Synthesis of New Axially Chiral Iodoarenes

Article abstract of DOI:10.1055/s-0035-1560512

A new family of axially chiral iodoarenes derived from commercially available (R)-1,1′-binaphthyl-2,2′-diamine have been synthesized and employed as catalysts in Kita's enantioselective oxidative spirolactonization of propanoic acid tethered 1-naphthol. Through this study, we explored the relationship between the hypervalent iodoarene geometry and enantioselectivity, contributing to the current understanding of axial-to-central chirality transfer in organoiodine(III) catalysis.

Full text of DOI:10.1055/s-0035-1560512

SYNTHESIS
0
0
3
9
-
7
8
8
1
1
4
3
7
-
2
1
0
X
© Georg Thieme Verlag Stuttgart · New York
2016, 48, 302–312
paper
302
M. Bekkaye, G. Masson
Paper
Synthesis
Synthesis of New Axially Chiral Iodoarenes
Mathieu Bekkaye
Ar
Géraldine Masson*
I
8 catalysts
X
Institut de Chimie des Substances Naturelles CNRS, Univ.
Paris-Sud, 1 Avenue de la Terrasse, 91198 Gif-sur-Yvette
Cedex, France
R
geraldine.masson@cnrs.fr
X = I or NHAc
R = H or Ar
(10 mol%)
OH
O
O
mCPBA (1.3 equiv)
*
O
OH
O
CHCl3, 0 °C, 3 h
50–67% yield
up to 36% ee
Received: 27.08.2015
Accepted after revision: 25.09.2015
Published online: 05.11.2015
ity (up to 92%, for 3b).4b Later, Ishihara et al. reported that a
new flexible C2-symmetric iodoarene 3c was an efficient
precatalyst for the same reaction, producing spirolactones
with high enantioselectivity (up to 92%).4c,d In 2015,
Ibrahim et al. identified a new anti-dimethanoanthracene
scaffold-based chiral iodoarene 3d that induced moderate
enantioselectivity in the spirolactonization.4e Also in 2015,
Ishihara et al. developed highly enantioselective oxidative
spirolactonization of 1-naphthol derivatives using chiral
ammonium hypoiodite catalysis.4f Despite these achieve-
ments,4,5 the development of new, efficient chiral hyperva-
lent iodine precursors and a better understanding of the
factors controlling the enantioselectivity in iodine(III) ca-
talysis is still highly desirable.2,4–6
DOI: 10.1055/s-0035-1560512; Art ID: ss-2015-z0503-op
Abstract A new family of axially chiral iodoarenes derived from com-
mercially available (R)-1,1′-binaphthyl-2,2′-diamine have been synthe-
sized and employed as catalysts in Kita’s enantioselective oxidative spi-
rolactonization of propanoic acid tethered 1-naphthol. Through this
study, we explored the relationship between the hypervalent iodoarene
geometry and enantioselectivity, contributing to the current under-
standing of axial-to-central chirality transfer in organoiodine(III) cataly-
sis.
Key words chiral iodane, hypervalent iodine, dearomatization, stereo-
selective synthesis, spirolactonization
The construction of complex molecules from simple
and easily available aromatic compounds using a dearoma-
tization strategy has been extensively explored by organic
chemists. Among these strategies, enantioselective dearo-
matization of phenol derivatives1 mediated by chiral hyper-
valent iodine reagents (iodanes) has drawn significant at-
tention due to their low toxicity, stability towards moisture,
and ease of handling.2 Moreover, these oxidants can be se-
lectively generated in situ,3 thus minimizing the accumula-
tion of unwanted waste. In spite of significant advances
over the years, the development of catalytic enantioselec-
tive dearomatizations still remains one of the most chal-
lenging areas in asymmetric hypervalent iodine cataly-
sis.2f,m In 2008, Kita et al. disclosed the first example of a
highly enantioselective oxidative spirolactonization of pro-
panoic acid tethered 1-naphthols with a novel rigid chiral
iodane(III) compound based on the spirobiindane backbone
3a (Scheme 1).4a While stoichiometric amounts of precata-
lyst 3a were required for high enantiomeric excess (86%),
moderate enantioselectivity was obtained with catalytic
loading. Subsequently, the same group found that substi-
tuting the ortho position provided the best enantioselectiv-
OH
O
O
3 (10–15 mol%)
mCPBA (1.3 equiv)
O
OH
O
CHCl3, 0 °C, 3 h
1
2
R
I
O
O
I
I
O
O
NHMes
MesHN
R
I
3c (92% ee)
3a, R = H (65% ee)
3b, R = Et (92% ee)
3d (40% ee)
Scheme 1 Previous work on enantioselective oxidative spirolactoniza-
tion of 1-naphthol 1
Based on our experience in organocatalysis7 and moti-
vated by our recent interest in hypervalent iodine chemis-
try,8 we have initiated a research project oriented toward
the development of a catalyst family displaying tunable
structural properties based on an axially chiral backbone.
Wirth et al. first reported, in 2007, the use of 2,2′-diiodo-
1,1′-binaphthyl (BINI) as a chiral iodine(III) precursor for
the enantioselective α-oxytosylation of ketones.9 In 2008
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2016, 48, 302–312

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M. Bekkaye, G. Masson
Paper
Synthesis
Kita et al.4a employed this oxidant precursor in stoichiomet-
ric amounts for enantioselective spirocyclization. In both
studies, the enantioselectivities achieved were low (<10%
ee). Due to poor enantioselectivity in both reactions, these
structures were overlooked until the Quideau group rein-
troduced BINOL-derived iodoarenes as a promising back-
bone in asymmetric hypervalent iodine organocatalysis.10
In 2013, Berthiol et al. also demonstrated that 3,3′-diiodo-
BINOL-fused maleimide derivatives could mediate the α-
functionalization of ketones with enantioselectivities com-
parable to the best results reported to date (46%5c vs 54% ee
by Legault et al.5a). Despite the potential of axial-to-central
chirality transfer in iodide(III) catalysis, existing scaffolds
are limited in their tunability and/or synthetically challeng-
ing.11 Taking into account the above-mentioned consider-
ations, we designed a family of 2,2′-diiodo-1,1′-binaphthyls
containing two main adjustable features: (i) modulation of
the steric hindrance surrounding the hypervalent iodine
center by introducing 3,3′-diaryl substituents on the
binaphthyl 4, (ii) modulation of the rigidity by additional
noncovalent interactions between the group X and the io-
dine center (Figure 1). We report our initial efforts toward
the development of novel chiral iodoarenes and their evalu-
ation in the enantioselective Kita’s spirolactonization.
