Synthesis of Aryl(2,4,6-trimethoxyphenyl)iodonium Trifluoroacetate Salts

Article abstract of DOI:10.1021/acs.joc.6b02811

The direct synthesis of aryl(2,4,6-trimethoxyphenyl)iodonium trifluoroacetate salts from aryl iodides is described. Stoichiometric quantities of trifluoroacetic acid and trimethoxybenzene are used as the counteranion and auxiliary precursors, respectively, under oxidizing conditions. The reaction occurs at mild temperature, is broad in scope, and does not require a separate anion exchange step to install the trifluoroacetate group. The intermediacy of two distinct dicarboxy aryl-λ³-iodanes is hypothesized in the mechanism.

Full text of DOI:10.1021/acs.joc.6b02811

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Note
Synthesis of Aryl(2,4,6-trimethoxyphenyl)iodonium Trifluoroacetate Salts
Virginie Carreras, Alexander H Sandtorv, and David Ross Stuart
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.6b02811 • Publication Date (Web): 21 Dec 2016
Downloaded from http://pubs.acs.org on December 23, 2016
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Synthesis of Aryl(2,4,6ꢀtrimethoxyphenyl)iodonium Trifluoroacetate Salts
Virginie Carreras, Alexander H. Sandtorv, and David R. Stuart*
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Department of Chemistry, Portland State University, Portland OR 97201, United States
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Abstract: The direct synthesis of aryl(2,4,6ꢀtrimethoxyphenyl)iodonium trifluoroacetate salts
from aryl iodides is described. Stoichiometric quantities of trifluoroacetic acid and
trimethoxybenzene are used as the counter anion and auxiliary precursors, respectively, under
oxidizing conditions. The reaction occurs at mild temperature, is broad in scope, and does not
require a separate anion exchange step to install the trifluoroacetate group. The intermediacy
of two distinct dicarboxy arylꢀλ3ꢀiodanes is hypothesized in the mechanism.
Oneꢀpot reactions are an efficient and attractive means to prepare diaryliodonium salts
from commercial arene building blocks and direct access to triflate,1 tosylate,2 and
tetrafluoroborate3 salts have been well described, particularly in the past decade. While these
methods have been a primary driving force for the utilization of diaryliodonium salts in novel
arylation reactions,4 direct access to diaryliodonium salts incorporating other counter anions are
relatively limited. Specifically, although diaryliodonium trifluoroacetates are useful salts in their
own right,5 we were surprised to find that a wellꢀestablished synthesis from aryl iodides has not
been reported;6,7 although they are suggested as intermediates in the synthesis of
diaryliodonium triflates with trifluoroacetic acid as solvent.1b,c Given empirical evidence for the
importance of counter anion identity on reactivity,4 the development of methods that deliver
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diaryliodonium trifluoroacetates directly, without recourse to anion exchange, would enable
reaction development with these reagents.
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We have recently described the Nꢀarylation of alicyclic amines with aryl(2,4,6ꢀ
trimethoxyphenyl)iodonium trifluoroacetate salts8 wherein the TFAꢀsalts were prepared by first
synthesizing the OTsꢀsalts and then performing a counter anion exchange with NaTFA.2e While
accessible, the yields for the TFAꢀsalts over this twoꢀstep procedure varied widely (15 – 85%;
average 51%)8 and we viewed this as an impractical procedure9 for future reaction development
with aryl(TMP)iodonium trifluoroacetate salts. We initially explored the possibility of replacing
toluenesulfonic acid with trifluoroacetic acid in a direct synthesis from aryl iodides with mꢀCPBA
as oxidant,2e but this resulted in low and variable yields (Scheme 1A).10 The combination of
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toluenesulfonic acid and mꢀCPBA is known to produce heteroleptic arylꢀλ3ꢀiodanes, such as
[hydroxyl(tosyloxy)iodo]arenes, from aryl iodides.2e,11 In this vein, we investigated the oxidation
of an aryl iodide with mꢀCPBA in the presence of stoichiometric trifluoroacetic acid. However,
we did not observe clean formation of a single arylꢀλ3ꢀiodane, although we did observe
[bis(trifluoroacetoxy)iodo]arenes 2a and 2b (Scheme 1B) and other unidentifiable signals in the
crude 19FꢀNMR spectra.12 Additionally, peaks consistent with the structures 2a' and 2b' were
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observed in the crude H NMR spectra.12,13 Reaction of 2b with trimethoxybenzene in
acetonitrile at 55 °C produced 1h in 42% yield (Scheme 1C). Given the observation of several
arylꢀλ3ꢀiodane intermediates under these conditions, we were intrigued by the possibility that a
dynamic equilibrium between these intermediates may be amenable to optimization and lead to
a practical direct synthesis of aryl(TMP)iodonium trifluoroacetate salts from aryl iodides.
Scheme 1. Identification and reactivity of potential reaction intermediates.
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We previously used design of experiment to optimize the reaction conditions for the
synthesis of aryl(TMP)iodonium tosylates which provided insight into the contribution of each
variable;2e temperature had the largest contribution on yield. We noted during our initial
screening experiments that each stage required longer reaction time with trifluoroacetic acid
relative to toluene sulfonic acid. Therefore, stage 1 was held for 50 minutes and stage 2 was
held for 15 minutes in our current optimization studies.
We focused on temperature,
stoichiometry of mꢀCPBA and trifluoroacetic acid (TFAH), and solvent in the optimization of
reaction conditions with trifluoroacetic acid as the acid source (Scheme 2). Higher yields are
consistently observed in acetonitrile over ethyl acetate as solvent (Scheme 2). Moreover, in
acetonitrile consistently higher yields were observed with a slight excess of mꢀCPBA (1.2
equiv.), whereas the stoichiometry of trifluoroacetic acid appeared to have little influence on
yield (Scheme 2). The temperature had a dramatic influence on yield and a maximum yield was
obtained at 51 °C as compared to 25 and 78 °C (Scheme 2). Based on these experiments the
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optimal conditions selected to evaluate the scope of the reaction were mꢀCPBA 1.2 equiv.,
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TFAH 1 equiv., at 50 °C in acetonitrile.
