Electrophilic Cyclization of Phenylalkynediols to Naphthyl(aryl)iodonium Triflates with Chelating Hydroxyls: Preparation and X-ray Analyses

Article abstract of DOI:10.1021/acs.joc.7b01619

Alkynediols containing one propargylic alcohol as well as a second alcohol, which is propargylic or homopropargylic, react with PhI⁺CN^-OTf (Stang's reagent) or 3,5-(CF₃)₂C₆H₃I⁺CN

Full text of DOI:10.1021/acs.joc.7b01619

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Article
Electrophilic Cyclization of Phenylalkynediols to Naphthyl(aryl)iodonium
Triflates with Chelating Hydroxyls: Preparation and X-ray Analyses
Robert James Hinkle, Sarah E. Bredenkamp, Robert David Pike, and Seong Ik Cheon
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.7b01619 • Publication Date (Web): 17 Aug 2017
Downloaded from http://pubs.acs.org on August 18, 2017
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Electrophilic Cyclization of Phenylalkynediols to Naphthyl(aryl)iodonium
Triflates with Chelating Hydroxyls: Preparation and X-ray Analyses
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*
†
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Robert J. Hinkle, Sarah E. Bredenkamp, Robert D. Pike and Seong Ik Cheon
Department of Chemistry, The College of William & Mary, P.O. Box 8795,
Williamsburg, Virginia 23187-8795, United States
rjhink@wm.edu
Abstract.
Alkynediols containing one propargylic alcohol as well as a second alcohol, which is
propargylic or homopropargylic, react with PhI+CN–OTf (Stang’s reagent) or 3,5ꢀ
(CF3)2C6H3I+CN–OTf to afford naphthyl(aryl)iodonium triflates. The reaction occurs at room
temperature over the course of 6ꢀ12 hours and provides 36ꢀ82% yields of microcrystalline solids.
Slow diffusion of Et2O into CH3CN solutions of the salts afforded Xꢀray quality crystals of five
compounds with hydroxyl groups forming fiveꢀ and sixꢀmembered chelation complexes with the
iodine atom. Crystallizations from larger scale reactions (≥ ~ 0.25 mmol) were generally facile
from CH2Cl2.
†
Detailed questions about X-ray structure analyses should be directed to Robert D. Pike, PhD, Department of
Chemistry, The College of William & Mary; rdpike@wm.edu.
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Introduction.
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Hypervalent iodine compounds are used extensively in many forms of organic and
polymer chemistry.1 DessꢀMartin periodinane2 is, perhaps, the most widelyꢀrecognized I(V)
compound whereas phenyliodine(III) diacetate (PIDA)3 and phenyliodine bis(trifluoroacetate)
(PIFA)4 are among the most recognized I(III) compounds. Many other derivatives, however, are
also known.1,5 Both PIDA and PIFA have been used extensively in a variety of reactions,
including CꢀH activation.6 Alkenyl, heteroaryl, and diaryl7 iodonium salts can be used for
alkenylations,8 crossꢀcoupling reactions,9 αꢀarylations of carbonyl compounds,10
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functionalization of indoles,11 and a host of other reactions.1 Typical syntheses of diaryl
iodonium salts include: (a) reactions of bis(acetoxy)iodoarenes, with TfOH in the presence of a
second aromatic compound to afford mixed diaryl salts;12 (b) reactions of arylboronic acids and
aryl iodides with mCPBA and acids;13 and (c) reactions of elemental iodine or aryl iodides with
aromatic compounds in the presence of strong oxidants.14 Stang and coꢀworkers developed a
particularly mild iodonium−transfer reagent, (PhI+CN–OTf),15 which is sometimes called
“Stang’s reagent.” This I(III) electrophile is generally used to convert aryl, alkynyl,15,16 or
alkenyl stannanes17 to the corresponding iodonium salts (eq 1), but has also been used to initiate
Pummererꢀlike rearrangements in the synthesis of alkaloids;18 analogs have also been used for
additions across alkynes19 and the synthesis of thiocyanates.20
In the course of developing a domino21 reaction involving an alkynylꢀPrins/Friedelꢀ
Crafts/aromatization cascade, we envisioned that Stang’s reagent might react with alkynediols
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containing one propargylic and one homopropargylic alcohol.22 Herein we report that Stang’s
reagent as well as the 3,5ꢀbis(CF3)phenyl analog can be used to synthesize naphthyl(aryl)ꢀ
iodonium triflate salts from alkyne diols in which at least one hydroxyl moiety is propargylic.
This represents a new and surprisingly efficient cyclizationꢀaromatization method for the
synthesis of novel naphthyl(aryl)iodonium salts.23
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Results and Discussion.
We initially reacted 1 equiv of Stang’s reagent (PhI+CN–OTf) with 6ꢀphenylhexꢀ3ꢀyneꢀ
1,5ꢀdiol 1a in CD3CN at room temperature. The reaction immediately began to turn light yellow
and then became darker over time. 1H NMR spectroscopic analyses (Fig. 1) over the course of 10
h clearly showed depletion of Stang’s reagent by disappearance of the orthoꢀhydrogen resonance
at 8.32 ppm and appearance of a much more complex series of resonances in the aromatic region,
the most downfield of which appeared at 8.26 ppm. The fact that the new resonance was still
below 8 ppm implied that a different iodonium salt had formed. Two new resonances also
appeared at 3.7 and 3.9 ppm while the two sets of methylene resonances of starting alkynediol 1a
(6ꢀphenylhexꢀ3ꢀyneꢀ1,5ꢀdiol) at 2.4 and 2.9 ppm decreased. With 1 equiv of Stang’s, however,
some starting alkynediol remained; subsequent analyses showed that between 1.2ꢀ1.3 equiv of
Stang’s reagent was required to completely consume the starting alkynediol in acetonitrile.
