, 980, 750, 550;
eluting with hexanes afforded the title compound as pale HRMS (ESI-TOF) m/z [M
NH4]+ calcd. for C18H13IN+:
yellow oil (169 mg, 0.658 mmol, 92%). 1H NMR (400 MHz, 370.00927; found: 370.00985.
CDCl3) δ 7.35 (d, J = 8.2 Hz, 2H), 7.13 (d, J = 8.0 Hz,2H), 2.64 (q, 3-(iodoethynyl)pyridine (2n): Following general procedure
A
+
A
J = 7.6 Hz, 1H), 1.22 (t, J = 7.6 Hz, 2H); 13C NMR (126 MHz, using 3-ethynylpyridine (1n, 100 mg, 0.970 mmol) and purified
CDCl3) δ 145.26, 132.26, 127.76, 120.56, 94.25, 28.80, 15.26, by silica gel column chromatography, eluting with hexanes
4.84; the overall spectroscopic data are in complete afforded the title compound as pale yellow solid (182 mg, 0.80
1
agreement with assigned structures and consistent with mmol, 82%). Mp. 104-106 °C; H NMR (400 MHz, ) δ 8.68 (s,
literature.9c
1H), 8.55 (d, J = 4.9 Hz, 1H), 7.75 (d, J = 7.8 Hz, 1H), 7.30 (d, J =
1-(tert-butyl)-4-(iodoethynyl)benzene (2j): Following general 6.9 Hz, 1H); 13C NMR (101 MHz, ) δ 152.66, 148.58, 139.55,
procedure
A
using 1-(tert-butyl)-4-ethynylbenzene (1j, 88 mg, 123.07, 120.74, 90.52, 11.66; IR (CHCl3, cm-1): 3057, 2880,
0.555 mmol) and purified by silica gel column chromatography, 2100, 1630, 1450, 720, 570; HRMS (ESI-TOF) m/z [M + H]+
eluting with hexanes afforded the title compound as pale calcd. for C7H5IN+: 229.94667; found: 229.94498.
yellow solid (151 mg, 0.532 mmol, 96%). Mp. 90-92 °C; 1-iododec-1-yne (2o): Following general procedure
A using
1
(literature 88-90 °C). H NMR (400 MHz, CDCl3) δ 7.37 (d, J = dec-1-yne (1o, 76.6 mg, 0.555 mmol) and purified by silica gel
8.7 Hz, 2H), 7.32 (d, J = 8.7 Hz, 2H), 1.30 (s, 9H); 13C NMR (126 column chromatography, eluting with hexanes afforded the
MHz, CDCl3) δ 151.99, 131.97, 125.15, 120.32, 94.17, 42.35, title compound as pale yellow oil (117 mg, 0.444 mmol, 80%).
34.71, 31.08, 30.92, 13.18; the overall spectroscopic data are 1H NMR (400 MHz, CDCl3) δ 2.35 (t, J = 7.1 Hz, 2H), 1.50 (dt, J =
in complete agreement with assigned structures and 7.5, 7.0 Hz, 2H), 1.40-1.26 (m, 10H), 0.88 (m, 3H). 13C NMR
consistent with literature.14
1-(iodoethynyl)-2-(trifluoromethyl)benzene (2k): Following 28.47, 22.64, 20.80, 14.10, -7.65; the overall spectroscopic
(101 MHz, CDCl3) δ 94.83, 31.80, 29.69, 29.13, 29.02, 28.77,
general
procedure
A
using
1-ethynyl-2- data are in complete agreement with assigned structures and