tively at the 3,3′-positions with N-bromosuccinimide allow-
ing subsequent arylation by Suzuki–Miyaura coupling.13b
Due to the moderate yield for the rearomatization of 8a
(<50%), we decided to continue the synthesis with the octa-
hydrogenated structure.14 With the desired 3,3′-diphenyl-
H8-BINAM (8a) in hand, the stage was set for the proposed
Sandmeyer reaction. At this step, we were particularly con-
cerned about partial racemization of 8a during the reac-
tion.15 Although stepwise methods involving the isolation
of diazonium mercurate salts have been developed to over-
come this issue,15c we wanted to develop a one-pot diazoti-
zation–iodination of the 3,3′-diphenyl (R)-H8-BINAM (8a)
without the use of toxic heavy metals (Table 1). Our first at-
tempts under classical conditions were unsuccessful (en-
tries 1–3). However, when the reaction was carried out
with sodium nitrite, potassium iodide, and trifluoroacetic
acid in water, the desired 3,3′-diphenyl-H8-BINI (4a) was
isolated in 11% yield without noticeable loss of enantiopuri-
ty. With this result in hand, a number of experiments were
Table 1 Survey of Conditions for the Sandmeyer Reactiona
Ph
Ph
NH2
NH2
I
I
nitrite, acid, KI
solvent, T °C
3
Ar
steric hindrance
8a
4a
I
dihedral angle value
Ph
Ph
X
X = I or NHCOR
Entry Nitrite
Acid
Solvent
T (°C)
Yieldb (%)
3'
Ar
hydrogen-bonding
interaction
1
2
3
4
5
6
7
8
9
t-BuONO
–
MeCN
MeCN
H2O
0 to 60
–
4
NaNO2
NaNO2
NaNO2
NaNO2
NaNO2
NaNO2
NaNO2
NaNO2
TFA
TFA
0
–
Figure 1 Targeted structures
0
11
–
After designing an appropriately modular scaffold start-
ing from commercially available (R)-1,1′-binaphthyl-2,2′-
diamine [(R)-BINAM, 5], a late-stage Sandmeyer reaction
was chosen to introduce the iodine atoms (Scheme 2), de-
spite the difficulties of such a reaction with hindered sub-
strates.12 This challenging system provided a platform to
develop a highly efficient protocol for the Sandmeyer reac-
tion with various 3,3′-diaryl (R)-BINAMs. First, 5 was re-
duced to (R)-H8-BINAM (6) with Ni/Al alloy in good yield
(Scheme 2).13a Compound 6 was then halogenated selec-
H2SO4
H2O
0
6 M aq HCl
H2O
0
36
41
50c
45
48
48% aq HBr
H2O
0
33% HBr in AcOH
33% HBr in AcOH
33% HBr in AcOH
DMSO
DMSO
DMF
r.t.
0 to r.t.
0 to r.t.
a General conditions: amine 7a (0.05 mmol), nitrile (0.40 mmol), KI (0.80
mmol), solvent (1.0 mL).
b Yields refer to chromatographically pure product.
c Undesired rearomatization was observed.16
R
NH2
NH2
ii,iii
NH2
NH2
i
NH2
NH2
90%
81%
over 2 steps
R
5 (R)-BINAM
6 (R)-H8-BINAM
7 R = Br
8a R = Ph
Scheme 2 Synthesis of 3,3′-diphenyl (R)-H8-BINAM (8a). Reagents and conditions: (i) Ni/Al alloy, i-PrOH–H2O, 90 °C, 120 h; (ii) NBS (2.2 equiv), THF,
0 °C, 1 min; (iii) Pd(OAc)2 (0.1 equiv), Ph3P (0.4 equiv), Ba(OH)2·8H2O (4 equiv), PhB(OH)2 (3 equiv), DME–H2O, reflux, 24 h.
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M. Bekkaye, G. Masson
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conducted to improve the yield. First, it was observed that
the reaction is significantly affected by the acid used, with
hydrobromic acid providing the best yield (entries 3–6). We
were pleased to see that when 33% hydrobromic acid in
acetic acid was employed, the desired product was isolated
in higher yield albeit with the formation of a rearomatized
side product (entry 7).16 This side reaction was completely
depressed by a modification of the reaction conditions,
with only a slight decrease in the yield of 4a (entry 8). We
obtained very similar results when N,N-dimethylform-
amide was used as the solvent (entry 9).
Ar
Ar
NH2
NH2
i
ii
I
I
7
Ar
Ar
8b, Ar = 1-naphthyl (58%)
4b, Ar = 1-naphthyl (39%)
4c, Ar = 9-phenanthryl (37%)
4d, Ar = 4-PhC6H4 (42%)
8c, Ar = 9-phenanthryl (69%)
8d, Ar = 4-PhC6H4 (89%)
With these results in hands, we next synthesized three
representative iodoarene precursors 4b–d possessing dif-
ferent steric environments at the 3,3′-positions in modest
yields (Scheme 3). A pair of unsubstituted catalysts 4e15e,16
and 4f16 were also synthesized to investigate the full range
of steric environments (Scheme 3). Next, we focused on the
synthesis of non-C2-symmetric hypervalent iodine precur-
sors. To that end, (R)-BINAM (5) and (R)-H8-BINAM (6) were
monoacylated with acetic anhydride in the presence of ace-
tic acid (Scheme 4). Disappointingly, the monoacylation of
3,3′-diphenyl-H8-BINAM (8a), resulted in an unsatisfactory
yield (<20%),17 so the synthesis was continued with only
unsubstituted BINAMs.
Product 9 was subjected to the bromination conditions
described above, but a mixture of mono- and dibrominated
products were isolated with a combined yield of 24%. Fortu-
nately, with a solution of bromine in acetic acid, the mono-
brominated H8-BINAM 10 could be isolated in 81% yield.
Despite all of our attempts to introduce a second bromine
on the more electron-poor acetanilide ring of 10, only deg-
radation was observed. The Suzuki–Miyaura coupling of
phenylboronic acid with monobrominated H8-BINAM 10
led to the desired coupling product in a good yield, which
was carried into a one-pot diazotization–iodination reac-
tion to afford the expected non-C2-symmetric product (R)-
4g. The unsubstituted iodoarene precatalyst 4h was pre-
pared from 5 by monoacylation and Sandmeyer reaction
(Scheme 4).
ii
48%
ii
I
I
I
5
6
50%
I
(R)-BINI
(R)-[H8]BINI
4f
4e
Scheme 3 Synthesis of new 3,3′-disubstituted H8-BINIs 4. Reagents and
conditions: (i) Pd(OAc)2 (0.1 equiv), Ph3P (0.4 equiv), Ba(OH)2·8H2O (4
equiv), ArB(OH)2 (3 equiv), DME–H2O (10:1), reflux, 24 h; (ii) NaNO2 (8
equiv), KI (10 equiv), DMSO, 0 °C to r.t.