The resulting microcrystalline solid could be precipitated from solution by addition of Et2O with
rapid stirring at room temperature. Slow diffusion of Et2O into a CD3CN NMR sample afforded
Xꢀray quality crystals, one of which was analyzed to reveal a naphthyl(phenyl)iodonium salt
(Fig. 2). Interestingly, the homopropargylic alcohol was still intact as shown in the
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Figure 1. Timeꢀarrayed 1H NMR spectra of reaction between Stang’s reagent and 1.0 equiv diol 1a. The
first spectrum was recorded at 10 min in CD3CN at rt and another spectrum taken every hour. The final
spectrum was recorded at 10h.
Xꢀray structure and 1H NMR spectrum, but it was coordinated to the iodine atom in a sixꢀ
membered ring chelate. To the best of our knowledge, no other crystal structures of compounds
with a simple, pendant hydroxyl moiety coordinated directly to an I(III) center have been
reported, although a number of other coordinating groups have been reported.1,24 The closestꢀ
contact triflate counterion in 2a (shown) appears in the neighboring unit cell and the hydroxyl
hydrogen was located during data acquisition (see supporting information).
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Figure 2. ORTEP representation of naphthyl(phenyl)iodonium triflate 2a. Thermal elipsoids are shown at
the 50% probability level. Selected bond distances and angles: I1ꢀC1 2.116(2) Å, I1ꢀC13 2.111(2) Å, I1ꢀ
O1 2.7645(17) Å, I1ꢀO4 2.9295(16) Å; C1ꢀI1ꢀC13 95.76(9) o, C1ꢀI1ꢀO1 78.83(7) o, C13ꢀI1ꢀO4 173.76(7)
o. The closestꢀcontact triflate ion is shown whereas the triflate within the same unit cell as the cationic
core was omitted for clarity.
We then performed the reaction with alkynediols 1b ꢀ 1d (eq 2) and found that the same
electrophilic cyclization, dehydration/aromatization process occurred to form fiveꢀ as well as sixꢀ
membered hydroxylꢀcoordinated naphthyl(aryl)iodonium salts 2b-2d, as shown in eq 2 and
Table 1. Alkynediol 1e, which would have led to a sevenꢀmembered chelation product only led
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to rapid decomposition. A final salt was synthesized by reaction of alkynediol 1a with the 3,5ꢀ
bis(trifluoromethyl)phenyl analog of Stang’s reagent15 to afford salt 2e.
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While we were able to isolate 2a-2e from reactions run in CH3CN, rapid addition of Et2O
solvent frequently led to oils rather than solids. We later found that isolation was far more
efficient if the reactions were run in CH2Cl2 for 6ꢀ12 hours followed by addition of Et2O and nꢀ
hexane. Although Stang’s reagent is only sparingly soluble in CH2Cl2, the reactions did become
homogeneous as the reactions progressed. In a direct comparison of different reactions in the two
solvents, salt 2b was isolated in 46% yield from CH3CN whereas it was obtained in 72% yield
from CH2Cl2 on a 0.28 mmol scale. Isolation from DCM was facile in all cases except for the
isopropylꢀsubstituted 5ꢀring chelate, 2d. In this particular example, the reaction in CH2Cl2 was
not nearly as clean as the others and the product was also more soluble in Et2O.
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Salts 2a-2e were fullyꢀcharacterized by 1H, 13C and 19F NMR spectroscopy as well as
high resolution mass spectrometry. The aromatic regions of 1H NMR spectra for 2a-2e were
surprisingly complex because of overlapping resonances with varying coupling constants. This
phenomenon is likely due to restricted rotation about the iodineꢀaryl bonds making positions on
the phenyl moiety diastereotopic.
All salts were also analyzed by Xꢀray diffraction25 of crystals grown by slow diffusion of
Et2O into CD3CN solutions at rt. The resulting crystallographic data displayed R1 values (Table
1, row 2) between 0.0142 and 0.0490, with the largest value resulting from analysis of 2e, which
contained three different CF3 moieties. The bond lengths for all I–C bonds in 2aꢀ2e are
remarkably consistent at 2.10–2.14 Å (Table 1, rows 3ꢀ4).
As with most iodonium salts, the crystal structure of 2a reveals a distorted Tꢀshape, but in
2a-2e, the coordination involves a hydroxyl, naphthyl, and phenyl moieties around the iodine(III)
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Table 1. Yields, analytical data and structural features of iodonium salts 2a-2e.
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OTf
CF3
OTf
OTf
OTf
OTf
i-Pr
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I
O
I
O
I
I
O
H
O
I
O
H
H
H
H
CF3
2a
2b
2c
2d
2e
Row
Compound
Mp (oC)
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2b
2c
2d
2e
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3a
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0.0205
125-131
0.0142
150-153
0.0147
193-196
0.0178
125-129
0.0490
X-ray data, R1
I-Cnaphth, (Å)
2.116(2)
2.1410(15)
2.1309(16)
2.1070(16)
95.48(6)
2.1341(16)
2.129(6)
4b
5 a,b
6a
I-CAr, (Å)
2.111(2)
95.76(9)
78.83(7)
2.1041(15)
95.08(6)
2.1002(16)
95.20(6)
2.124(4)
95.1(2)
Cnaphth-I-CAr (o)
HO-I-Cnaphth (o)
HO-I-CAr (o)
I-OH, Å
71.78(5)
72.47(5)
72.23(5)
77.92(18)
171.37(17)
2.691(5)
2.759(5)
-0.238(8)
7b
173.76(7)
2.7645(17)
2.9295(16)
0.149(3)
166.08(5)
2.6164(11)
3.0143(12)
0.203(2)
166.17(5)
2.5953(12)
2.9330(12)
0.299(2)
158.66(5)
2.6046(12)
2.9660(13)
-0.751(2)
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I-OTf, Å
10b
HO-planeCIC (Å)
a Cnaphth indicates the carbon on the naphthyl moiety to which the iodine atom is attached.