(trifluoromethyl)benzene (1k, 122 mg, 0.718 mmol) and consistent with literature.9g
purified by silica gel column chromatography, eluting with (iodoethynyl)cyclopropane (2p): Following general procedure
hexanes afforded the title compound as pale yellow solid (195
A using ethynylcyclopropane (1p, 80 mg, 1.207 mmol) and
mg, 0.661 mmol, 92%). Mp. 62-63 °C; (literature 64-65 °C). 1H purified by silica gel column chromatography, eluting with
NMR (500 MHz, CDCl3) δ 8.50 (d, J = 9.1 Hz, 1H), 8.20 (d, J = 7.6 hexanes afforded the title compound as pale yellow oil (186
Hz, 1H), 8.17 (d, J = 7.6 Hz, 1H), 8.13 (d, J = 9.1 Hz, 1H), 8.09 - mg, 1.050 mmol, 87%). 1H NMR (400 MHz, CDCl3) δ 1.49 (tdd, J
8.04 (m, 3H), 8.00 (dd, J = 12.2, 4.6 Hz, 2H); 13C NMR (101 MHz, = 6.4, 5.5, 3.2 Hz, 1H), 1.02-0.95 (m, 2H), 0.90-0.84 (m, 2H); 13
C
CDCl3) δ 132.90, 131.50, 131.11, 130.92, 130.32, 128.60, NMR (101 MHz, CDCl3) δ 124.35, 28.74, 16.95, 12.80; the
128.42, 127.09, 126.24, 125.74, 125.69, 125.15, 124.24, overall spectroscopic data are in complete agreement with
124.20, 124.14, 117.72, 93.44, 10.94; the overall spectroscopic assigned structures and consistent with literature.12
data are in complete agreement with assigned structures and (iodoethynyl)cyclopentane (2q): Following general procedure
consistent with literature.14
2-(iodoethynyl)-6-methoxynaphthalene (2l): Following general purified by silica gel column chromatography, eluting with
procedure using 2-ethynyl-6-methoxynaphthalene (1l, 100 hexanes afforded the title compound as pale yellow oil (169
A using ethynylcyclopentane (1q, 81 mg, 0.863 mmol) and
A
1
mg, 0.549 mmol) and purified by silica gel column mg, 0.768 mmol, 89%). H NMR (400 MHz, ) δ 2.52 (ddd, J =
chromatography, eluting with hexanes afforded the title 12.7, 8.9, 3.5 Hz, 1H), 1.77 (dd, J = 8.4, 5.6 Hz, 2H), 1.68 (ddd, J
compound as pale yellow solid (159 mg, 0.516 mmol, 94%). = 8.8, 8.1, 4.9 Hz, 2H), 1.54-1.38 (m, 2H), 1.33-1.18 (m, 2H); 13
C
Mp. 94-96 °C; (literature 95-96 °C). 1H NMR (500 MHz, CDCl3) δ NMR (101 MHz, CDCl3) δ 131.06, 56.48, 34.36, 29.69, 25.28; IR
7.88 (s, 1H), 7.69-7.63 (m, 2H), 7.43 (dd, J = 8.4, 1.6 Hz, 1H), (CHCl3, cm-1): 3250, 2810, 2150, 1700, 620, 520; HRMS (ESI-
7.15 (dd, J = 8.9, 2.5 Hz, 1H), 7.08 (d, J = 2.3 Hz, 1H), 3.91 (s, TOF) m/z [M + NH4]+ calcd. for C7H13IN+: 238.00927; found:
3H); 13C NMR (101 MHz, CDCl3) δ 158.52, 134.35, 132.34, 238.00959.