To test the potential application of these new chiral io-
doarenes as hypervalent iodine organocatalysts, we used
Kita’s spirolactonization as a model reaction (Table 2).4 On
the basis of previous work,4a,b 10 mol% of (R)-BINI 4e and
1.3 equivalents of 3-chloroperbenzoic acid were premixed
for 10 minutes at 0 °C to preform the active hypervalent
species,18 then propanoic acid tethered 1-naphthol 1 was
added. Chloroform was selected as a non-coordinating apo-
lar solvent to favor an associative mechanism for the spiro-
cyclization.19 Precatalyst 4e afforded the desired spirolac-
tone 7 in 55% yield with <5% ee (entry 1) which is consis-
tent with previous observations reported by Kita’s group.4a
Interestingly, non-C2-symmetric iodoarene precatalyst 4h
gave better enantioselectivity (23% ee) than C2-symmetric
(R)-BINI 4e (entry 1 vs 2). Similarly, substituting H8-BINI 4f
for BINI 4e in the spirolactonization reaction afforded an in-
crease in enantioselectivity, presumably due to variation in
Br
Ph
i
iii, iv
ii
NH2
NH2
I
6
60%
81%
NHAc
NHAc
NHAc
4g
9
10
24% over 2 steps
iv
i
NH2
I
5
63%
51%
NHAc
NHAc
11
4h
Scheme 4 Synthesis of non-C2-symmetric BINIs 4. Reagents and conditions: (i) AcOH (10.0 equiv) Ac2O (1.1 equiv), CH2Cl2, 0 °C to r.t., 12 h; (ii) Br2 (20
equiv), AcOH, r.t., 20 min; (iii) Pd(OAc)2 (0.1 equiv), Ph3P (0.4 equiv), Ba(OH)2·8H2O (4 equiv), PhB(OH)2 (3 equiv), DME–H2O, reflux, 24 h; (iv) NaNO2 (8
equiv), KI (10 equiv), DMSO, 0 °C to r.t., 6 h.
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M. Bekkaye, G. Masson
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the dihedral angle of 4. Strikingly, a reversal of enantiose-
lectivity was observed that is directly related to the pres-
ence of the amide function. Indeed, the combination of
both features (non-C2-symmetric and partially hydrogenat-
ed backbone) in 4a provided the opposite enantiomer as
the major product with similar enantioselectivity (entry 4).
The introduction of aryl groups at the 3,3′-positions exert-
ed a beneficial effect on the enantioselectivity with the 1-
naphthyl-substituted catalyst 4b performing slightly better
than the other catalysts (entries 5–8). Finally, lowering the
temperature to –30 °C did not improve the enantioselectiv-
ity and gave lower yields (entry 10).
Entry
4
Yieldb (%) eec (%) Configd
I
I
7
59
30
S
Table 2 Evaluation of Precatalysts in the Spirolactonization of 1a
4c
Ph
OH
O
4 (10 mol%)
mCPBA (1.3 equiv)
O
O
CHCl3, 0 °C, 16 h
O
OH
I
I
2
1
8
53
33
S
Entry
1
4
Yieldb (%) eec (%) Configd
BINI 4e
55
61
67
2
23
22
S
R
S
Ph
4d
4a
4a
4a
9e
10f
11g
60
50
61
30
31
1
S
S
S
I
2
3
NHAc
a General conditions: 1 (0.05 mmol), CHCl3 (1.0 mL).
b Yields refer to chromatographically pure product.
c Determined by HPLC analysis on chiral stationary phase.
4h
H8-BINI 4f
d Absolute stereochemistry by comparing the optical rotation.4
e AcOH (5 equiv) was added.
Ph
f Reaction conducted at –30 °C.
g MeCN was used as the solvent.
I
4
62
24
R
NHAc
Since iodanes generally adopt a T-shaped conforma-
tion20 with elongated I–O bonds,21 the hypervalent form of
4 can exist as an iodine(III) tetracarboxylate 12 or a μ-oxo-
bridged diodine(III) 13, the latter being demonstrated by
the group of Ochiai with the X-ray crystal structure of diac-
etoxy-λ3-iodobinaphthyl (Ar1 = Ar2 = H, L = OAc, Scheme
5).6d In addition, other, X-ray crystallographic studies have
shown that aryl-λ3-iodanes free of acid can exist in an
oligomeric state where they are linked by μ-oxo bridges.21
On the other hand, aryl-λ3-iodanes mainly adopt an un-
bridged structure where two carboxylate groups are at-
tached to the same iodine in the presence of an external
acid source. This difference in structure is mainly due to the
lability of μ-oxo-bridged iodine(III) under acidic condi-
tions.6d,22 Thus, the generation of 3-chlorobenzoic acid in
the course of the spirolactonization should favor the forma-
tion of iodine(III) tetracarboxylate 12 (Scheme 5).6d As a re-
sult, the active catalyst could be 12 rather than μ-oxo-
bridged species 13. To support this, a control experiment
was performed in which the oxidative lactonization was
4g
Ph
I
I
5
64
31
S
Ph
4a
I
I
6
63
36
S
4b
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2016, 48, 302–312

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M. Bekkaye, G. Masson
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to the formation of racemic product 1. By analogy with
Ishihara’s catalyst,4c,d two possible conformations are con-
ceivable for the iodane precatalysts 4g,h containing an am-
ide group. The first conformer 14 would form a hydrogen
bond between the amide and the ligands attached to the io-
dine atom, while the second one 15 could be stabilized by
n–σ* interactions between the iodine(III) center and car-
bonyl oxygen (Figure 2). These additional non-covalent in-
teractions may favor the transition states leading to the op-
posite enantiomer of 1 with the same enantioselectivity as
obtained with 4a–d.
Ar1
Ar1
L
L
O
L
hydrolysis
I
I
I
I
L
L
μ-oxo bridge formation
L
(slow)
Ar2
Ar2
12
13
O
L =
R = 3-ClC6H4, Me
Scheme 5 Possible of active catalyst form
O
R
O
H
carried out in the presence of excess acetic acid (Table 2, en-
try 9). As expected, the desired spirolactone 2 was isolated
with similar yield and enantioselectivity, indicating the
possibility of an unbridged active catalyst.22a
Me
Me
N
I
L
N
I
L
H
O
L
L
15
14
Ar2
Ar2
To rationalize the moderate enantiomeric excess ob-
tained for this new series of chiral precatalysts 4, we hy-
pothesize that the iodine(III) tetracarboxylate 12 may inter-
convert between four transient intermediates A–D through
ligand-exchange reactions between the phenol and io-
dine(III) carboxylate (Scheme 6). Accordingly, two subunits
of 4 (i.e., 1,1′-binaphthyl moiety and 3,3′-diaryl-substitu-
ents) could govern the stereocontrol of the spirocyclization.