b CAr indicates the carbon on the phenyl or 3,5-bis(trifluoromethyl)phenyl moiety to which the iodine is
attached.
c Deviation of hydroxylic oxygen from least-squares plane defined by the iodine-bonded aromatic carbons
and iodine.
center.1 If one also considers the triflate counterꢀion, however, the geometry is approximately
square planar around the iodine. The Cnapth–I– CPh bond angle of 2a (Table 1, row 5) is 95.76(9)
o, which is similar to bond angles typical of other diaryl salts (ca. 90 o)1 as well as
alkenyl(aryl)iodonium triflates we reported.26 There is little deviation from this angle in any of
the other structures.
The HO–I–Cnapth bond angle (Table 1, row 6) is, however, reduced from ca. 79 o in 2a to
near 72 o in the fiveꢀmembered hydroxylꢀchelated structures 2b-d because of geometric
constraints. As might be expected, the HO–I–CPh angle (row 7) also decreases from a nearly
linear relationship of approximately 174 o for 2a and 171 o for 2e to a low of 158 o for 2d.
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For 2a, the chelated hydroxyl revealed an I–OH interaction of 2.7645(17) Å (Table 1,
row 8), but the fiveꢀmembered ring chelated structures 2bꢀ2d had I–OH distances that were
significantly shorter, ranging from approximately 2.60 to 2.62 Å.
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For most iodonium salts, the I–O distances between the iodine atom and anion range
from 2.3ꢀ2.7 Å1 and in alkenyl(aryl)iodonium triflates we reported,26 the I–OTf distances ranged
from 2.77 to 2.91 Å. In 2aꢀ2e, the I–OTf distances of 2.76ꢀ3.01 Å (Table 1, row 9), were similar
to the alkenyl(aryl)iodonium triflates, with the most electronꢀdeficient salt, 2e, displaying the
shortest of the IꢀOTf interactions. All of these IꢀO distances are, however, wellꢀwithin the 3.5 Å
sum of the van der Waals radii for iodine and oxygen.27 Other heterocyclic, fiveꢀmembered ring
systems such as those described by Togni and coꢀworkers contain much shorter (2.1176(14) Å)
covalent bonds between oxygen and iodine.28
We also used the iodine and ipso carbons of both the aryl and naphthyl moieties to define
a plane and calculated how much the hydroxyl oxygen deviated from that plane (Table 1, row
10). The isopropylꢀsubstituted salt, 2d, showed the greatest deviation from the plane at 0.751(2)
Å and this is surely the result of steric congestion.
A proposed mechanism for this new electrophilic cyclization to naphthyl(aryl)iodonium
salts is shown in Scheme 1. The I–OTf interaction is largely ionic leaving [Ph–I+–CN] as the
electrophile that the alkyne πꢀelectrons attack to generate an incipient alkenyl cation.
Coordination with either of the two hydroxyls could assist in initial delivery of the alkyne to the
electrophile. Coordination would also assist in departure of cyanide, which does not appear in
any of the Xꢀray structures. Attack of the pendant phenyl would then afford an arenium ion that
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Scheme 1. Proposed mechanism for electrophilic cyclization of alkynediols.
would reꢀaromatize. Subsequent protonation of the propargylic hydroxyl by HCN and final
dehydration would afford the second ring of the naphthyl moiety and generate the observed salts
with H2O and HCN as byproducts. The hypothesis that hydroxyl coordination assists in the
reaction is supported by the fact that decomposition occurred almost instantaneously when
Stang’s reagent was reacted with 1ꢀphenylheptꢀ3ꢀyneꢀ2,7ꢀdiol 1e, which would form a sevenꢀ
membered chelate rather than the fiveꢀ or sixꢀmembered chelates observed.
Conclusions.
We have discovered that alkynediols containing a tethered phenyl moiety react with
Stang’s reagent (PhI+CN–OTf) or the bis(trifluoromethyl)phenyl analog to form
naphthyl(aryl)iodonium triflate compounds. The reaction occurs over the course of 6ꢀ12 hours at
room temperature by initial attack of the alkyne on the electrophilic, hypervalent iodine center.
Subsequent FriedelꢀCrafts reaction and dehydration then afford the majority of salts in greater
than 70% yield. This reaction represents a novel reaction manifold for Stang’s reagent(s) and a
new method for synthesizing unsymmetric diaryliodonium salts.
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Experimental
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Materials and Methods. All reactions were carried out under argon gas unless otherwise noted.
Dichloromethane and CH3CN were distilled from CaH2. Flash column chromatography was
performed on silica gel (200ꢀ400 mesh). Thin layer chromatography was conducted using
generalꢀpurpose silica gel TLC plates on glass. Visualization was accomplished with UV light or
by heating plates dipped in cerium ammonium molybdate (CAM) or basic potassium
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permanganate staining solutions. Fourier transform infrared (FTꢀIR) spectra were recorded as
ATR samples on an FTIR spectrophotometer. 1H NMR spectra were recorded at 400 MHz and
are reported in ppm using solvent or TMS as internal standards. When a resonance appears as a
simplified splitting pattern, “app” is used as an abbreviation for “apparent.” 19F NMR spectra
were recorded at 376 MHz using CFCl3 as an external standard (0.0 ppm). Protonꢀdecoupled 13Cꢀ
NMR spectra (attached proton test) were recorded at 100 MHz and are reported in ppm using
solvent or TMS as internal standards. Quaternary (C) and methylene (CH2) carbons, which are
positive in the apt spectra, are listed as (e), whereas methine (CH) and methyl carbons (CH3) are
listed as (o). All HRMS analyses were obtained using positiveꢀion mode electrospray ionization.