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Scheme 2. Effect of variables on reaction yield.
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The reaction scope is presented in Table 1. The scope aryl iodide substrates that
participate in this reaction is broad (> 20 examples) and the reactions proceed with high yield
(77% average yield). Electronꢀrich and electronꢀdeficient aryl iodides are compatible in this
reaction as evidenced by the 14 examples that bear monoꢀfunctionalized aryl moieties (Table 1,
entries 1 – 14, 1a-n, 70ꢀ94%). Polyfunctional aryl moieties are also compatible and this point
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reinforces the importance of using unsymmetrical iodonium salts for nucleophile arylation
reactions (Table 1, entries 15 – 21, 1o-u, 68 – 88%). Moreover, the synthesis of (1ꢀ
naphthyl)(TMP)iodonium trifluoroacetate was possible under these conditions which we were
unable to isolate in our previous work.2e The synthesis of pyridineꢀcontaining 1v is also
possible, albeit in moderate yield of 42% and may allow Cꢀ3 functionalization of the pyridyl
moiety (Table 1, entry 22).14 The oxidation of two iodide groups on a substrate to yield
bis(iodonium) compounds was also possible here and 1w and 1x were obtained in 90 and 76%
yield, respectively (Table 1, entry 23 and 24). The Mes group, which is useful in both metalꢀ
catalyzed4,15 and metalꢀfree16 reactions, may also be introduced by this method, albeit in
moderate yield (Table 1, 1b and 1f, 51 and 49%, respectively).
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Table 1. Reaction scope.
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aConditions: aryl iodide (1 mmol, 1 equiv.), mꢀCPBA (1.2 mmol, 1.2 equiv.), TFAH (1 mmol, 1
equiv.), MeCN (1 mL), 55 °C, 50 min, 1,3,5ꢀtrimethoxybenzene (1 mmol, 1 equiv.), 55 °C, 15
min. bReaction conducted on 2 mmolꢀscale of aryl iodide. cMesitylene (1.5 mmol, 1 equiv.)
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instead of 1,3,5ꢀtrimethoxybenzene, 77oC for 22h. EtOAc (1 mL) used as solvent.
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In conclusion, we have demonstrated a practical and highꢀyielding method to access
diverse and highlyꢀfunctionalized aryl(TMP)iodonium trifluoroacetate salts directly from aryl
iodides. This method utilizes commercially available reagents, is straight forward to conduct, is
functional group tolerant, and provides a mild approach to trifluoroacetate salts that does not
require a subsequent anion exchange step. We anticipate that this method will engender the
use of iodonium trifluoroacetate salts in organic synthesis.
Experimental Section
General considerations. Commercially available reagents and solvents were used without
further purification unless stated otherwise. mꢀCPBA was dried overꢀnight under vacuum. 2b
was prepared by literature procedure.17 1H, 13C{1H}, 19F{1H} NMR spectra were recorded in
CDCl3 or DMSOꢀd6 on a 400 MHz spectrometer at 298 K, unless stated otherwise. The following
abbreviations are used to indicate the multiplicity of the signals: br, broad; s, singlet; d, doublet;
t, triplet; q, quartet; m, multiplet; dd, doublet of doublets. IR data were obtained as thin films.
Highꢀresolution mass spectrometry (HRMS) data were obtained by electrospray ionization (ESI)
with an ion trap mass analyzer. Melting points (m.p.) are reported uncorrected.
General procedure for unsymmetrical aryl(TMP)iodonium trifluoroacetate synthesis (1a –
1x). Aryl iodide (1 mmol, 1 equiv) and acetonitrile (1 mL) were added to a 5 mL vial, equipped
with a magnetic stir bar. mꢀCPBA (1.2 mmol, 0.208 g, 1.2 equiv) was added in one portion,
followed by the dropꢀwise addition of TFA (1 mmol, 76 ꢁL, 1 equiv). After sealing the tube with a
screwꢀcap, the reaction was placed in an oil bath set to 55°C and stirred. After 50 min, 1,3,5ꢀ
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trimethoxybenzene (1 mmol, 0.168 g, 1 equiv) was added in one portion and the mixture was
stirred at 55°C for 15 min. The postꢀreaction mixture was removed from heat and concentrated
under reduced pressure and the crude residue was triturated with diethyl ether (10 mL). The
solid was collected by vacuum filtration and washed by slurry filtration with diethyl ether (3 × 10
mL). After drying under reduced pressure, the diaryliodonium salt was obtained in analytically
pure form.
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Phenyl(2,4,6-trimethoxyphenyl)iodonium trifluoroacetate 1a. Isolated as a white solid
(0.907 g, 94%). 1HꢀNMR (400 MHz, CDCl3) δ (ppm): 7.90 (dd, J1 = 8.4 Hz, J2 = 1.0 Hz, 2H), 7.47
(t, J = 7.4 Hz, 1H), 7.33 (t, J = 8.1 Hz, 2H), 6.16 (s, 2H), 3.87 (s, 6H), 3.86 (s, 3H). 13C{1H}ꢀNMR
(101 MHz, CDCl3) δ (ppm): 166.8, 161.9 (q, JCꢀF = 34.0 Hz), 160.7, 133.9, 131.4, 131.2, 117.2,
116.7 (q, JCꢀF = 295.1 Hz), 91.5, 86.0, 56.9, 56.0. 19F{1H}ꢀNMR (376 MHz, CDCl3) δ (ppm): ꢀ
75.3. FTꢀIR: 3071 (br), 2986 (br), 2954 (br), 2850 (br), 1676 (s), 1580 (s), 1460 (m), 1161 (m),
+
1112 (s), 795(m), 716 (m) cmꢀ1. HRꢀMS (EI) m/z [MꢀTFA]+ calcd. for C15H16IO3 : 371.0139,
found: 371.0133. M.p. (Et2O): 160ꢀ165 °C.