129.34, 129.26, 128.17, 126.74, 119.49, 118.25, 105.75, 94.61, (iodoethynyl)cyclohexane (2r): Following general procedure
A
55.34, 5.20; the overall spectroscopic data are in complete using ethynylcyclohexane (1r, 83 mg, 0.766 mmol) and purified
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Journal Name
by silica gel column chromatography, eluting with hexanes 0.873 mmol) and purified by silica gel column chromatography,
View Article Online
afforded the title compound as pale yellow oil (154 mg, 0.659 eluting with hexanes afforded the titlDeOcI:o1m0.1p0o39u/nCd7OaBs030p7a6lBe
mmol, 86%). 1H NMR (400 MHz, ) δ 2.52 (ddd, J = 12.7, 8.9, 3.5 orange oil (293 mg, 0.786 mmol 90%). 1H NMR (400 MHz,
Hz, 1H), 1.77 (ddd, J = 8.4, 8.1, 5.6 Hz, 2H), 1.68 (ddd, J = 8.8, CDCl3) δ 7.34 (dd, J = 8.2, 5.5 Hz, 1H), 7.25 (s, 1H), 7.04 (dd, J =
8.1, 4.9 Hz, 2H), 1.54-1.36 (m, 3H), 1.35-1.17 (m, 3H); 13C NMR 8.2, 0.5 Hz, 1H); 13C NMR (101 MHz, CDCl3) δ 163.58, 161.09,
(101 MHz, CDCl3) δ 98.92, 32.39, 31.14, 25.71, 25.69, 24.70, - 138.94, 138.91, 130.55, 130.46, 115.56, 115.34, 94.91, 81.61;
7.13; the overall spectroscopic data are in complete the overall spectroscopic data are in complete agreement with
agreement with assigned structures and consistent with assigned structures and consistent with literature.18b
literature.9g
Representative procedure for the synthesis of (E)-1,2- general procedure
(E)-1-(1,2-diiodovinyl)-3-methoxybenzene (3e): Following
using 1-ethynyl-3-methoxybenzene (1e,
B
diiodoalkenes (B); A preformed solution of Me3SI (484 mg, 2.2 104 mg, 0.787 mmol) and purified by silica gel column
mmol, 2.2 equiv.) and PhI(OAc)2 (354 mg, 1.1 mmol, 1.1 equiv.) chromatography, eluting with hexanes afforded the title
1
1a, 102 mg, 110 uL, compound as pale yellow oil (301 mg, 0.78 mmol, 99%). H
in water (2 mL) was treated with alkyne
1
(
1.0 mmol, 1.0 equiv.) at room temperature. After the NMR (400 MHz, CDCl3) δ 7.26 (s, 1H), 7.25 (s, 1H), 6.97-6.92
completion of reaction, the reaction was diluted with EtOAc (m, 1H), 6.89-6.85 (m, 2H), 3.83 (s, 1H); 13C NMR (101 MHz,
(10 mL), quenched with saturated NaHCO3 (5 mL), saturated CDCl3) δ 159.14, 144.15, 129.45, 120.76, 114.74, 113.75, 95.84,
aqueous sodium thiosulfate (2 mL) and extracted with EtOAc 80.83, 55.33; IR (CHCl3, cm-1): 2932, 1576, 1260, 758; HRMS
(3 X 30 mL). The combined organic layers were washed with (ESI-TOF) m/z [M + NH4]+ calcd. for C9H12I2NO+: 403.90028;
brine solution, dried over anhydrous Na2SO4, concentrated in found: 403.90212.
vacuo and purified by silica gel column chromatography to (E)-1-(1,2-diiodovinyl)-4-methoxybenzene (3f): Following
obtain the desired (E)-1,2-diiodoalkenes (3a-3v). All the general procedure B using 1-ethynyl-4-methoxybenzene (1f,
1
products were fully characterised by H and 13C spectroscopy 102 mg, 0.771 mmol) and purified by silica gel column
and MS spectrometry and were in complete agreement with chromatography, eluting with hexanes afforded the title
1
compound as pale yellow oil (295 mg, 0.764 mmol, 99%). H
the assigned structure and correlated with literature data.