XꢀRay quality crystals of naphthyl(aryl)iodonium triflates 2aꢀ2e were obtained by slow
diffusion of Et2O into CD3CN solutions of the corresponding salts at room temperature. Details
of the Xꢀray experiments and crystal data are summarized in the supporting information (CIF
files). Selected bond lengths and bond angles are given in Table 1. Crystallographic data for the
structures reported herein have been deposited with the Cambridge Crystallographic Data Centre
and allocated the deposition numbers CCDC 1559387ꢀ1559391. These data can be obtained free
of charge from the Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif.
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General Procedure; preparation of 6-Phenylhex-3-yne-1,5-diol (1a). 3ꢀButyneꢀ1ꢀol (5.40 mL,
71.3 mmol) was dissolved in dry THF (100 mL), the solution cooled to ꢀ78 oC, and nꢀBuLi (2.5
M, 57 mL, 144 mmol) added dropwise to afford a suspension. The resulting suspension was
stirred for 45 minutes and phenylacetaldehyde (8.10 mL, 69.4 mmol) was added dropwise via
syringe. The cold bath was removed and the solution allowed to warm for 1 h. The reaction was
quenched with NH4Claq (50 mL). The reaction mixture was extracted with Et2O (3 x 50 mL), the
organic portion dried (MgSO4) and concentrated in vacuo. The diol was then purified by column
chromatography using gradient elution of hexanes/EtOAc (1/1 ꢀ 2/3) to afford 5.79g (43%) of the
diol as a viscous, light yellow oil that solidified upon standing: mp = 51ꢀ53 oC; Rf = 0.30 (1/1
hexanes/EtOAc); IR (ATR) 3240 (s), 2941 (w), 2918 (w), 1493 (m), 1175 (s), 1136 (s), 1055
(vs), 1020 (vs) cmꢀ1; 1H NMR (400 MHz, CDCl3) δ = 7.22ꢀ7.32 (m, 5H), 4.55 (td, J = 5.8, 1.8 Hz,
1H), 3.64 (t, J = 6.4 Hz, 2H), 2.97 (d, J = 6.4 Hz, 2H), 2.42 (td, J = 6.0, 1.8 Hz, 2H); 13C{1H} (apt)
NMR (100 MHz, CDCl3) δ = 137.07 and 137.06 (e, diastereomeric pair), 129.9 (o), 128.6 (o), 127.1
(o), 83.4 (e), 82.6 (e), 63.5 (o), 61.0 (e), 44.4 (e), 23.2 (e); HRMS (ESI) for sodiumꢀbound dimer
m/z [2xM+Na]+ calcd for C24H28O4Na: 403.1874; found: 403.1878.
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5-phenylpent-2-yne-1,4-diol (1b). This known29 alkynediol was made according to the general
procedure with propargyl alcohol (3.0 mL, 55.3 mmol) and phenylacetaldehyde (6.5 mL, 55.3
mol). The diol was then purified by column chromatography using hexanes/EtOAc (1/1) as
eluent to afford 3.73 g (38%) of the diol as a light yellow oil that solidified upon standing: mp =
53ꢀ55 oC; Rf = 0.28 (1/1 hexanes/EtOAc; IR (ATR) 3238 (s), 2941 (w), 2918 (w), 1493 (m),
1175 (s), 1136 (s), 1055 (vs), 1020 (v)s cmꢀ1; 1H NMR (400 MHz, CDCl3) δ = 7.22ꢀ7.34 (m,
5H), 4.58 (br s, 1H), 4.21 (br s, 2H), 2.98 (d, J = 6.4Hz, 2H); 13C{1H} (apt) NMR (100 MHz,
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CDCl3) δ = 136.8 (e), 129.9 (o), 128.6 (o), 127.1 (o), 86.2 (e), 84.1 (e), 63.3 (o), 50.9 (e), 44.1
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(e).