Of the four transition state models, A and/or B are expected
to be favored for the catalyst bearing substituents on the
3,3′-positions of BINI 4a–d because C and D exhibit a desta-
bilizing interaction between the aryl group of 4a–d and
naphthol derivative 1. This could explain the better enan-
tioselectivities observed with disubstituted precatalysts
4a–d. Alternatively, the unsubstituted C2-symmetric prec-
atalyst 4e could coexist in the four transition states leading
O
L =
O
R
Figure 2 Two possible conformations of the active catalyst derived
from 4g,h
In summary, we have developed a suitable pathway to
access a new family of axially chiral iodoarenes derived
from commercially available (R)-BINAM. We have demon-
strated the efficiency of these new iodoarenes as catalysts
in Kita’s spirolactonization of propanoic acid tethered 1-
naphthol. Both the 3,3′-diaryl substituents and the H-bond
amide donor in the octahydrogenated BINI backbone were
key structural features for controlling stereoselectivity. The
highly versatile synthetic approach should allow for modu-
lation and optimization of the catalytic behavior of these
precatalysts. Efforts towards achieving this goal are under-
way in our laboratory and will be reported in due course.
CO2H
HO2C
Ar2
All reagents were obtained from commercial suppliers and used
without further purification unless otherwise noted. Analytical TLC
was performed on plates precoated with silica gel layers. NMR spectra
(1H, 13C) were recorded with 500 and 300 MHz spectrometers. Flash
column chromatography was carried out using Merck Geduran 40–63
μm particle size silica gel. Preparative TLC was performed using
Merck silica gel 60 F254. HRMS were recorded using ESI and a TOF an-
alyzer, in positive-ion or negative-ion detection mode.
O
O
Ar1
Ar1
I
I
Ar2
X
X
A
B
L
L
(R)-5,5′,6,6′,7,7′,8,8′-Octahydro-1,1′-binaphthyl-2,2′-diamine (6)
(R)-BINAM (5, 1 g, 3.52 mmol) and Ni–Al alloy (1:1, 7.04 g) were sus-
pended in H2O–i-PrOH (1:1, 800 mL). The mixture was heated to re-
flux with intensive stirring, and then 1% aq NaOH solution (800 mL)
was added dropwise via an addition funnel over 1 h. When the addi-
tion was complete, the mixture was stirred vigorously at reflux for 5
d. The mixture was then cooled to r.t., filtered through a pad of Celite
and the Celite was washed with EtOAc. The resulting biphasic solu-
tion was transferred into a separatory funnel, the layers were separat-
ed, and the aqueous layer was extracted with EtOAc (3 ×). The com-
bined organic extracts were washed with water (2 ×) and brine, and
L
L
I
Ar1
Ar1
I
Ar2
Ar2
X
X
O
O
CO2H
HO2C
C
D
Scheme 6 Putative intermediates 4
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M. Bekkaye, G. Masson
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Synthesis
dried (Na2SO4). The inorganic salts were removed by filtration, and
the organic layer was concentrated under reduced pressure with silica
gel to afford a crude residue that was purified by chromatography
(silica gel, heptane–EtOAc, gradient from 95:5 to 90:10) to afford the
product as a white solid; yield: 999 mg (90%); mp 209–211 °C.
concentrated under reduced pressure with silica gel to afford a crude
residue that was purified by chromatography (silica gel, heptane–
EtOAc, gradient from 99:1 to 95:5) to afford the product as a white
solid; yield: 166 mg (90%); mp 228–230 °C.
[α]D25 –40.0 (c 0.8, CHCl3).
IR (neat): 3446, 3360, 3008, 2950, 2937, 2911, 1561, 1473, 1410,
IR (neat): 3469, 3374, 3055, 2927, 2854, 2834, 1606, 1495, 1458,
1362, 1251, 1189, 1141, 1080, 1010, 805, 701 cm–1
.
1414, 1264, 776, 738, 703 cm–1
.
1H NMR (300 MHz, CDCl3): δ = 6.91 (d, J = 8.0 Hz, 2 H), 6.60 (d, J = 8.0
Hz, 2 H), 3.32 (br s, 4 H), 2.73–2.69 (m, 4 H), 2.32–2.11 (m, 4 H), 1.76–
1.61 (m, 8 H).
13C NMR (75 MHz, CDCl3): δ = 141.6 (2 Cq), 136.2 (2 Cq), 129.3 (2 CH),
127.7 (2 Cq), 122.0 (2 Cq), 113.1 (2 CH), 29.4 (2 CH2), 27.0 (2 CH2),
23.5 (2 CH2), 23.3 (2 CH2).
1H NMR (300 MHz, CDCl3): δ = 7.54–7.46 (m, 4 H), 7.46–7.36 (m, 4 H),
7.35–7.27 (m, 2 H), 6.92 (s, 2 H), 3.37 (br s, 4 H), 2.86–2.66 (m, 4 H),
2.48–2.18 (m, 4 H), 1.84–1.64 (m, 8 H).
13C NMR (75 MHz, CDCl3): δ = 140.1 (2 CAr), 138.8 (2 CAr), 135.6 (2 CAr),
130.3 (2 CAr), 129.2 (4 CAr), 128.6 (4 CAr), 127.4 (2 CAr), 126.8 (2 CAr),
125.7 (2 CAr), 122.3 (2 CAr), 29.3 (2 CH2), 27.0 (2 CH2), 23.5 (2 CH2),
23.3 (2 CH2).
HRMS (ES+): m/z [M + Na]+ calcd for C20H24N2Na: 315.1832; found:
315.1837.
HRMS (ES+): m/z [M + Na]+ calcd for C32H32N2Na: 467.2458; found:
467.2464.
(R)-3,3′-Dibromo-5,5′,6,6′,7,7′,8,8′-octahydro-1,1′-binaphthyl-2,2′-
diamine (7)
(R)-3,3′-Di(1-naphthyl)-5,5′,6,6′,7,7′,8,8′-octahydro-1,1′-binaph-
thyl-2,2′-diamine (8b)
To a stirred suspension of (R)-H8-BINAM 6 (537 mg, 1.84 mmol) in
THF, cooled to approx. 0 °C with an NaCl/ice-water bath, was added
NBS (720 mg, 4.04 mmol, 2.2 equiv) in one portion. The mixture was
stirred vigorously at 0 °C for 1 min, during which time the solution
progressively turned dark brown. The mixture was then quenched
with sat. NaHCO3 and sat. Na2SO3 at 0 °C, and stirred vigorously for
several minutes. The mixture was then diluted with EtOAc and H2O
and poured into a separatory funnel, the layers were separated, and
the aqueous layer was extracted with EtOAc (3 ×). The combined or-
ganic extracts were washed with brine and dried (Na2SO4). The inor-
ganic salt was removed by filtration, and the organic layer was con-
centrated under reduced pressure with silica gel to afford crude resi-
due that was purified by chromatography (silica gel, heptane–EtOAc,
gradient from 99:1 to 90:10) to afford the product as a brownish sol-
id; yield: 780 mg (90%); mp 170–172 °C.
Following the typical procedure for 8a using (R)-3,3′-dibromo-H8-
BINAM 7 (177 mg, 395 μmol) with naphthalen-1-ylboronic acid (204
mg, 1185 μmol, 3 equiv) afforded the product as a white solid; yield:
125 mg (58%).