4-methylphenyl(2,4,6-trimethoxyphenyl)iodonium trifluoroacetate 1b. Isolated as a
white solid (0.462 g, 93%) 1HꢀNMR (400 MHz, CDCl3) δ (ppm): 7.77 (d, J = 8.4 Hz, 2H), 7.12 (d,
13
J = 8.3 Hz, 2H), 6.15 (s, 2H), 3.87 (s, 6H), 3.85 (s, 3H), 2.33 (s, 3H). C{1H}ꢀNMR (101 MHz,
CDCl3) δ (ppm): 166.70, 161.71 (q, JCꢀF = 34.0 Hz), 160.56, 141.98, 133.96, 132.15, 116.68 (q,
19
JCꢀF = 295.1 Hz), 113.41, 91.47, 85.93, 56.84, 55.96, 21.33. F{1H}ꢀNMR (376 MHz, CDCl3) δ
(ppm): ꢀ75.2. FTꢀIR: 2990 (br), 2949 (br), 2885 (br), 2852 (br), 1655 (m), 1581 (s), 1458 (m),
+
1162 (s), 1117 (s), 795 (s), 716 (s) cmꢀ1. HRꢀMS (EI) m/z [MꢀTFA]+ calcd. for C16H18IO3 :
385.0295, found: 385.0289. M.p. (Et2O): 163ꢀ165 °C.
4-isopropylphenyl(2,4,6-trimethoxyphenyl)iodonium trifluoroacetate 1c. Isolated as a white
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solid (0.432 g, 82%) HꢀNMR (400 MHz, CDCl3) δ (ppm): 7.81 (d, J = 8.6 Hz, 2H), 7.17 (d, J =
8.5 Hz, 2H), 6.16 (s, 2H), 3.88 (s, 6H), 3.86 (s, 3H), 2.88 (m, 1H), 1.20 (d, J = 6.9 Hz, 6H).
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13C{1H}ꢀNMR (101 MHz, CDCl3) δ (ppm): 166.7, 161.8 (q, JCꢀF = 33.9 Hz), 160.6, 152.6, 134.0,
129.7, 116.7 (q, JCꢀF = 295.1 Hz), 113.4, 91.5, 85.9, 56.8, 56.0, 34.0, 23.7. 19F{1H}ꢀNMR (376
MHz, CDCl3) δ (ppm): ꢀ75.3. FTꢀIR: 3054 (br), 3014 (br), 2969 (br), 2947 (br), 1659 (s), 1580 (s),
1463 (m), 1410 (m), 1160 (s), 1121 (s), 795 (m), 719 (m) cmꢀ1. HRꢀMS (EI) m/z [MꢀTFA]+ calcd.
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+
for C18H22IO3 : 413.0608, found: 413.0600. M.p. (Et2O): 168ꢀ171 °C.
4-tert-butylphenyl(2,4,6-trimethoxyphenyl)iodonium trifluoroacetate 1d. Isolated as a white
solid (0.480 g, 89%) 1HꢀNMR (400 MHz, DMSOꢀd6) δ (ppm): 7.83 (d, J = 8.7 Hz, 2H), 7.48 (d, J
= 8.7 Hz, 2H), 6.46 (s, 2H), 3.95 (s, 6H), 3.87 (s, 3H), 1.24 (s, 9H). 13C{1H}ꢀNMR (101 MHz,
CDCl3) δ (ppm): 166.7, 161.9 (q, JCꢀF = 34.0 Hz), 160.7, 154.9, 133.7, 128.7, 116.7 (q, JCꢀF
=
294.9 Hz), 113.3, 91.5, 85.9, 56.9, 56.0, 35.1, 31.1. 19F{1H}ꢀNMR (376 MHz, DMSOꢀd6) δ (ppm):
ꢀ73.4. FTꢀIR: 2970 (br), 2951 (br), 2904 (br), 2867 (br), 1670 (s), 1657 (s), 1585 (s), 1409 (m),
1159 (s), 1121 (s), 794 (m), 718 (m) cmꢀ1. HRꢀMS (EI) m/z [MꢀTFA]+ calcd. for C19H24IO3 :
+
427.0765, found: 427.0755. M.p. (Et2O): 180ꢀ185 °C.
4-fluorophenyl(2,4,6-trimethoxyphenyl)iodonium trifluoroacetate 1e. Isolated as a white
solid (0.935 g, 93%). 1HꢀNMR (400 MHz, DMSOꢀd6) δ (ppm): 7.97 (q, J = 4.0 Hz, 2H), 7.33 (t, J
= 8.9 Hz, 2H), 6.46 (s, 2H), 3.94 (s, 6H), 3.87 (s, 3H). 13C{1H}ꢀNMR (101 MHz, DMSOꢀd6) δ
(ppm): 166.2, 163.6 (d, JCꢀF = 250.2 Hz), 159.5, 158.2 (q, JCꢀF = 30.9 Hz), 137.1 (d, JCꢀF = 8.9
Hz), 118.8 (d, JCꢀF = 22.7 Hz), 117.3 (q, JCꢀF = 300.0 Hz), 110.9 (d, JCꢀF = 3.1 Hz), 92.1, 88.1,
57.3, 56.1. 19F{1H}ꢀNMR (376 MHz, DMSOꢀd6) δ (ppm): ꢀ73.4, ꢀ107.5. FTꢀIR: 3074 (br), 3022
(br), 2988 (br), 2956 (br), 1683 (s), 1575 (s), 1157 (s), 1117 (s), 799 (s), 716 (s) cmꢀ1. HRꢀMS
(EI) m/z [MꢀTFA]+ calcd. for C15H15FIO3 : 389.0044, found: 389.0039. M.p. (Et2O): 165ꢀ169 °C.