(E)-(1,2-diiodovinyl)benzene (3a): Following general procedure NMR (500 MHz, CDCl3) δ 7.33 (d, J = 8.9 Hz, 1H), 7.19 (s, 1H),
using ethynylbenzene (1a, 93 mg, 0.912 mmol) and purified 6.87 (d, J = 8.8 Hz, 1H), 3.83 (s, 1H); 13C NMR (101 MHz, CDCl3)
B
by silica gel column chromatography, eluting with hexanes δ 159.70, 135.14, 130.17, 113.60, 96.59, 79.87, 55.29; the
afforded the title compound as pale yellow solid (308 mg, overall spectroscopic data are in complete agreement with
0.866 mmol, 95%). Mp. 71-73 °C; (literature 72-74 °C). 1H NMR assigned structures and consistent with literature.18b
(400 MHz, CDCl3) δ 7.38-7.32 (m, 5H), 7.26 (s, 1H); 13C NMR (E)-1-(1,2-diiodovinyl)-3-methylbenzene
(101 MHz, CDCl3) δ 142.97, 128.89, 128.44, 128.36, 96.19, general procedure using 1-ethynyl-3-methylbenzene (1g, 90
(3g):
Following
B
80.83; the overall spectroscopic data are in complete mg, 0.775 mmol) and purified by silica gel column
agreement with assigned structures and consistent with chromatography, eluting with hexanes afforded the title
literature.18b
1
compound as pale yellow oil (252 mg, 0.682 mmol, 88%). H
(E)-1-chloro-2-(1,2-diiodovinyl)benzene
(3b):
Following NMR (400 MHz, CDCl3) δ 7.25 (d, J = 7.3 Hz, 1H), 7.22 (s, 1H),
general procedure
B
using 1-chloro-2-ethynylbenzene (1b, 125 7.16 -7.10 (m, 1H), 2.36 (s, 1H); 13C NMR (101 MHz, CDCl3) δ
mg, 0.919 mmol) and purified by silica gel column 142.84, 138.07, 129.68, 128.91, 128.21, 125.44, 96.47, 80.55,
chromatography, eluting with hexanes afforded the title 21.36; the overall spectroscopic data are in complete
1
compound as light brown oil (329 mg, 0.845 mmol, 92%). H agreement with assigned structures and consistent with
NMR (400 MHz, CDCl3) δ 7.41-7.35 (m, 1H), 7.33 (s, 1H), 7.31- literature.18b
7.25 (m, 2H), 7.21-7.17 (m, 1H); 13C NMR (101 MHz, CDCl3) δ (E)-1-(1,2-diiodovinyl)-4-methylbenzene
(3h):
Following
141.76, 131.41, 130.06, 130.04, 129.37, 127.12, 92.24, 84.93; general procedure B using 1-ethynyl-4-methylbenzene (1h, 92
IR (CHCl3, cm-1): 3016, 1435, 1215, 744; HRMS (ESI-TOF) m/z mg, 0.79 mmol) and purified by silica gel column
+
[M + H]+ calcd. for C8H6ClI2 : 390.82417; found: 390.82559.
chromatography, eluting with hexanes afforded the title
1
Following compound as pale yellow oil (236 mg, 0.639 mmol, 81%). H
(E)-1-bromo-4-(1,2-diiodovinyl)benzene
(3c):
general procedure using 4-bromo-2-ethynylbenzene (1c, 100 NMR (400 MHz, CDCl3) δ 7.27 (d, J = 8.2 Hz, 1H), 7.22 (s, 1H),
B
mg, 0.552 mmol) and purified by silica gel column 7.16 (d, J = 8.0 Hz, 1H), 2.36 (s, 1H); 13C NMR (126 MHz, CDCl3)
chromatography, eluting with hexanes afforded the title δ 140.13, 139.05, 129.05, 128.44, 96.57, 80.17, 77.25, 77.00,
compound as pale yellow solid (225 mg, 0.52 mmol, 94%). Mp. 77.00, 76.75, 21.42; the overall spectroscopic data are in