[α]D25 –50.0 (c 0.4, CHCl3).
IR (neat): 3465, 3372, 2922, 2853, 1604, 1506, 1452, 1418, 1391,
1353, 1336, 1313, 1263, 1242, 1212, 1084, 976, 913, 879, 822, 801,
776, 733, 666 cm–1
.
1H NMR (300 MHz, CDCl3): δ = 7.99–7.28 (m, 14 H), 6.94 and 6.93 (br
s, 2 H), 2.98 (br s, 4 H), 2.87–2.65 (m, 4 H), 2.62–2.31 (m, 4 H), 1.93–
1.69 (m, 8 H).
13C NMR (75 MHz, CDCl3): δ = 139.6 (2 CAr), 137.6 (2 CAr), 135.9 (2 CAr),
133.9 (2 CAr), 131.9 (2 CAr), 131.0 (2 CAr), 131.0 (2 CAr), 128.3 (2 CAr),
127.7 (2 CAr), 127.2 (2 CAr), 126.3 (2 CAr), 126.1 (2 CAr), 126.0 (2 CAr),
125.8 (2 CAr), 124.0 (2 CAr), 122.0 (2 CAr), 29.3 (2 CH2), 27.1 (2 CH2),
23.7 (2 CH2), 23.4 (2 CH2).
IR (neat): 3468, 3376, 2926, 2854, 1602, 1457, 1276, 1260, 762, 751
cm–1
.
1H NMR (300 MHz, CDCl3): δ = 7.21 (s, 2 H), 3.69 (br s, 4 H), 2.70 (t,
J = 6.0 Hz, 4 H), 2.30–2.01 (m, 4 H), 1.77–1.58 (m, 8 H).
HRMS (ES+): m/z [M + H]+ calcd for C40H37N2: 545.2951; found:
13C NMR (75 MHz, CDCl3): δ = 139.2 (2 Cq), 135.7 (2 Cq), 132.3 (2 CH),
129.0 (2 Cq), 122.4 (2 Cq), 107.0 (2 CH), 29.0 (2 CH2), 26.7 (2 CH2),
23.2 (2 CH2), 23.0 (2 CH2).
545.2952.
(R)-3,3′-Di(phenanthren-9-yl)-5,5′,6,6′,7,7′,8,8′-octahydro-1,1′-
binaphthyl-2,2′-diamine (8c)
HRMS (ES+): m/z [M + Na]+ calcd for C20H22Br2N2Na: 471.0042; found:
471.0046.
Following the typical procedure for 8a using (R)-3,3′-dibromo-H8-
BINAM 7 (177 mg, 395 μmol) with phenanthren-9-ylboronic acid
(263.2 mg, 1185 μmol, 3 equiv) afforded the product as a white solid;
yield: 176 mg (69%).
(R)-3,3′-Diphenyl-5,5′,6,6′,7,7′,8,8′-octahydro-1,1′-binaphthyl-2,2′-
diamine (8a); Typical Procedure
[α]D25 –63.0 (c 1.0, CHCl3).
This compound was prepared according to the procedure of Maruoka
et al.:13b In an oven-dried flask, equipped with a stir bar and a reflux
condenser, were placed (R)-3,3′-dibromo-H8-BINAM 7 (177 mg, 395
μmol), Pd(OAc)2 (9 mg, 39.5 μmol, 0.1 equiv), phenylboronic acid
(144.6 mg, 1185 μmol, 3 equiv), Ph3P (42 mg, 160 μmol, 0.4 equiv),
and Ba(OH)2·8H2O (498 mg, 1580 μmol, 4 equiv), and the flask was
purged with argon. Then, a degassed mixture of DME–H2O (10:1, 10
mL) was added through the condenser. The resulting mixture was
stirred vigorously and refluxed for 24 h under argon. The brown mix-
ture was cooled to r.t., diluted with brine and EtOAc, and transferred
to a separatory funnel; the layers were separated and the aqueous
layer was extracted with EtOAc (3 ×). The combined organic extracts
were washed with brine and dried (Na2SO4). The inorganic salts were
removed by filtration through a short pad of Celite. The filtrate was
IR (neat): 3464, 3375, 2923, 2853, 1602, 1527, 1492, 1461, 1447,
1422, 1354, 1314, 1244, 1212, 1164, 1134, 1115, 1097, 1040, 967,
948, 894, 769, 745, 724, 676 cm–1
.
1H NMR (300 MHz, CDCl3): δ = 8.84–8.64 (m, 4 H), 7.97–7.52 and
7.51–7.38 (m, 14 H), 7.02 and 7.00 (br s, 2 H), 3.11 (br s, 4 H), 2.90–
2.68 (m, 4 H), 2.66–2.33 (m, 4 H), 1.96–1.70 (m, 8 H).
13C NMR (75 MHz, CDCl3): δ = 139.8 (2 CAr), 136.1 (2 CAr), 136.1 (2 CAr),
135.9 (2 CAr), 131.9 (2 CAr), 131.1 (2 CAr), 130.7 (2 CAr), 130.1 (2 CAr),
128.7 (2 CAr), 128.3 (2 CAr), 127.3 (2 CAr), 127.0 (2 CAr), 126.8 (4 CAr),
126.6 (4 CAr), 123.9 (2 CAr), 122.9 (2 CAr), 122.5 (2 CAr), 122.0 (2 CAr),
29.3 (2 CH2), 27.2 (2 CH2), 23.7 and 23.6 (2 CH2), 23.4 (2 CH2).
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M. Bekkaye, G. Masson
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Synthesis
HRMS (ES+): m/z [M + H]+ calcd for C48H41N2: 645.3264; found:
645.3269.
(R)-2,2′-Diiodo-3,3′-di(1-naphthyl)-5,5′,6,6′,7,7′,8,8′-octahydro-
1,1′-binaphthyl (4b)
Following the typical procedure for 4a using (R)-3,3′-di(1-naphthyl)-
H8-BINAM 8b (150 mg, 276 μmol) afforded the product as a yellowish
solid; yield: 149 mg (39%).
(R)-3,3′-Di(biphenyl-4-yl)-5,5′,6,6′,7,7′,8,8′-octahydro-1,1′-binaph-
thyl-2,2′-diamine (8d)
[α]D25 – 78.0 (c 1.0, CHCl3).
Following the typical procedure for 8a using (R)-3,3′-dibromo-H8-
BINAM 7 (177 mg, 395 μmol) with biphenyl-4-ylboronic acid (234.5
mg, 1185 μmol, 3 equiv) afforded the product as a brownish solid;
yield: 210 mg (89%).
IR (neat): 2922, 2854, 1507, 1486, 1440, 1392, 1353, 820, 799, 773,
733 cm–1
.
1H NMR (300 MHz, CDCl3): δ = 7.99–7.83 (m, 4 H), 7.75–7.27 (m, 10
H), 7.17–7.07 (m, 2 H), 2.91–2.75 (m, 4 H), 2.69–2.23 (m, 4 H), 1.95–
1.73 (m, 8 H).