+
4-chlorophenyl(2,4,6-trimethoxyphenyl)iodonium trifluoroacetate 1f. Isolated as a white
solid (0.477 g, 81%). 1HꢀNMR (400 MHz, DMSOꢀd6) δ (ppm): 7.91 (d, J = 8.8 Hz, 2H), 7.53 (d, J
= 8.8 Hz, 2H), 6.47 (s, 2H), 3.94 (s, 6H), 3.87 (s, 3H). 13C{1H}ꢀNMR (101 MHz, DMSOꢀd6) δ
(ppm): 166.2, 159.4, 157.9 (q, JCꢀF = 30.6 Hz), 136.6, 136.1, 131.4, 117.3 (q, JCꢀF = 300.9 Hz),
114.2, 92.1, 87.6, 57.3, 56.2. 19F{1H}ꢀNMR (376 MHz, DMSOꢀd6) δ (ppm): ꢀ73.4. FTꢀIR: 3081
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(br), 3062 (br), 3000 (br), 2955 (br), 1682 (m), 1577 (s), 1345 (m), 1176 (s), 1116 (s), 794 (m),
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715 (s) cmꢀ1. HRꢀMS (EI) m/z [MꢀTFA]+ calcd. for C15H15ClIO3 : 404.9749, found: 404.9744.
+
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M.p. (Et2O): 168ꢀ172 °C.
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4-bromophenyl(2,4,6-trimethoxyphenyl)iodonium trifluoroacetate 1g. Isolated as a white
solid (0.969 g, 86%). 1HꢀNMR (400 MHz, DMSOꢀd6) δ (ppm): 7.83 (d, J = 8.6 Hz, 2H), 7.66 (d, J
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= 8.6 Hz, 2H), 6.47 (s, 2H), 3.94 (s, 6H), 3.87 (s, 3H).
13C{1H}ꢀNMR (101 MHz, DMSOꢀd6) δ
(ppm): 166.2, 159.4, 157.9 (q, JCꢀF = 30.7 Hz), 136.2, 134.3, 125.3, 117.3 (q, JCꢀF = 300.8 Hz),
114.9, 92.1, 87.5, 57.3, 56.2. 19F{1H}ꢀNMR (376 MHz, DMSOꢀd6) δ (ppm): ꢀ73.4. FTꢀIR: 3085
(br), 3001 (br), 2948 (br), 2844 (br), 1656 (m), 1581 (s), 1352 (m), 1175 (s), 1118 (s), 799 (s),
+
716 (s) cmꢀ1. HRꢀMS (EI) m/z [MꢀTFA]+ calcd. for C15H15BrIO3 : 448.9244, found: 448.9240. M.p.
(Et2O): 171ꢀ173 °C.
4-methylbenzoxycarbonyl(2,4,6-trimethoxyphenyl)iodonium trifluoroacetate 1h. Isolated
as a white solid (0.520 g, 84%). 1HꢀNMR (400 MHz, CDCl3) δ (ppm): 7.97 (br, 4H), 6.17 (s, 2H),
3.91 (s, 3H), 3.87 (s, 9H). 13C{1H}ꢀNMR (101 MHz, CDCl3) δ (ppm): 167.0, 165.7, 162.0 (q, JCꢀF
= 34.4 Hz), 160.7, 133.7, 132.7, 132.1, 121.9, 116.6 (q, JCꢀF = 294.6 Hz), 91.6, 86.4, 56.9, 56.0,
19
52.7. F{1H}ꢀNMR (376 MHz, CDCl3) δ (ppm): ꢀ75.3. Spectral data was in accordance with the
literature.8
4-cyanophenyl(2,4,6-trimethoxyphenyl)iodonium trifluoroacetate 1i. Isolated as a white
solid (0.405 g, 80%). 1HꢀNMR (400 MHz, DMSOꢀd6) δ (ppm): 8.06 (d, J = 8.6 Hz, 2H), 7.92 (d, J
= 8.6 Hz, 2H), 6.49 (s, 2H), 3.93 (s, 6H), 3.88 (s, 3H). 13C{1H}ꢀNMR (101 MHz, DMSOꢀd6) δ
(ppm): 166.4, 159.5, 157.8 (q, JCꢀF = 30.5 Hz), 134.8, 134.7, 121.2, 117.6, 117.3 (q, JCꢀF = 301.0
Hz), 114.1, 92.2, 87.3, 57.4, 56.2. 19F{1H}ꢀNMR (376 MHz, DMSOꢀd6) δ (ppm): ꢀ73.4. FTꢀIR:
3090 (br), 3022 (br), 2953 (br), 2845 (br), 2230 (m), 1713 (m), 1661 (s), 1578 (s), 1414 (m),
+
1162 (s), 1117 (s), 827 (s), 719 (s) cmꢀ1. HRꢀMS (EI) m/z [MꢀTFA]+ calcd. for C16H15INO3 :
396.0091, found: 396.0086. M.p. (Et2O): 166ꢀ167 °C.
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4-nitrophenyl(2,4,6-trimethoxyphenyl)iodonium trifluoroacetate 1j. Isolated as an offꢀwhite
solid (0.273 g, 70%). 1HꢀNMR (400 MHz, DMSOꢀd6) δ (ppm): 8.23 (d, J = 9.0 Hz, 2H), 8.15 (d, J
= 8.9 Hz, 2H), 6.50 (s, 2H), 3.95 (s, 6H), 3.88 (s, 3H). 13C{1H}ꢀNMR (101 MHz, DMSOꢀd6) δ
(ppm): 166.5, 159.5, 158.0 (q, JCꢀF = 30.8 Hz), 149.1, 135.4, 126.0, 122.8, 117.2 (q, JCꢀF = 300.7
Hz), 92.2, 87.6, 57.4, 56.2. 19F{1H}ꢀNMR (376 MHz, DMSOꢀd6) δ (ppm): ꢀ73.5. Spectral data
was in accordance with the literature.8
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4-biphenyl(2,4,6-trimethoxyphenyl)iodonium trifluoroacetate 1k. Isolated as an offꢀwhite
solid (0.362 g, 68%) using ethyl acetate as solvent. 1HꢀNMR (400 MHz, DMSOꢀd6) δ (ppm): 8.48
(dd, J1 = 7.4 Hz, J2 = 0.8 Hz, 1H), 8.22 (dd, J1 = 8.3 Hz, J2 = 2.9 Hz, 2H), 8.03 (d, J = 8.1 Hz,
1H), 7.86ꢀ7.82 (m, 1H), 7.72ꢀ7.68 (m, 1H), 7.56 (t, J = 7.7 Hz, 1H), 6.39 (s, 2H), 3.95 (s, 6H),
3.80 (s, 3H). 13C{1H}ꢀNMR (101 MHz, DMSOꢀd6) δ (ppm): 165,9, 159.4, 157.8 (q, JCꢀF = 30.6
Hz), 137.4, 134.0, 132.9, 131.0, 129.3, 129.2, 127.7, 127.3, 119.5, 117.4 (q, JCꢀF = 301.1 Hz),
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92.0, 87.3, 57.2, 56.1. F{1H}ꢀNMR (376 MHz, DMSOꢀd6) δ (ppm): ꢀ75.4. Spectral data was in
accordance with the literature.2e
3-cyanophenyl(2,4,6-trimethoxyphenyl)iodonium trifluoroacetate 1l. Isolated as a white
solid (0.430 g, 84%). 1HꢀNMR (400 MHz, DMSOꢀd6) δ (ppm): 8.47 (br, 1H), 8.19 (d, J = 8.2 Hz,
1H), 8.08 (d, J = 7.9 Hz, 1H), 7.65 (t, J = 8.0 Hz, 1H), 6.47 (s, 2H), 3.95 (s, 6H), 3.87 (s, 3H).