63-64 °C; (literature 63-64 °C). 1H NMR (400 MHz, CDCl3) δ 7.49 complete agreement with assigned structures and consistent
(d, J = 8.7 Hz, 1H), 7.28 (s, 1H), 7.22 (d, J = 8.7 Hz, 1H); 13C NMR with literature.18b
(101 MHz, CDCl3) δ 141.79, 131.60, 130.09, 123.03, 94.57, (E)-1-(1,2-diiodovinyl)-4-ethylbenzene (3i): Following general
81.78; the overall spectroscopic data are in complete procedure
agreement with assigned structures and consistent with mmol) and purified by silica gel column chromatography,
literature.18b
eluting with hexanes afforded the title compound as pale
(E)-1-(1,2-diiodovinyl)-4-fluorobenzene (3d): Following general orange oil (236 mg, 0.615 mmol, 86%). 1H NMR (500 MHz,
procedure using 4-fluoro-2-ethynylbenzene (1d, 105 mg, CDCl3) δ 7.29 (d, J = 8.2 Hz, 1H), 7.22 (s, 1H), 7.19 (d, J = 8.4 Hz,
A using 1-ethynyl-4-ethylbenzene (1i, 93 mg, 0.715
B
8 | J. Name., 2012, 00, 1-3
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1H), 2.66 (q, J = 7.6 Hz, 1H), 1.26 (t, J = 7.6 Hz, 2H); 13C NMR (E)-3-(1,2-diiodovinyl)pyridine (3n): Following general
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(126 MHz, CDCl3) δ 145.25, 140.24, 128.54, 127.82, 96.66, procedure
B
using 3-ethynylpyridine (1n,D1O0I:010m.1g0,390/.C977O0Bm03m07o6lB)
80.05, 28.68, 15.12; the overall spectroscopic data are in and purified by silica gel column chromatography, eluting with
complete agreement with assigned structures and consistent 50:1 hexanes/EtOAc afforded the inseparable mixture of title
with literature.18b
compound as pale yellow solid (221 mg, 0.621 mmol, 64%)
1
(E)-1-(tert-butyl)-4-(1,2-diiodovinyl)benzene (3j): Following along with 2n. H NMR (400 MHz, CDCl3) δ 8.66 (s, 1H), 8.55-
general procedure using 1-(tert-butyl)-4-ethynylbenzene (1j, 8.53 (m, 1H), 7.75 (d, J = 7.8 Hz, 1H), 7.37 (s, 1H), 7.35-7.27 (m,
B
88 mg, 0.555 mmol) and purified by silica gel column 1H); 13C NMR (101 MHz, CDCl3) δ 149.32, 148.06, 136.17,
chromatography, eluting with hexanes afforded the title 134.93, 123.27, 107.85, 83.23; IR (CHCl3, cm-1): 3057, 2880,
compound as pale yellow solid (187 mg, 0.455 mmol, 82%). 2100, 1630, 1450, 720, 570; HRMS (ESI-TOF) m/z [M + H]+
1
Mp. 63-64 °C. H NMR (400 MHz, CDCl3) δ 7.36 (d, J = 8.4 Hz, calcd. for C7H6I2N+: 357.85841; found: 357.85508.
2H), 7.31 (d, J = 8.6 Hz, 2H), 7.22 (s, 1H), 1.33 (s, 9H); 13C NMR (E)-1,2-diiododec-1-ene (3o): Following general procedure
B
(101 MHz, CDCl3) δ 152.07, 131.83, 128.35, 125.23, 96.76, using dec-1-yne (1o, 77 mg, 0.555 mmol) and purified by silica
79.82, 34.78, 31.19; IR (CHCl3, cm-1): 3066, 2954, 2926, 2858, gel column chromatography, eluting with hexanes afforded the
1607, 1498, 1458, 1150, 829, 777, 597; HRMS (ESI-TOF) m/z [M title compound as pale yellow oil (178 mg, 0.455 mmol, 82%).
+ Na]+ calcd. for C12H14I2Na+: 434.90826; found: 434.90542.