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1-Phenylhex-3-yne-2,5-diol (1c). This known compound30 was prepared by the general method
from 3ꢀbutyneꢀ2ꢀol (3.2g, 45.5 mmol), nꢀBuꢀLi (36.4 mL, 91.1mmol) and phenylacetaldehyde
(4.8 mL, 41.0 mmol). Chromatographic purification using hexanes/EtOAc (1/1) afforded 4.58 g
(52.9%) of 1c as a light yellow oil which contained a mixture of diastereomers: Rf = 0.37 (1/1
hexanes/EtOAc); IR (ATR) 3316 (m), 3030 (w), 2984 (w), 2932 (w), 1667 (w), 1371 (m), 1454
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(m), 1144 (s), 1079 (w), 1030 (vs), cmꢀ1; H NMR (400 MHz, CDCl3) δ = 7.18ꢀ7.31 (m, 5H),
4.52 (ddd, J = 6.4Hz, 6.2Hz, 1.2Hz, 1H), 4.45 (dq, J = 6.4Hz, 6.8Hz, 1H), 3.55 (br s, 1H), 2.94
13
(d, J = 6.4Hz, 2H), 1.36 (d, J = 6.4Hz, 1.5H), 1.35 (d, J = 6.8Hz, 1.5H); C{1H} (apt) NMR
(100 MHz, CDCl3) δ = 136.8 (e), 130.0 (o), 128.6 (o), 127.1 (o), 87.9 (e), 84.6 (e), 63.3 (o), 58.4
(o), 44.18 (e), 44.15 (e), 24.29 (o), 24.27 (o); HRMS (ESI) m/z [M+Na]+ calcd for C12H14O2Na:
213.0886; found: 213.0884
6-Methyl-1-phenylhept-3-yne-2,5-diol (1d). The title compound was isolated as a byproduct of
the synthesis of 6ꢀmethylꢀ1ꢀphenylheptꢀ3ꢀyneꢀ2,6ꢀdiol according to the published method22 with
1ꢀphenylꢀ3ꢀbutyneꢀ2ꢀol (3.11 g, 21.3 mmol), nꢀBuLi (17.9 mL, 44.7 mmol) and isobutylene
oxide (4.00 mL, 32.8 mmol). The diol was then isolated by column chromatography using
hexanes/EtOAc (1/1) as eluent to afford 0.49 g (11%) of the diol as a light yellow oil: Rf = 0.47
(1/1 hexanes/EtOAc); IR (ATR) 3335 (m), 2961 (m), 2926 (m), 1705 (m), 1497 (m), 1250 (w),
1142 (w), 1028 (vs) cmꢀ1. 1H NMR (400 MHz, CD3CN) δ = 7.25ꢀ7.35 (m, 4H), 7.19ꢀ7.24 (m,
1H), 4.51 (br s, 1H), 4.02ꢀ4.08 (m, 1H), 3.32ꢀ3.41 (m, 1H), 3.14 (br s, 1H), 2.93 (dd, J = 13.2,
6.8 Hz, 1H), 2.88 (dd, J = 12.8, 7.2 Hz, 1H), 1.66ꢀ1.77 (m, 1H), 0.89 (dd, J = 6.6, 1.2 Hz, 3H),
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0.89 (d, J = 6.4Hz, 3H). 13C{1H} (apt) NMR (100 MHz, CD3CN) δ = 139.1 (e), 131.1 (o) 129.4
5
(o), 127.8(o), 87.1 (e), 87.0 (e), 86.3 (e), 86.3 (e), 68.2 (o), 64.0 (o), 45.47 (e), 45.45 (e), 35.8 (o),
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18.8 (o), 18.2 (o). HRMS (
ESI) m/z [M+Na]+ calcd for C14H18O2Na: 241.1199; found: 241.1198.
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7-Phenylhept-4-yne-1,6-diol (1e). The title compound was prepared according to the general
procedure with 4ꢀpentyneꢀ1ꢀol (5.93 g, 70.5 mmol) and phenylacetaldehyde (8.60 mL, 73.5 mol)
added dropwise via syringe. The diol was then purified by column chromatography using
hexanes/EtOAc (1/1) as eluent to afford 4.81 g (33%) of the diol as a light yellow oil, which is a
mixture of diastereomers: Rf = 0.33 (1/1 hexanes/EtOAc); IR (ATR) 3333 (m), 2943 (w), 2879
(w), 1496 (m), 1453 (m), 1077 (m), 1030 (vs) cmꢀ1; 1H NMR (400 MHz, CDCl3) δ = 7.20ꢀ7.32
(m, 5H), 4.52 (tt, J = 6.6, 2.0, Hz, 1H), 3.62 (t, J = 6.2 Hz, 2H), 2.94 (d, J = 6.6 Hz, 2H), 2.80ꢀ
3.02 (br s, 2H), 2.28 (dt, J = 6.2, 2.0 Hz, 2H), 1.67 (quintet, J = 6.2 Hz, 2H); 13C{1H} (apt)
NMR (100 MHz, CDCl3) δ = 137.2 (e), 130.0 (o), 128.6 (o), 127.0 (o), 85.8 (e), 81.6 (e), 63.6
(o), 61.8 (e), 44.7 (e), 31.4 (e), 15.5 (e); HRMS (ESI) m/z [M+Na]+ calcd for C13H16O2Na:
:
227.1043; found: 227.1041.
General Procedure for Preparation of Naphthyl(aryl)iodonium Triflates. (1-(2-
Hydroxyethyl)naphthalen-2-yl)(phenyl)iodonium trifluoromethanesulfonate (2a). 6ꢀ
Phenylhexꢀ3ꢀyneꢀ1,5ꢀdiol 1a (50 mg, 0.26 mmol) was dissolved in CH2Cl2 and Stang’s reagent
(132 mg, 0.35 mmol) was added. After stirring at rt overnight, the product was precipitated by
slowly adding 5 mL Et2O followed by 2 mL nꢀhexane to the CH2Cl2 solution, then cooling in
freezer for 48 h. Isolation by vacuum filtration afforded 81 mg (82%) of 2a as an offꢀwhite
microcrystalline solid: mp = 118ꢀ120 oC; IR (ATR) 3374 (m), 3094 (w), 2916 (w), 2880 (w),
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1231 (vs), 1221 (vs), 1161 (vs), 1022 (vs) cmꢀ1; 1H NMR (400 MHz, CD3CN) δ = 8.22ꢀ8.30 (m,
1H), 8.10ꢀ8.15 (m, 2H), 7.94ꢀ8.01 (m, 1H), 7.80 (d, J = 9.2 Hz, 1H), 7.70ꢀ7.77 (m, 3H), 7.68 (d,
J = 9.2 Hz, 1H), 7.56 (app tt, J = 8.1, 2.0 Hz, 2H), 4.15 (t, J = 4.1 Hz, 1H), 3.88 (dt, J = 5.5, 4.1
Hz, 2H), 3.73 (t, J = 5.5 Hz, 2H); 19F NMR (376 MHz, CD3CN) δ = −78.05; 13C{1H} (apt) NMR
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(100 MHz, CD3CN) δ = 141.2 (e), 137.4 (o), 136.1 (e), 134.3 (o), 133.6 (e), 133.4 (o), 132.7 (o),
130.5 (o), 130.4 (o), 130.2 (o), 129.9 (o), 126.6 (o), 120.4 (e), 115.7 (e), 62.7 (e), 38.5 (e);
HRMS (ESI) m/z [MꢀOTf]+ calcd for C18H16IO: 375.0240; found: 375.0234.