13C{1H}ꢀNMR (101 MHz, DMSOꢀd6) δ (ppm): 166.3, 159.5, 158.1 (q, JCꢀF = 30.9 Hz), 138.8,
137.4, 135.1, 132.2, 117.2 (q, JCꢀF = 300.3 Hz), 117.1, 116.6, 113.6, 92.1, 87.7, 57.3, 56.2.
19F{1H}ꢀNMR (376 MHz, DMSOꢀd6) δ (ppm): ꢀ73.4. Spectral data was in accordance with the
literature.8
3-nitrophenyl(2,4,6-trimethoxyphenyl)iodonium trifluoroacetate 1m. Isolated as a white
1
solid (0.401 g, 76%). HꢀNMR (400 MHz, DMSOꢀd6) δ (ppm): 8.70 (br, 1H), 8.39 (dd, J1 = 8.2
Hz, J2 = 1.9 Hz, 1H), 8.25 (d, J = 8.0 Hz, 1H), 7.74 (t, J = 8.1 Hz, 1H), 6.50 (s, 2H), 3.96 (s, 6H),
3.88 (s, 3H). 13C{1H}ꢀNMR (101 MHz, DMSOꢀd6) δ (ppm): 166.5, 159.5, 158.0 (q, JCꢀF = 30.8
Hz), 148.3, 139.8, 132.6, 128.5, 126.1, 117.2 (q, JCꢀF = 300.5 Hz), 116.2, 92.2, 87.7, 57.4, 56.2.
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19F{1H}ꢀNMR (376 MHz, DMSOꢀd6) δ (ppm): ꢀ73.5. Spectral data was in accordance with the
literature.8
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3-trifluoromethylphenyl(2,4,6-trimethoxyphenyl)iodonium trifluoroacetate 1n. Isolated as a
white solid (0.456 g, 83%). 1HꢀNMR (400 MHz, DMSOꢀd6) δ (ppm): 8.33 (s, 1H), 8.13 (d, J = 8.2
Hz, 1H), 7.99 (d, J = 7.9 Hz, 1H), 7.69 (t, J = 8.0 Hz, 1H), 6.48 (s, 2H), 3.94 (s, 6H), 3.87 (s,
3H). 13C{1H}ꢀNMR (101 MHz, DMSOꢀd6) δ (ppm): 166.4, 159.5, 158.1 (q, JCꢀF = 30.9 Hz), 138.0,
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132.5, 131.1 (q, JCꢀF = 32.7 Hz), 130.7 (d, JCꢀF = 3.9 Hz), 128.1 (d, JCꢀF = 3.6 Hz), 123.0 (q, JCꢀF
=
273.1 Hz), 117.2 (q, JCꢀF = 300.3 Hz), 116.8, 92.1, 87.7, 57.3, 56.2. 19F{1H}ꢀNMR (376 MHz,
DMSOꢀd6) δ (ppm): ꢀ61.4, ꢀ73.5. Spectral data was in accordance with the literature.8
1-naphtyl(2,4,6-trimethoxyphenyl)iodonium trifluoroacetate 1o. Isolated as an offꢀwhite
solid (0.362 g, 68%) using ethyl acetate as solvent. 1HꢀNMR (400 MHz, DMSOꢀd6) δ (ppm): 8.48
(dd, J1 = 7.4 Hz, J2 = 0.8 Hz, 1H), 8.22 (dd, J1 = 8.3 Hz, J2 = 2.9 Hz, 2H), 8.03 (d, J = 8.1 Hz,
1H), 7.86ꢀ7.82 (m, 1H), 7.72ꢀ7.68 (m, 1H), 7.56 (t, J = 7.7 Hz, 1H), 6.39 (s, 2H), 3.95 (s, 6H),
3.80 (s, 3H). 13C{1H}ꢀNMR (101 MHz, DMSOꢀd6) δ (ppm): 165,9, 159.4, 157.8 (q, JCꢀF = 30.6
Hz), 137.4, 134.0, 132.9, 131.0, 129.3, 129.2, 127.7, 127.3, 119.5, 117.4 (q, JCꢀF = 301.1 Hz),
92.0, 87.3, 57.2, 56.1. 19F{1H}ꢀNMR (376 MHz, DMSOꢀd6) δ (ppm): ꢀ75.4. FTꢀIR: 3047 (br), 3013
(br), 2951 (br), 2839 (br), 1678 (m), 1656 (s), 1584 (s), 1341 (s), 1160 (s), 1123 (s), 802 (s), 717
+
(m) cmꢀ1. HRꢀMS (EI) m/z [MꢀTFA]+ calcd. for C19H18IO3 : 421.0295, found: 421.0286. M.p.