1H NMR (500 MHz, CDCl3) δ 6.80 (s, 1H), 2.53-2.47 (m, 2H),
(E)-1-(1,2-diiodovinyl)-2-(trifluoromethyl)benzene
(3k): 1.58-1.49 (m, 4H), 1.36-1.24 (m, 6H), 0.89 (t, J = 6.9 Hz, 3H); 13
C
Following general procedure
B
using 1-ethynyl-2- NMR (101 MHz, CDCl3) δ 104.47, 78.95, 44.61, 31.81, 29.36,
(trifluoromethyl)benzene (1k, 122 mg, 0.718 mmol) and 29.15, 28.14, 28.12, 22.65, 14.15; the overall spectroscopic
purified by silica gel column chromatography, eluting with data are in complete agreement with assigned structures and
hexanes afforded the title compound as light brown oil (289 consistent with literature.16f
1
mg, 0.68 mmol, 95%). H NMR (400 MHz, CDCl3) δ 7.68 (d, J = (E)-(1,2-diiodovinyl)cyclopropane (3p): Following general
7.9 Hz, 1H), 7.60 (t, J = 7.6 Hz, 1H), 7.48 (t, J = 7.7 Hz, 1H), 7.37 procedure
B using ethynylcyclopropane (1p, 80 mg, 1.207
(s, 1H), 7.24 (d, J = 7.7 Hz, 1H); 13C NMR (101 MHz, CDCl3) δ mmol) and purified by silica gel column chromatography,
142.26, 132.44, 129.78, 129.01, 126.84, 126.79, 90.40, 85.57; eluting with hexanes afforded the title compound as pale
IR (CHCl3, cm-1): 3052, 3002, 2941, 2843, 2165, 1626, 1598, yellow oil (324 mg, 1.014 mmol, 84%). 1H NMR (400 MHz,
1480, 1388, 1228, 1172, 1161, 1026, 900, 550, 750; HRMS (ESI- CDCl3) δ 6.86 (s, 1H), 1.50 (ttd, J = 7.5, 5.2, 0.8 Hz, 1H), 0.82
TOF) m/z [M + NH4]+ calcd. for C9H9I2N+: 441.87764; found: (dqd, J = 3.9, 2.0, 0.7 Hz, 4H); 13C NMR (101 MHz, CDCl3) δ
441.87903.
(E)-2-(1,2-diiodovinyl)-6-methoxynaphthalene (3l): Following (ESI-TOF) m/z [M + Na]+ calcd. for C5H6I2Na+: 342.84566; found:
general procedure using 2-ethynyl-6-methoxynaphthalene 342.84417.
1l, 100 mg, 0.549 mmol) and purified by silica gel column (E)-(1,2-diiodovinyl)cyclopentane (3q): Following general
chromatography, eluting with hexanes afforded the title procedure using ethynylcyclopentane (1q, 81 mg, 0.863
109.78, 23.07, 9.51; IR (CHCl3, cm-1): 2953, 1216, 749; HRMS
B
(
B
compound as white solid (234 mg, 0.538 mmol, 98%). Mp. mmol) and purified by silica gel column chromatography,
117-119 °C. 1H NMR (400 MHz, CDCl3) δ 7.78 (d, J = 1.5 Hz, 1H), eluting with hexanes afforded the title compound as pale
7.75 (d, J = 9.0 Hz, 1H), 7.72 (d, J = 8.6 Hz, 1H), 7.41 (dd, J = 8.5, yellow oil (276 mg, 0.794 mmol, 92%). 1H NMR (400 MHz,
1.8 Hz, 1H), 7.30 (s, 1H), 7.17 (dd, J = 8.5, 1.8 Hz, 1H), 7.13 (d, J CDCl3) δ 6.79 (s, 1H), 2.62-2.45 (m, 1H), 1.82-1.71 (m, 4H),
= 2.4 Hz, 1H); 13C NMR (126 MHz, CDCl3) δ 158.60, 137.99, 1.69-1.57 (m, 2H), 1.48-1.38 (m, 2H); 13C NMR (75 MHz, CDCl3)
134.51, 129.80, 128.09, 127.92, 126.95, 126.51, 119.53, δ 115.46, 77.32, 50.34, 33.11, 25.53; IR (CHCl3, cm-1): 3075,
105.82, 96.78, 80.40, 55.38; IR (CHCl3, cm-1): 3075, 2835, 2300, 1421, 951, 748; HRMS (ESI-TOF) m/z [M + NH4]+ calcd. for
2024, 1595, 1490, 1462, 1433, 1254, 1114, 1047, 1023, 751, C7H14I2N+: 365.92156; found: 365.92247.