13C NMR (75 MHz, CDCl3): δ = 144.7, 143.7, 143.6, 143.4, 143.2, 141.5,
140.1, 139.8, 139.4, 139.2, 139.0, 138.0, 137.8, 137.7, 137.1, 137.0,
136.8, 136.7, 136.2, 136.1, 135.6, 135.5, 133.5, 133.4, 131.9, 131.8,
131.7, 130.7, 130.6, 128.3, 128.0, 127.9, 127.8, 127.4, 127.3, 126.8,
126.6, 126.5, 126.1, 126.0, 125.8, 125.7, 125.3, 125.1, 122.7, 60.4, 60.0,
59.8, 29.1, 28.9, 28.4, 28.2, 23.6, 23.5, 23.4, 23.3 (mixture of rotam-
ers/atropoisomers).
[α]D25 –340.0 (c 1.0, CHCl3).
IR (neat): 3450, 3366, 3027, 2923, 1602, 1519, 1486, 1436, 1394,
1355, 1308, 1263, 1242, 1075, 1007, 842, 825, 769, 734, 695 cm–1
.
1H NMR (300 MHz, CDCl3): δ = 7.74–7.53 and 7.52–7.40 and 7.40–
7.31 (m, 18 H), 6.98 (s, 2 H), 2.85–2.73 (m, 4 H), 2.50–2.21 (m, 4 H),
1.85 (br s, 4 H), 1.90–1.62 (m, 8 H).
13C NMR (75 MHz, CDCl3): δ = 140.9 (2 CAr), 139.7 (2 CAr), 139.1 (2 CAr),
138.8 (2 CAr), 135.8 (2 CAr), 130.4 (4 CAr), 129.6 (4 CAr), 128.9 (4 CAr),
127.6 (2 CAr), 127.4 (4 CAr), 127.3 (2 CAr), 127.1 (2 CAr), 125.2 (2 CAr),
122.5 (2 CAr), 29.4 (2 CH2), 27.1 (2 CH2), 23.6 (2 CH2), 23.4 (2 CH2).
HRMS (ES+): m/z [M]+ calcd for C40H32I2: 766.0588; found: 766.0590.
HRMS (ES+): m/z [M + H]+ calcd for C44H41N2: 597.3264; found:
597.3269.
(R)-2,2′-Diiodo-3,3′-di(phenanthren-9-yl)-5,5′,6,6′,7,7′,8,8′-octahy-
dro-1,1′-binaphthyl (4c)
(R)-2,2′-Diiodo-3,3′-diphenyl-5,5′,6,6′,7,7′,8,8′-octahydro-1,1′-
binaphthyl (4a); Typical Procedure
Following the typical procedure for 4a using (R)-3,3′-di(phenanthren-
9-yl)-H8-BINAM 8c (150 mg, 276 μmol) afforded the product as a yel-
lowish solid; yield: 88 mg (37%).
In an oven-dried flask equipped with a stir bar, were placed (R)-3,3′-
diphenyl-H8-BINAM 8a (223 mg, 500 μmol), NaNO2 (276 mg, 4 mmol,
8 equiv), and KI (830 mg, 5 mmol, 10 equiv). Then, DMSO (10 mL) was
added, and the suspension was gently stirred at r.t. to allow complete
dissolution of the solids. The solution was then cooled to approx. 0 °C
with an NaCl/ice-water bath, and stirred vigorously to avoid solidifi-
cation of the solvent. 33% HBr in AcOH (1 mL) was added dropwise
quickly, but carefully, leading to a visible gas evolution. The resulting
black solution was stirred for several hours, monitoring the reaction
by TLC. The solution was then poured into sat. aq NaHCO3 solution,
and diluted with CH2Cl2. The resulting biphasic solution was trans-
ferred to a separatory funnel and the layers were separated; the aque-
ous layer was extracted with CH2Cl2 (3 ×). The combined organic ex-
tracts were washed with NaHSO3 and brine, and dried (Na2SO4). The
inorganic salts were removed by filtration, and the organic layer was
concentrated under reduced pressure with silica gel to afford a crude
residue that was purified by chromatography (silica gel, heptane–
CH2Cl2, gradient from 100:0 to 85:15) to afford the product as a yel-
lowish solid; yield: 150 mg (45%).
IR (neat): 3469, 3374, 3055, 2927, 2854, 2834, 1606, 1495, 1458,
1414, 1264, 776, 738, 703 cm–1
.
1H NMR (300 MHz, CDCl3): δ = 8.86–8.70 (m, 4 H), 8.00–7.81, 7.78–
7.52, 7.49–7.35, and 7.24–7.10 (m, 16 H), 2.92–2.76 (m, 4 H), 2.73–
2.26 (m, 4 H), 1.97–1.72 (m, 8 H).
13C NMR (75 MHz, CDCl3): δ = 148.5, 145.6, 145.4, 144.7, 143.7, 143.6,
142.3, 141.9, 141.7, 141.5, 139.4, 139.2, 138.8, 138.4, 138.0, 138.0,
137.1, 136.9, 136.4, 136.3, 136.3, 135.7, 132.0, 131.8, 131.6, 131.4,
131.4, 131.2, 131.1, 131.1, 130.9, 130.8, 130.8, 130.5, 130.4, 130.3,
130.1, 129.9, 128.9, 128.7, 128.5, 128.4, 128.2, 128.1, 127.9, 127.7,
127.6, 127.5, 127.4, 127.3, 127.1, 127.1, 127.0, 126.9, 126.8, 126.8,
126.5, 126.4, 122.9, 122.7, 122.6, 30.2, 29.7, 29.7, 29.2, 28.9, 28.4,
28.4, 28.2, 23.6, 23.5, 23.5, 23.4, 23.3, 23.3, 23.2, 22.7, 22.7 (mixture of
rotamers/atropoisomers).
HRMS (ES+): m/z [M]+ calcd for C48H36I2: 866.0901; found: 866.0901.
(R)-3,3′-Di(biphenyl-4-yl)-2,2′-diiodo-5,5′,6,6′,7,7′,8,8′-octahydro-
1,1′-binaphthyl (4d)
[α]D25 –31.0 (c 10.0, CHCl3).
Following the typical procedure for 4a using (R)-3,3′-di(biphenyl-4-
yl)-H8-BINAM 8d (300 mg, 500 μmol) afforded the product as a
brownish solid; yield: 172 mg (42%).
IR (neat): 3055, 3026, 2929, 1495, 1443, 1432, 1420, 1373, 1352,
1308, 1279, 1170, 1028, 910, 874, 822, 766, 696 cm–1
.
1H NMR (300 MHz, CDCl3): δ = 7.53–7.30 (m, 10 H), 7.07 (s, 2 H),
2.91–2.72 (m, 4 H), 2.53–2.33 and 2.30–2.11 (m, 4 H), 1.88–1.65 (m, 8
H).