(1-(Hydroxymethyl)naphthalen-2-yl)(phenyl)iodonium trifluoromethanesulfonate (2b). 5ꢀ
Phenylꢀ2ꢀpentyneꢀ1,4ꢀdiol 1b (51 mg, 0.29 mmol) was dissolved in CH2Cl2 and Stang’s reagent
(146 mg, 0.38 mmol) was added. After stirring at rt for 8 h, the product was precipitated by
slowly adding 8 mL Et2O to the CH2Cl2 solution. Isolation by vacuum filtration afforded 112 mg
(76%) of 2b as an offꢀwhite microcrystalline solid: mp = 125ꢀ131 oC; IR (ATR) 3242 (m), 1277
(vs), 1234 (vs), 1221 (vs), 1163 (vs), 1022 (vs) cmꢀ1; 1H NMR (400 MHz, CD3CN) δ = 8.15 (m,
2H), 8.01ꢀ8.08 (m, 1H), 7.95ꢀ8.01 (m, 1H), 7.88 (app tt, J = 7.8 Hz, 1.3 Hz, 1H), 7.81 (d, J = 9.2
Hz, 1H), 7.70ꢀ7.75 (m, 2H), 7.67 (app tt, J = 7.8 Hz, 1.7 Hz, 2H), 7.06 (d, J = 9.2 Hz, 1H), 5.60
(br quintet, J = 5.1 Hz, 1H), 5.49 (d, J = 5.1 Hz, 2H); 19F NMR (376 MHz, CD3CN) δ = −78.10;
13C{1H} (apt) NMR (100 MHz, CD3CN) δ = 139.3 (o), 137.8 (e), 135.1 (o), 135.0 (e), 133.9 (o),
132.9 (o), 132.8 (e), 130.3 (o), 130.1 (o), 129.7 (o), 126.4 (o), 124.4 (o), 111.8 (e), 109.4 (e),
62.5 (e); HRMS (ESI) m/z [MꢀOTf]+ calcd for C17H14IO: 361.0084; found: 361.0079.
(1-(1-Hydroxyethyl)naphthalen-2-yl)(phenyl)iodonium trifluoromethanesulfonate (2c). 1ꢀ
Phenylhexꢀ3ꢀyneꢀ2,5ꢀdiol 1c (51 mg, 0.27 mmol) was dissolved in CH2Cl2 and Stang’s reagent
(132 mg, 0.35 mmol) added. After stirring at rt overnight, the product was precipitated by slowly
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adding 10 mL Et2O followed by 8 mL nꢀhexane to the CH2Cl2 solution, then cooling in the
freezer for 48 h. Isolation by vacuum filtration afforded 81 mg (80%) of 2c as an offꢀwhite
microcrystalline solid: mp = 150ꢀ153 oC; IR (ATR) 3254 (m), 3084 (w), 2980 (w), 2928 (w),
1229 (vs), 1219 (vs), 1163 (vs), 1022 (vs) cmꢀ1; 1H NMR (400 MHz, CD3CN) δ = 8.16 (dd, J =
8.1, 1.2 Hz, 2H), 8.07 (d, J = 8.1 Hz, 1H), 7.96 (dd, J = 6.2, 2.4 Hz, 1H), 7.88 (t, J = 7.6 Hz, 1H),
7.77 (d, J = 9.0, 1H), 7.63ꢀ7.74 (m, 4H), 6.96 (d, J = 9.0, 1H), 5.98ꢀ6.11 (overlapping br s, 1H; q,
J = 6.7 Hz, 1H), 1.69 (d, J = 6.7 Hz, 3H); 19F NMR (376 MHz, CD3CN) δ = −78.09; 13C{1H}
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(apt) NMR (100 MHz, CD3CN) δ
= 141.6 (e), 139.5 (o), 135.1 (e), 135.1 (o), 133.8 (o), 132.9
(o), 132.5 (e), 130.4 (o), 129.8 (o), 129.7 (o), 125.9 (o), 124.5 (o), 112.0 (e), 107.4 (e), 68.6 (o),
22.9 (o); HRMS (ESI) m/z [MꢀOTf]+ calcd for C18H16IO: 375.0240; found: 375.0236.