550; HRMS (ESI-TOF) m/z [M + Na]+ calcd. for C13H10I2Na+: (E)-(1,2-diiodovinyl)cyclohexane (3r): Following general
458.87178; found: 458.87929.
procedure
B using ethynylcyclohexane (1r, 83 mg, 0.767 mmol)
(E)-1-(1,2-diiodovinyl)pyrene
(3m):
Following
general and purified by silica gel column chromatography, eluting with
procedure B using 4-ethynylpyrene (1m, 100 mg, 0.438 mmol) hexanes afforded the title compound as pale yellow oil (249
and purified by silica gel column chromatography, eluting with mg, 0.69 mmol, 90%). 1H NMR (400 MHz, CDCl3) δ 6.78 (s, 1H),
hexanes afforded the title compound as pale yellow oil (194 2.08 (tt, J = 10.8, 3.5 Hz, 1H), 1.80 (ddd, J = 10.0, 4.8, 2.0 Hz,
1
mg, 0.403 mmol, 92%). H NMR (400 MHz, CDCl3) δ 8.29-8.22 1H), 1.74-1.66 (m, 1H), 1.62-1.52 (m, 1H), 1.50-1.11 (m, 7H);
(m, 3H), 8.18 (d, J = 7.9 Hz, 2H), 8.14 (d, J = 9.3 Hz, 1H), 8.06 (d, 13C NMR (101 MHz, CDCl3) δ 114.37, 76.42, 48.78, 32.29,
J = 9.3 Hz, 1H), 8.02 (d, J = 7.6 Hz, 1H), 7.88 (d, J = 7.9 Hz, 1H), 25.46, 25.20; IR (CHCl3, cm-1): 2925, 1729, 772; HRMS (ESI-TOF)
7.66 (s, 1H); 13C NMR (101 MHz, CDCl3) δ 137.88, 131.62, m/z [M + NH4]+ calcd. for C8H16I2N+: 379.93721; found:
131.30, 131.10, 129.45, 128.20, 128.20, 127.38, 126.47, 379.93624; the overall spectroscopic data are in complete
125.52, 125.37, 125.09, 124.90, 124.70, 124.37, 95.14, 84.70; agreement with assigned structures and consistent with
IR (CHCl3, cm-1): 3050, 2250, 1690, 1500, 980, 750, 550 HRMS literature.16f
(ESI-TOF) m/z [M + NH4]+ calcd. for C18H14I2N+: 497.92156; (E)-(1,2-diiodoprop-1-en-1-yl)benzene (3s): Following general
found: 497.92092.
procedure B using prop-1-yn-1-ylbenzene (1s, 93 mg, 0.80
mmol) and purified by silica gel column chromatography,
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J. Name., 2013, 00, 1-3 | 9
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Organic & Biomolecular Chemistry
Page 10 of 11
ARTICLE
Journal Name
Aguilar, L. Wang, M. Lautens, Org. Lett., 201V0ie,w1Ar2ti,cle5O0n9li2ne-
5095; (c) J. A. Crossley, D. L. Browne, JD. OOIr:g1.0C.1h03e9m/C.,72O0B10030, 7765B
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Panda, A. Ramaraju, J. Org. Chem., 2017, 82, 944-949.
(a) For insights of the Cadiot-Chodkiewicz reaction, see: Tsuji,
J. In Palladium Reagents and Catalysis: New Perspectives for
the 21st Century, 2nd ed.; Wiley: Chichester, 2004; Chapter
3, pp 22-228 and references cited therein; (b) M. Alami, F.
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eluting with hexanes afforded the title compound as pale
yellow oil (236 mg, 0.640 mmol, 80%). 1H NMR (400 MHz,
CDCl3) δ 7.35-7.32 (m, 2H), 7.29 (d, J = 7.2 Hz, 1H), 7.26 (s, 1H),
7.22 (dd, J = 8.2, 1.4 Hz, 1H), 2.80 (s, 3H); 13C NMR (101 MHz,
CDCl3) δ 148.09, 128.43, 128.38, 128.22, 96.30, 95.47, 40.18;
the overall spectroscopic data are in complete agreement with
assigned structures and consistent with literature.18b
,
8
,
3
(E)-(1,2-diiodobut-1-en-1-yl)benzene (3t): Following general
procedure
B using but-1-yn-1-ylbenzene (1t, 92 mg, 0.704
mmol) and purified by silica gel column chromatography,
eluting with hexanes afforded the title compound as pale
yellow oil (243 mg, 0.634 mmol, 90%). 1H NMR (500 MHz,
CDCl3) δ 7.35 (dd, J = 10.2, 4.6 Hz, 2H), 7.30-7.26 (m, 1H), 7.22-
4
(a) D. L. Usanov, H. Yamamoto, J. Am. Chem. Soc., 2011, 133,
7.18 (m, 1H), 2.88 (q, J = 7.4 Hz, 2H), 1.18 (t, J = 7.4 Hz, 3H); 13
C
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Org. Chem., 2011, 76, 2072-2083; (c) H. Liu, C. Chen, L.