(Et2O): 164ꢀ166 °C.
3-trifluoromethyl-6-chlorophenyl(2,4,6-trimethoxyphenyl)iodonium trifluoroacetate 1p.
1
Isolated as a white solid (0.407 g, 69%). HꢀNMR (400 MHz, DMSOꢀd6) δ (ppm): 8.63 (br, 1H),
8.04ꢀ7.97 (m, 2H), 6.44 (s, 2H), 3.92 (s, 6H), 3.85 (s, 3H). 13C{1H}ꢀNMR (101 MHz, DMSOꢀd6) δ
(ppm): 166.2, 159.4, 157.8 (q, JCꢀF = 30.6 Hz), 140.2, 135.6 (d, JCꢀF = 3.9 Hz), 131.0, 130.4 (d,
JCꢀF = 3.4 Hz), 129.1 (q, JCꢀF = 33.3 Hz), 122.6 (q, JCꢀF = 273.0 Hz), 120.1, 117.3 (q, JCꢀF = 300.8
Hz), 92.1, 87.6, 57.0, 56.1. 19F{1H}ꢀNMR (376 MHz, DMSOꢀd6) δ (ppm): ꢀ61.1, ꢀ73.4. Spectral
data was in accordance with the literature.8
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3-chloro-4-fluorophenyl(2,4,6-trimethoxyphenyl)iodonium trifluoroacetate 1q. Isolated as a
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white solid (0.427 g, 80%). HꢀNMR (400 MHz, DMSOꢀd6) δ (ppm): 8.23 (dd, J1 = 6.8 Hz, J2 =
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2.2 Hz, 1H), 7.91ꢀ7.88 (m, 1H), 7.53 (t, J = 9.1 Hz, 1H), 6.47 (s, 2H), 3.95 (s, 6H), 3.87 (s, 3H).
13C{1H}ꢀNMR (101 MHz, DMSOꢀd6) δ (ppm): 166.3, 159.0 (d, JCꢀF = 252.6 Hz), 159.4, 158.1 (q,
JCꢀF = 31.0 Hz), 136.1, 135.4 (d, JCꢀF = 8.2 Hz), 121.8 (d, JCꢀF = 18.6 Hz), 119.9 (d, JCꢀF = 22.3
Hz), 117.2 (q, JCꢀF = 300.2 Hz), 110.9 (d, JCꢀF = 4.0 Hz), 92.1, 88.1, 57.3, 56.2. 19F{1H}ꢀNMR (376
MHz, DMSOꢀd6) δ (ppm): ꢀ73.4, ꢀ110.4. FTꢀIR: 3082 (br), 3016 (br), 1686 (s), 1576 (s), 1466 (s),
1349 (s), 1120 (s), 825 (m), 715 (m), 697 (s) cmꢀ1. HRꢀMS (EI) m/z [MꢀTFA]+ calcd. for
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C15H14ClFIO3 : 422.9655, found: 422.9648. M.p. (Et2O): 168 °C.
3-chloro-4-methylphenyl(2,4,6-trimethoxyphenyl)iodonium trifluoroacetate 1r. Isolated as
1
a white solid (0.466 g, 88%). HꢀNMR (400 MHz, DMSOꢀd6) δ (ppm): 7.98 (d, J = 1.8 Hz, 1H),
7.74 (dd, J1 = 8.2 Hz, J2 = 1.8 Hz, 1H), 7.44 (d, J = 8.2 Hz, 1H), 6.47 (s, 2H), 3.95 (s, 6H), 3.87
(s, 3H), 2.34 (s, 3H). 13C{1H}ꢀNMR (101 MHz, DMSOꢀd6) δ (ppm): 166.2, 159.4, 157.8 (q, JCꢀF
=
30.5 Hz), 139.8, 134.8, 133.7 (d, JCꢀF = 8.1 Hz), 132.8, 117.3 (q, JCꢀF = 301.2 Hz), 113.0, 92.1,
87.5, 57.3, 56.2, 30.7, 19.5. 19F{1H}ꢀNMR (376 MHz, DMSOꢀd6) δ (ppm): ꢀ73.4. FTꢀIR: 3100 (br),
3007 (br), 2949 (br), 2919 (br), 2843 (br), 1659 (s), 1585 (s), 1470 (m), 1347 (s), 1122 (s), 1055
+
(m), 809 (s), 718 (s) cmꢀ1. HRꢀMS (EI) m/z [MꢀTFA]+ calcd. for C16H17ClIO3 : 418.9905, found:
418.9900. M.p. (Et2O): 168ꢀ173 °C.
3-bromo-4-methylphenyl(2,4,6-trimethoxyphenyl)iodonium trifluoroacetate 1s. Isolated as
1
a white solid (0.467 g, 81%)ꢀ HꢀNMR (400 MHz, DMSOꢀd6) δ (ppm):8.12 (d, J = 1.8 Hz, 1H),
7.77 (dd, J1 = 8.1 Hz, J2 = 1.8 Hz, 1H), 7.44 (d, J = 8.7 Hz, 1H), 6.47 (s, 2H), 3.95 (s, 6H), 3.87
(s, 3H), 2.36 (s, 3H). 13C{1H}ꢀNMR (101 MHz, DMSOꢀd6) δ (ppm): 166.2, 159.4, 157.8 (q, JCꢀF
=
30.5 Hz), 141.6, 136.6, 133.5 (q, JCꢀF = 43.0 Hz), 125.5, 117.3 (q, JCꢀF = 301.1 Hz), 113.2, 92.1,
87.5, 57.3, 56.2, 30.7, 22.3. 19F{1H}ꢀNMR (376 MHz, DMSOꢀd6) δ (ppm): ꢀ73.4. FTꢀIR: 3099 (br),
3008 (br), 2949 (br), 2843 (br), 1682 (m), 1660 (s), 1585 (s), 1466 (m), 1346 (s), 1121 (s), 1056
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(m), 817 (s), 718 (s), 697 (m) cmꢀ1. HRꢀMS (EI) m/z [MꢀTFA]+ calcd. for C16H17BrIO3: 462.9400,
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4-methyl-3-nitrophenyl(2,4,6-trimethoxyphenyl)iodonium
trifluoroacetate
1t.