(1-(1-Hydroxy-2-methylpropyl)naphthalen-2-yl)(phenyl)iodonium trifluoromethane-
sulfonate (2d). 6ꢀMethylꢀ1ꢀphenylheptꢀ3ꢀyneꢀ2,5ꢀdiol 1d (50 mg, 0.23 mmol) was dissolved in
CH2Cl2 and Stang’s reagent (109 mg, 0.29 mmol) was added. After stirring at rt overnight, the
product was precipitated by slowly adding 5 mL Et2O followed by 2 mL nꢀhexane to the CH2Cl2
solution. Isolation by vacuum filtration afforded 41 mg (36%) of 2d as an offꢀwhite
microcrystalline solid: mp = 193ꢀ196 oC; IR (ATR) 3227 (w), 2965 (w), 2932 (w), 2876 (w),
1229 (vs), 1219 (vs), 1161 (vs), 1022 (vs) cmꢀ1. 1H NMR (400 MHz, CD3CN) δ = 8.16ꢀ8.19 (m,
2H), 8.08ꢀ8.13 (m, 1H), 7.93ꢀ8.00 (m, 1H), 7.90 (app tt, J = 7.5 Hz, 1.2 Hz, 1H), 7.81 (d, J = 9.2
Hz, 1H), 7.66ꢀ7.74 (m, 4H), 6.98 (d, J = 9.2 Hz, 1H), 5.97 (d, J = 5.1 Hz, 1H), 5.74 (dd, J = 5.1,
4.7 Hz, 1H), 2.40 (app dsept, J = 6.6, 4.7 Hz, 1H), 1.094 (d, J = 6.6 Hz, 3H), 1.092 (d, J = 6.6
Hz, 3H). 19F NMR (376 MHz, CD3CN) δ = −78.10; 13C{1H} (apt) NMR (100 MHz, CD3CN) δ =
140.0 (e), 139.6 (o), 135.2 (e), 135.2 (o), 133.9 (o), 133.5 (e), 133.0 (o), 130.4 (o), 129.8 (o),
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129.5 (o), 125.9 (o), 125.2 (o), 111.6 (e), 108.8 (e), 76.0 (o), 35.7 (o), 20.7 (o), 17.6 (o); HRMS
(ESI) m/z [MꢀOTf ]+ calcd for C20H20IO: 403.0553; found: 403. 0547.
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(3,5-bis(trifluoromethyl)phenyl)(1-(2-hydroxyethyl)naphthalen-2-yl)iodonium
trifluoromethanesulfonate (2e). 6ꢀPhenylhexꢀ3ꢀyneꢀ1,5ꢀdiol 1a (27 mg, 0.14 mmol) was
dissolved in CD3CN and (3,5ꢀbis(trifluoromethyl)phenyl)(cyano)ꢀλ3ꢀiodanyl
trifluoromethanesulfonate (87 mg, 0.17 mmol) added. After stirring at rt overnight, Et2O was
added to the sample to induce crystallization. The solid was then dissolved in CH2Cl2 and Et2O
added to produce a solid. Isolation by vacuum filtration afforded 57 mg (62%) of 2e as an offꢀ
white microcrystalline solid: mp = 125ꢀ129 oC; IR (ATR) 3362 (w), 3075 (w), 2965 (w), 2897
(w), 1275 (vs), 1248 (vs), 1165 (vs), 1130 (vs), 1028 (vs) cmꢀ1; 1H NMR (400 MHz, CD3CN) δ =
8.71 (s, 2H), 8.35 (s, 1H), 8.27ꢀ8.33 (m, 1H), 7.99ꢀ8.06 (m, 1H), 7.85 (d, J = 9.0 Hz, 1H), 7.72ꢀ
7.79 (m, 2H), 7.68 (d, J = 9.0 Hz, 1H), 4.35 (t, J = 4.1 Hz, 1H), 3.90 (dt, J = 5.5, 4.1 Hz, 2H),
3.77 (t, J = 5.5 Hz, 2H); 19F NMR (376 MHz, CD3CN) δ = −78.13; 13C{1H} (apt) NMR (100
MHz, CD3CN) δ = 141.7 (e), 138.1 (o; mult), 136.3 (e), 135.0 (e; q, JCF = 35 Hz), 133.5 (e),
133.0 (o), 130.7 (o), 130.6 (o), 130.5 (o), 130.1 (o), 128.4 (o; m), 126.7 (o), 123.7 (e; q, JCF
=
273 Hz), 122.4 (e; q, JCF = 320 Hz), 121.1 (e), 116.3 (e), 62.8 (e), 38.3 (e); HRMS (ESI) m/z [Mꢀ
OTf]+ calcd for C20H14F6OI: 510.9988; found: 510.9984.
AUTHOR INFORMATION
Corresponding Author
*Eꢀmail: rjhink@wm.edu
Notes
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The authors declare no competing financial interest.
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ACKNOWLEDGMENTS
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We thank the National Science Foundation for direct support of this work (CHEꢀ1012305) as
well as for funding the purchase of the NMR spectrometer (MRIꢀ1337295) and Xꢀray
diffractometer (CHEꢀ0443345). We also thank Daniel J. Speer for recording analytical data.
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Supporting Information
The Supporting information is available free of charge on the ACS Publications website at DOI:
XXXXacs.joc.XXX.
Characterization data, including 1H and 13C APT spectra, for alkynediols 1a–1d as well as
all naphthyl(aryl)iodonium products 2a–2e.
ORTEPS for naphthyl(aryl)iodonium products 2a–2e Xꢀray as well as crystallographic
details (CIF).
Notes and References.
1 A number of review articles have appeared outlining the preparation and uses of hypervalent iodine
compounds: (a) Yoshimura, A.; Zhdankin, V. V. Chem. Rev. 2016, 116, 3328. (b) Yusubov, M. S.; Maskaev,
A. V.; Zhdankin, V. V. ARKIVOC 2011, i, 370. (c) Zhdankin, V. V.; Stang, P. J. Chem. Rev. 2008, 108, 5299.
(d) Stang, P. J.; Zhdankin, V. V. Chem. Rev. 1996, 96, 1123.
2
Dess-Martin periodinane is widely available from commercial sources. Dess, D. B.; Martin, J. C. J. Org.
Chem. 1983, 48, 4155.