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Tetrahedron Lett., 1987, 28, 3463-3466; (f) K. Takai, T.
Kuroda, S. Nakatsukasa, K. Oshima, H. Nozaki, Tetrahedron
Lett., 1985, 26, 5585-5588.
NMR (101 MHz, CDCl3) δ 147.96, 128.43, 128.34, 128.13,
106.49, 93.66, 44.83, 12.92; the overall spectroscopic data are
in complete agreement with assigned structures and
consistent with literature.18b
(E)-1,2-diiodo-1,2-diphenylethene (3u): Following general
procedure
B using 1,2-diphenylethyne (1u, 100 mg, 0.561
5
6
7
(a) J. E. Hein, J. C. Tripp, L. B. Krasnova, K. B. Sharpless, V. V.
Fokin, Angew. Chem. Int. Ed., 2009, 48, 8018-8021; (b) B.
Wang, J. Zhang, X. Wang, N. Liu, W. Chen, Y. Hu, J. Org.
Chem., 2013, 78, 10519-10523.
mmol) and purified by silica gel column chromatography,
eluting with hexanes afforded the title compound as white
solid (204 mg, 0.472 mmol, 84%). Mp. 149-151 °C; (literature
1
148-150 °C). H NMR (400 MHz, ) δ 7.56 -.751 (m, 3H), 7.40-
(a) K. C. Nicolaou, Angew. Chem. Int. Ed. Engl., 1993, 32
,
7.31 (m, 7H); 13C NMR (101 MHz, ) δ 147.60, 131.59, 128.54,
128.40, 128.33, 128.24, 123.24, 89.34; the overall
spectroscopic data are in complete agreement with assigned
structures and consistent with literature.18b
1377-1385; (b) J. M. Tedder, A. Nechvatal, A. W. Murray, J.
Carnduff in Basic Organic Chemistry, Vol. 4, John Wiley &
Sons, London, 1971.
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Wilhelm, A. Sun, C. P. Grey, J. W. Lauher, N. S. Goroff, J. Am.
Chem. Soc., 2008, 130, 7702-7709; (c) A. Sun, J. W. Lauher, N.
S. Goroff, Science, 2006, 312, 1030-1034.
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Agrofoglio, Tetrahedron, 2008, 64, 4444-4452; (b) G. W.
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B
using hex-3-yne (1v, 72 mg, 0.881 mmol) and purified by silica
gel column chromatography, eluting with hexanes afforded the
title compound as pale yellow oil (266 mg, 0.793 mmol, 90%).
8
9
1
Mp. 149-151 °C; (literature 148-150 °C). H NMR (500 MHz,
CDCl3) δ 2.70 (q, J = 7.3 Hz, 2H), 1.05 (t, J = 7.3 Hz, 3H); 13C
NMR (101 MHz, CDCl3) δ 102.46, 77.32, 77.00, 77.00, 76.68,
45.05, 12.69; the overall spectroscopic data are in complete
agreement with assigned structures and consistent with
literature.16b
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Acknowledgements
SK gratefully acknowledge the Department of Science and
Technology, India for the INSPIRE Faculty award (IFA12-CH-54)
and Start-up Research Grant for Young Scientists (SB/FT/CS-
024/2014).
C. U. Maheswari, S. P. Kumar, Tetrahedron Lett., 2010, 51
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