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Isolated as a yellow solid (0.444 g, 80%). HꢀNMR (400 MHz, DMSOꢀd6) δ (ppm): 8.51 (d, J =
1.9 Hz, 1H), 8.06 (dd, J1 = 8.2 Hz, J2 = 1.9 Hz, 1H), 7.58 (d, J = 8.7 Hz, 1H), 6.48 (s, 2H), 3.95
(s, 6H), 3.87 (s, 3H), 2.52 (s, 3H). 13C{1H}ꢀNMR (101 MHz, DMSOꢀd6) δ (ppm): 166.4, 159.4,
157.9 (q, JCꢀF = 30.7 Hz), 149.4, 138.1, 136.5, 135.4, 129.7, 117.3 (q, JCꢀF = 300.7 Hz), 112.8,
92.1, 87.6, 57.4, 56.2, 19.4. 19Fꢀ{1H}NMR (376 MHz, DMSOꢀd6) δ (ppm): ꢀ73.4. Spectral data
was in accordance with the literature.8
3-bromo-4-fluoro-6-methylphenyl(2,4,6-trimethoxyphenyl)iodonium trifluoroacetate 1u.
1
Isolated as a yellow solid (0.494 g, 83%). HꢀNMR (400 MHz, DMSOꢀd6) δ (ppm): 8.39 (d, J =
6.9 Hz, 1H), 7.60 (d, J = 9.9 Hz, 1H), 6.45 (s, 2H), 3.95 (s, 6H), 3.86 (s, 3H), 2.55 (s, 3H).
13C{1H}ꢀNMR (101 MHz, DMSOꢀd6) δ (ppm): 166.0, 160.1 (d, JCꢀF = 250.7 Hz), 159.3, 158.1 (q,
JCꢀF = 30.9 Hz), 143.5 (d, JCꢀF = 8.4 Hz), 140.9, 118.8 (d, JCꢀF = 23.5 Hz), 117.2 (q, JCꢀF = 300.4
Hz), 116.2 (d, JCꢀF = 3.5 Hz), 106.7 (d, JCꢀF = 22.1 Hz), 92.1, 87.8, 57.1, 56.1, 24.4. 19F{1H}ꢀNMR
(376 MHz, DMSOꢀd6) δ (ppm): ꢀ73.4, ꢀ102.9. FTꢀIR: 3096 (br), 3034 (br), 3000 (br), 2957 (br),
2852 (br), 1680 (m), 1594 (m), 1528 (m), 1345 (m), 1115 (s), 827 (s), 716 (m) cmꢀ1. HRꢀMS (EI)
+
m/z [MꢀTFA]+ calcd. for C16H16BrFIO3 : 480.9306, found: 480.9299. M.p. (Et2O): 164ꢀ165 °C.
2-chloropyridine(2,4,6-trimethoxyphenyl)iodonium trifluoroacetate 1v. Isolated as an offꢀ
1
white solid (0.220 g, 42%). HꢀNMR (400 MHz, DMSOꢀd6) δ (ppm): 8.87 (d, J = 2.1 Hz, 1H),
8.36 (dd, J1 = 8.5 Hz, J2 = 2.4 Hz, 1H), 7.64 (d, J = 8.5 Hz, 1H), 6.46 (s, 2H), 3.95 (s, 6H), 3.87
(s, 3H). 13C{1H}ꢀNMR (101 MHz, DMSOꢀd6) δ (ppm): 166.3, 159.3, 158.0 (q, JCꢀF = 30.9 Hz),
153.5, 152.6, 145.0, 127.4, 117.2 (d, JCꢀF = 300.4 Hz), 114.2, 92.1, 87.7, 57.3, 56.2. 19F{1H}ꢀ
NMR (376 MHz, DMSOꢀd6) δ (ppm): ꢀ73.5. Spectral data was in accordance with the literature.8
1,3-phenyl(2,4,6-trimethoxyphenyl)diiodonium bis-trifluoroacetate 1w. Deviation from
general procedure: mꢀCPBA (2.4 equiv.), TFA (2 equiv.), TMB (2 equiv.). Isolated as a white
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solid (0.800 g, 90%). 1HꢀNMR (400 MHz, DMSOꢀd6) δ (ppm): 8.20 (t, J = 1.6 Hz, 1H), 8.08 (dd,
J1 = 8.0 Hz, J2 = 1.6 Hz, 2H), 7.54 (t, J = 8.0 Hz, 1H), 6.48 (s, 4H), 3.90ꢀ3.88 (2s, 18H). 13C{1H}ꢀ
NMR (101 MHz, DMSOꢀd6) δ (ppm): 166.4, 159.4, 157.9 (q, JCꢀF = 30.7 Hz), 137.7, 136.6,
134.2, 117.5, 117.3 (q, JCꢀF = 300.8 Hz), 92.1, 87.5, 57.4, 56.2. 19F{1H}ꢀNMR (376 MHz, DMSOꢀ
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d6) δ (ppm): ꢀ73.4. FTꢀIR: 3079 (br), 2996 (br), 2956 (br), 2845 (br), 1663 (s), 1579 (s), 1348
2+
(m), 1164 (s), 1118 (s), 797 (m), 716 (s) cmꢀ1. HRꢀMS (EI) m/z [Mꢀ2TFA]2+ calcd. for C12H13IO3
:
331.9904, found: 331.9904. M.p. (Et2O): 189 °C.