IR (neat): 2960, 2847, 2828, 1451, 1430, 765, 699 cm–1
.
1H NMR (300 MHz, CDCl3): δ = 7.77–7.30 (m, 18 H), 7.12 (s, 2 H),
13C NMR (75 MHz, CDCl3): δ = 148.9 (2 CAr), 145.4 (2 CAr), 145.2 (2 CAr),
137.8 (2 CAr), 135.3 (2 CAr), 131.3 (CAr), 129.8 (2 CAr), 129.6 (2 CAr),
129.6 (2 CAr), 127.9 (CAr), 127.8 (2 CAr), 127.3 (2 CAr), 102.2 (2 CAr), 29.6
(2 CH2), 29.1 (2 CH2), 23.5 (2 CH2), 22.7 (2 CH2).
2.91–2.73 (m, 4 H), 2.57–2.37 and 2.32–2.13 (m, 4 H), 1.92–1.67 (m, 8
H).
13C NMR (75 MHz, CDCl3): δ = 149.0 (2 CAr), 144.8 (2 CAr), 144.3 (2 CAr),
140.9 (2 CAr), 140.0 (2 CAr), 137.9 (2 CAr), 135.4 (4 CAr), 130.0 (2 CAr),
129.9 (2 CAr), 128.8 (2 CAr), 127.4 (2 CAr), 127.3 (4 CAr), 127.1 (2 CAr),
126.6 (2 CAr), 126.5 (2 CAr), 102.1 (2 CAr), 29.7 (2 CH2), 29.1 (2 CH2),
23.5 (2 CH2), 22.7 (2 CH2).
HRMS (ES+): m/z [M]+ calcd for C32H28I2: 666.0275; found: 666.0275.
HRMS (ES+): m/z [M]+ calcd for C44H36I2: 818.0901; found: 818.0906.
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M. Bekkaye, G. Masson
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Synthesis
(R)-2,2′-Diiodo-1,1′-binaphthyl (4e)
13C NMR (75 MHz, CDCl3): δ = 147.0 (2 Cq), 138.0 (2 Cq), 136.7 (2 CH),
135.8 (2 Cq, 130.4 (2 CH), 97.1 (2 Cq), 29.7 (2 CH2), 28.9 (2 CH2), 23.3
(2 CH2), 22.5 (2 CH2).
This compound was prepared according to the procedure of Quideau
et al.:10b To a solution of concd H2SO4 (65 mL) at –10 °C was added
portionwise NaNO2 (1.9 g, 275 mmol). The resulting suspension was
allowed to warm up to r.t. until complete dissolution was observed
and then it was cooled down again to –10 °C. A solution of commer-
cial (R)-BINAM (5, 1.65 g, 5.81 mmol) in pyridine (10 mL) was slowly
added and the resulting mixture was stirred at –10 °C for 2 h. The
mixture was transferred to a large Erlenmeyer flask at 0 °C and ice
was regularly added to the mixture over 1 h and, 30 min later, an ice-
cooled aq urea solution (1.65 g, 41 mL, 0.0165 mol) was slowly added.
This addition of urea caused abundant foam formation. To this mix-
ture was added an aqueous solution of ZnI2 (5.2 g, 0.0165 mol) and KI
(8.75 g, 0.0495 mmol) (16 mL). After filtration of the resulting brown-
ish suspension, the brown solid was triturated with Et2O and the re-
sulting red filtrate was discolored by washing with sat. aq NaHSO3
solution and dried (Na2SO4). The inorganic salts were removed by fil-
tration, and the organic layer was concentrated under reduced pres-
sure with silica gel to afford a crude residue that was purified by col-
umn chromatography (silica gel, heptane–CH2Cl2, gradient from
100:0 to 85:15) to afford the product as a yellowish solid; yield: 1.47 g
(50%); mp 206–208 °C.
HRMS (ES+): m/z [M]+ calcd for C20H20I2: 513.9649; found: 513.9649.
(R)-N-(2′-Amino-5,5′,6,6′,7,7′,8,8′-octahydro-1,1′-binaphthalen-2-
yl)acetamide (9)
Following the typical procedure for 11 using (R)-H8-BINAM 6 (292
mg, 1.0 mmol) afforded the product as a white foam; yield: 214 mg
(60%).
[α]D25 +27.0 (c 1.0, CHCl3).
IR (neat): 3430, 3370, 1681, 1602, 1591, 1496, 1342, 1241, 1150,
1040, 966, 830, 747, 670 cm–1
.
1H NMR (300 MHz, CDCl3): δ = 8.11 (d, J = 8.5 Hz, 1 H), 7.11 (d, J = 8.5
Hz, 1 H), 6.96 (d, J = 8.5 Hz, 1 H), 6.75 (br s, 1 H), 6.63 (d, J = 8.5 Hz, 1
H), 3.30 (br s, 2 H), 2.84–2.67 (m, 4 H), 2.36–2.01 (m, 4 H), 1.91 (s, 3
H), 1.81–1.43 (m, 8 H).
13C NMR (75 MHz, CDCl3): δ = 169.3 (Cq), 141.4 (CAr), 134.9 (CAr),
132.2 (CAr), 131.3 (CAr), 130.1 (CAr), 129.5 (CAr), 129.3 (CAr), 127.9 (CAr),
127.2 (CAr), 124.3 (CAr), 118.3 (CAr), 113.2 (CAr), 29.6 (2 CH2), 29.3 (2
CH2), 27.2 (2 CH2), 27.0 (2 CH2), 23.2 and 22.9 (CH3).
IR (neat): 2970, 1459, 812 cm–1
.
HRMS (ES+): m/z [M + Na]+ calcd for C22H26N2ONa: 357.1937; found:
357.1934.
1H NMR (300 MHz, CDCl3): δ = 8.07 (d, J = 8.0 Hz, 2 H), 7.94 (d, J = 8.0
Hz, 2 H), 7.72 (d, J = 8.0 Hz, 2 H), 7.54–7.48 (m, 2 H), 7.33–7.26 (m, 2
H), 7.10 (d, J = 8.0 Hz, 2 H).
13C NMR (75 MHz, CDCl3): δ = 144.7 (2 Cq), 135.6 (2 CH), 133.0 (2 Cq),
129.6 (2 CH), 128.2 (2 CH), 127.9 (2 CH), 127.3 (2 CH), 126.6 (2 CH),
126.4 (2 CH), 99.7 (2 Cq).
(R)-N-(2′-Amino-3′-bromo-5,5′,6,6′,7,7′,8,8′-octahydro-1,1′-
binaphthalen-2-yl)acetamide (10); Typical Procedure
To a stirred suspension of (R)-N-(2′-amino-1,1′-binaphthalen-2-yl)acet-
amide 9 (150 mg, 449 μmol) in glacial AcOH, maintained at r.t. with a
water bath, was added Br2 (460 μL, 8.98 mmol, 20 equiv) dropwise.