3 Phenyliodine diacetate (PIDA) is available from many commercial sources and also commonly called
iodobenzene diacetate and (diacetoxyiodo)benzene (DIB). For very recent studies involving PIDA, see:
(a) Derrien, N.; Sharley, J. S.; Rubtsov, A. E.; Malkov, A. V. Org. Lett. 2017, 19, 234. (b) Nicolaou, K. C.; Liu,
G.; Beabout, K.; McCurry, M. D.; Shamoo, Y. J. Am. Chem. Soc. 2017, 139, 3736. (c) Smith, D. T.; Vitaku,
E.; Njardarson, J. T. Org. Lett. 2017, 19, 3508. (d) Danneman, M. W.; Hong, K. B.; Johnston, J. N. Org.
Lett. 2015, 17, 3806. and references therein.
4 Phenyliodine(III) bis(trifluoroacetate) (PIFA), which is also known as [Bis(trifluoroacetoxy)iodo]benzene
(BTI), is commercially-available from a number of sources. For very recent articles utilizing PIFA, see: (a)
Meucci, E. A.; Camasso, N. M.; Sanford, M. S. Organomet. 2017, 36, 247. (b) Rong, H.-J.; Yao, J.-J.; Li, J.-
K.; Qu, J. J. Org. Chem. 2017, 82, 5557. (c) Beltran, R.; Nocquet-Thibault, S.; Blanchard, F.; Dodd, R. H.;
Cariou, K. Org. Biomol. Chem. 2016, 14, 8448. and references therein.
5 For a recent example of benzoxylation of arenes with PhI(OBz)2, see: Li, L.; Wang, Y.; Yang, T.; Zhang,
Q.; Li, D. Tetrahedron Lett. 2016, 57, 5859.
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6 (a) Smalley, A. P.; Cuthbertson, J. D.; Gaunt, M. J. J. Am. Chem. Soc. 2017, 139, 1412. (b) Xu, Y.; Young,
M. C.; Wang, C.; Magness, D. M.; Dong, G. Angew. Chem., Int. Ed. 2016, 55, 9084. (c) Cook, A. K.;
Sanford, M. S. J. Am. Chem. Soc. 2015, 137, 3109. (d) Panda, N.; Mattan, I.; Nayak, D. K. J. Org. Chem.
2015, 80, 6590. (e) Wu, X.; Yang, Y.; Han, J.; Wang, L. Org. Lett. 2015, 17, 5654. (f) Sreenithya, A.; Sunoj,
R. B. Org. Lett. 2014, 16, 6224.
7 For a very recent review of Cu-catalyzed reactions of diaryliodonium salts, see: Fañanás-Mastral, M.
Synthesis 2017, 49, 1905.
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8 Skucas, E.; MacMillan, D. W. C. J. Am. Chem. Soc. 2012, 134, 9090.
9 For a review on diazonium vs. iodonium cross-coupling, see: (a) Bonin, H.; Fouquet, E.; Felpin, F.-X. Adv.
Synth. Catal. 2011, 353, 3063. and references therein.
10 (a) Jia, Z.; Gálvez, E.; Sebastián, R. M.; Pleixats, R.; Álvarez-Larena, Á.; Martin, E.; Vallribera, A.; Shafir,
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16 Feldman, K. S.; Perkins, A. L.; Masters, K. M. J. Org. Chem. 2004, 69, 7928.
17 Hinkle, R. J.; Stang, P. J. Synthesis 1994, 313.
18 (a) Feldman, K. S.; Nuriye, A. Y.; Li, J. J. Org. Chem. 2011, 76, 5042. (b) Feldman, K. S.; Nuriye, A. Y. Org.
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19 Wang, X.; Studer, A. J. Am. Chem. Soc. 2016, 138, 2977.
20 Zhu, D.; Chang, D.; Shi, L. Chem. Commun. 2015, 51, 7180.
21 Domino reactions have become more common in efforts to improve efficiency. The terms “domino”
and “cascade” are often used interchangeably, as we use them. For reviews, see: (a) Nicolaou, K. C.;
Chen, J. S. Chem. Soc. Rev. 2009, 38, 2993. (b) Tietze, L.-F. Domino Reactions in Organic Synthesis; Wiley-
VCH: Weinheim, 2006.
22 Hinkle, R. J.; Lewis, S. E. Org. Lett. 2013, 15, 4070.
23 One example of a naphthyl(phenyl)iodonium salt was found in the literature: Halton, B.; Kay, A. J.;
McNichols, A. T.; Stang, P. J.; Apeloig, Y.; Boese, R.; Maulitz, A. H.; Haumann, T. ARKIVOC 2001, vii, 8.
24 For a recent review on hypervalent iodine reagents with secondary bonds to iodine, see: Zhdankin, V.
V.; Protasiewicz, J. D. Coord. Chem. Rev. 2014, 275, 54.
25 For complete, detailed X-ray data, including atomic coordinates (including hydrogens), bond lengths,
bond angles, etc., see the CIF files in the supporting information.
26 Hinkle, R. J.; McDonald, R. Acta Crystallogr., Sect. C: Cryst. Struct. Commun. 2002, C58, o117.
27 Dohi, T.; Kato, D.; Hyodo, R.; Yamashita, D.; Shiro, M.; Kita, Y. Angew. Chem., Int. Ed. 2011, 50, 3784.
28 Kieltsch, I.; Eisenberger, P.; Togni, A. Angew. Chem., Int. Ed. Engl. 2007, 46, 754.
29 Waldo, J. P.; Zhang, X.; Shi, F.; Larock, R. C. J. Org. Chem. 2008, 73, 6679.
30 This alkynediol was described in 1966 and 1955, but no NMR spectral data were listed: (a) Mavrov, M.
V.; Kucherov, V. F. Izv. Akad. Nauk SSSR, Ser. Khim. 1966, 871. (b) Reppe, W. et al., Justus Liebigs Ann.
Chem. 1955, 596, 25.
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