1’,1-biphenyl-bis-(2,4,6-trimethoxyphenyl)diiodonium bis-trifluoroacetate 1x. Deviation
from general procedure: mꢀCPBA (2.4 equiv.), TFA (2 equiv.), TMB (2 equiv.). Isolated as an
offꢀwhite solid (0.730 g, 76%). 1HꢀNMR (400 MHz, DMSOꢀd6) δ (ppm): 7.98 (d, J = 8.6 Hz, 4H),
7.73 (q, J = 8.7 Hz, 4H), 6.48 (s, 4H), 3.95 (s, 12H), 3.87 (s, 6H). 13C{1H}ꢀNMR (101 MHz,
DMSOꢀd6) δ (ppm): 166.2, 159.4, 157.8 (q, JCꢀF = 30.6 Hz), 141.2, 137.9, 134.8, 129.9, 129.3 (q,
JCꢀF = 35.1 Hz), 117.3 (q, JCꢀF = 300.9 Hz), 116.0, 92.1, 87.3, 57.4, 56.2. 19F{1H}ꢀNMR (376 MHz,
DMSOꢀd6) δ (ppm): ꢀ73.4. FTꢀIR: 3080 (br), 2988 (br), 2954 (br), 2852 (br), 1676 (m), 1660 (m),
1583 (s), 1342 (m), 1162 (s), 1118 (s), 990 (s), 796 (s), 718 (s) cmꢀ1. HRꢀMS (EI) m/z [Mꢀ
2TFA]2+ calcd. for C15H15IO32+: 370.0060, found: 370.0060. M.p. (Et2O): 215 °C.
General procedure for unsymmetrical aryl(mesityl)iodonium trifluoroacetate synthesis
(1b-Mes and 1f-Mes). Aryl iodide (1 mmol, 1 equiv) and acetonitrile (1 mL) were added to a 5
mL vial, equipped with a magnetic stir bar. mꢀCPBA (1.2 mmol, 0.208 g, 1.2 equiv) was added
in one portion, followed by the dropꢀwise addition of TFA (1 mmol, 76 ꢁL, 1 equiv). After sealing
the tube with a screwꢀcap, the reaction was placed in an oil bath set to 77°C and stirred. After
50 min, 1,3,5ꢀtrimethylbenzene (1.5 mmol, 413ꢁL, 1.5 equiv) was added in one portion and the
mixture was stirred at 77°C for 22h. The postꢀreaction mixture was removed from the heat,
concentrated under reduced pressure and the crude residue was triturated with diethyl ether (10
mL). The solid was collected by vacuum filtration and washed by slurry filtration with diethyl
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ether (3 × 10 mL). After drying under reduced pressure the diaryliodonium salt was obtained in
analytically pure form.
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4-methylphenyl(2,4,6-trimethylphenyl)iodonium trifluoroacetate 1b-Mes. Isolated as a
white solid (0.255 g, 51%). 1HꢀNMR (400 MHz, CDCl3) δ (ppm): 7.55 (d, J = 8.4 Hz, 2H), 7.16 (d,
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J = 8.1 Hz, 2H), 7.05 (s, 2H), 2.63 (s, 6H), 2.34 (s, 3H), 2.32 (s, 3H). C{1H}ꢀNMR (101 MHz,
CDCl3) δ (ppm): 161.7 (q, JCꢀF = 34.0 Hz), 143.4, 142.0, 141.9, 133.0, 133.5, 130.0, 122.8, 116.5
(q, JCꢀF = 295.1 Hz), 110.9, 27.0, 21.3, 21.1. 19F{1H}ꢀNMR (376 MHz, CDCl3) δ (ppm): ꢀ75.3. FTꢀ
IR: 3058 (br), 3030 (br), 2990 (br), 2920 (br), 2864 (br), 1659 (s), 1453 (m), 1171 (s), 1124 (s),
824 (m), 797 (s), 715 (s) cmꢀ1. HRꢀMS (EI) m/z [MꢀTFA]+ calcd. for C16H18I+: 337.0448, found:
337.0448. M.p. (Et2O): 169ꢀ170 °C.
4-chlorophenyl(2,4,6-trimethylphenyl)iodonium trifluoroacetate 1f-Mes. Isolated as a white
solid (0.231 g, 49%). 1HꢀNMR (400 MHz, CDCl3) δ (ppm): 7.68 (d, J = 8.7 Hz, 2H), 7.33 (d, J =
8.7 Hz, 2H), 7.09 (s, 2H), 2.66 (s, 6H), 2.35 (s, 3H). 13C{1H}ꢀNMR (101 MHz, CDCl3) δ (ppm):
161.6 (q, JCꢀF = 34.3 Hz), 143.6, 141.8, 137.8, 134.4, 131.7, 130.0, 123.2, 116.4 (q, JCꢀF = 294.9
Hz), 112.1 (d, JCꢀF = 10.1 Hz), 27.0, 21.1. 19F{1H}ꢀNMR (376 MHz, CDCl3) δ (ppm): ꢀ75.4. FTꢀIR:
3082 (br), 3063 (br), 2981 (br), 2924 (br), 2868 (br), 1656 (s), 1469 (m), 1384 (m), 1186 (s),
1172 (s), 1125 (s), 1085 (s), 999 (s), 825 (s), 812 (s), 796 (s), 717 (s) cmꢀ1. HRꢀMS (EI) m/z [Mꢀ
TFA]+ calcd. for C15H15ClI+: 356.9902, found: 356.9904. M.p. (Et2O): 162ꢀ163 °C.
Corresponding Author
*Email: dstuart@pdx.edu
Notes
The authors declare no competing financial interest.
Acknowledgments
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We acknowledge Portland State University and the donors of the American Chemical Society
Petroleum Research Fund (PRF DNI1 #54405) for support of this research. V.C. is grateful to
Université Paul Sabatier (Toulouse III) and Bourse à la mobilité de la Région Languedoc
Roussillon Midi Pyrénées for financial support. A.H.S is grateful to Fulbright Norway for
financial support. Thomas Seidl is thanked for helpful discussion during the preparation of this
manuscript.
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Supporting Information
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Copies of 1H, C{1H}, F{1H} NMR spectra of all new compounds is provided. This material is
available free of charge via the Internet at http://pubs.acs.org
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7 For synthesis by counter anion exchange from a pre-formed diaryliodonium salt, see: Wagner, A. M.; Hickman, A.
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12 See the ESI for representative crude 1H and 19F NMR spectra.
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