The resulting black suspension was stirred vigorously for several min-
utes, monitoring the reaction by TLC. Once all the starting material
had been consumed, the solution was cooled to approx. 0 °C with an
NaCl/ice-water bath, carefully quenched by slow addition of aq
NaHSO3 solution, and stirred vigorously until almost complete decol-
oration. AcOH was neutralized by slow addition of a non-sat. NaHCO3
solution and diluted with CH2Cl2. The resulting biphasic solution was
transferred to a separatory funnel, the layers were separated, and the
aqueous layer was extracted with CH2Cl2 (3 ×). The combined organic
extracts were washed with H2O and brine, and dried (Na2SO4). The in-
organic salts were removed by filtration, and the organic layer was
concentrated under reduced pressure with silica gel to afford a crude
residue that was purified by chromatography (silica gel, heptane–
EtOAc, gradient from 95:5 to 90:10) to afford the product as a white
foam; yield: 150 mg (81%).
HRMS (ES+): m/z [M]+ calcd for C20H12I2: 505.9023; found: 505.9026.
(R)-2,2′-Diiodo-5,5′,6,6′,7,7′,8,8′-octahydro-1,1′-binaphthyl (4f);
Typical Procedure
This compound was prepared according to the procedure of Yamamoto
et al.,16 with slight modifications: In an oven-dried flask equipped
with a stir bar, were placed (R)-H8-BINAM 6 (146 mg, 500 μmol),
NaNO2 (276 mg, 4 mmol, 8 equiv), and KI (830 mg, 5 mmol, 10 equiv).
Then, DMF (10 mL) was added, and the suspension was gently stirred
at r.t. to allow complete dissolution of the solids. The solution was
then cooled to approximately 0 °C with an NaCl/ice-water bath, and
stirred vigorously to avoid solidification of the solvent. 33% HBr in
AcOH (1 mL) was added dropwise quickly, but carefully, leading to
visible gas evolution. The resulting black solution was stirred for sev-
eral hours, monitoring the reaction by TLC. The solution was then
poured in sat. aq NaHCO3 solution and diluted with CH2Cl2. The re-
sulting biphasic solution was transferred to a separatory funnel, the
layers were separated, and the aqueous layer was extracted with
CH2Cl2 (3 ×). The combined organic extracts were washed with
NaHSO3 and brine, and dried (Na2SO4). The inorganic salts were re-
moved by filtration, and the organic layer was concentrated under re-
duced pressure with silica gel to afford a crude residue that was puri-
fied by chromatography (silica gel, heptane–CH2Cl2, gradient from
100:0 to 85:15) to afford the product as a yellowish solid; yield: 123
mg (48%); slightly contaminated with an unknown compound.
[α]D25 –10.0 (c 0.8, CHCl3).
IR (neat): 3432, 3367, 1690, 1599, 1540, 1430, 1397, 1312, 1267,
1221, 1170, 1039, 1018, 961, 832, 801 cm–1
.
1H NMR (300 MHz, CDCl3): δ = 8.09 (d, J = 8.5 Hz, 1 H), 7.24 (s, 1 H),
7.13 (d, J = 8.5 Hz, 1 H), 6.66 (br s, 1 H), 3.70 (br s, 2 H), 2.85–2.63 (m,
4 H), 2.34–1.97 (m, 4 H), 1.91 (s, 3 H), 1.81–1.54 (m, 8 H).
13C NMR (75 MHz, CDCl3): δ = 168.3 (Cq), 142.2 (CAr), 139.3 (CAr),
135.7 (CAr), 134.2 (CAr), 133.2 (CAr), 132.8 (CAr), 129.7 (CAr), 129.0 (CAr),
125.8 (CAr), 119.9 (CAr), 118.8 (CAr), 107.0 (CAr), 31.9 (2 CH2), 29.5 (2
CH2), 29.0 (2 CH2), 27.0 and 26.9 (2 CH2), 23.0 and 22.8 (CH3).
IR (neat): 2980, 1450, 1236, 1070, 1030, 881 cm–1
1H NMR (300 MHz, CDCl3): δ = 7.69 (d, J = 8.0 Hz, 2 H), 6.85 (d, J = 8.0
.
HRMS (ES+): m/z [M + H]+ calcd for C22H26BrN2O: 413.1223; found:
413.1221.
Hz, 2 H), 2.89–2.69 (m, 4 H), 2.41–2.00 (m, 4 H), 1.80–1.60 (m, 8 H).
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(R)-N-(2′-Iodo-3′-phenyl-5,5′,6,6′,7,7′,8,8′-octahydro-1,1′-binaph-
thalen-2-yl)acetamide (4g)
IR (neat): 3412, 3310, 3055, 2956, 2924, 1671, 1621, 1596, 1518,
1497, 1457, 1423, 1366, 1335, 1274, 1304, 1274, 1147, 1105, 1061,
827, 811, 773, 745, 691 cm–1
.
Following the typical procedures for 8a and 4a using (R)-N-(2′-ami-
no-3′-phenyl-5,5′,6,6′,7,7′,8,8′-octahydro-1,1′-binaphthalen-2-yl)acet-
amide (10, 206 mg, 500 μmol) afforded the product as a white solid;
yield: 93 mg (34%).
1H NMR (300 MHz, CDCl3): δ = 8.56 (d, J = 8.5 Hz, 1 H), 8.11 (d, J = 8.5
Hz, 1 H), 8.04 (d, J = 8.5 Hz, 1 H), 7.97–7.88 (m, 2 H), 7.75 (d, J = 8.5 Hz,
1 H), 7.53 (t, J = 8.5 Hz, 1 H), 7.42 (t, J = 8.5 Hz, 1 H), 7.33–7.21 (m, 2
H), 7.14 (d, J = 8.5 Hz, 1 H), 6.91 (d, J = 8.5 Hz, 1 H), 6.62 (br s, 1 H),
1.85 (s, 3 H).
13C NMR (75 MHz, DMSO-d6): δ = 171.1 (Cq), 145.0 (CAr), 135.9 (2 CAr),
133.1 (CAr), 130.4 (2 CAr), 129.4 (2 CAr), 128.3 (2 CAr), 128.2 (2 CAr),
127.9 (2 CAr), 127.1 (CAr), 126.8 (CAr), 126.4 (CAr), 125.1 (2 CAr), 121.0
(CAr), 24.0 (CH3).
[α]D25 –20.0 (c 1.0, CHCl3).
IR (neat): 3411, 3293, 2927, 2856, 2833, 1676, 1595, 1506, 1433,
1413, 1371, 1310, 1288, 1241, 1146, 1028, 911, 813, 766, 699 cm–1
.
1H NMR (300 MHz, CDCl3): δ = 7.48–7.28 (m, 5 H), 7.21–7.05 (m, 3 H),
6.50 (br s, 1 H), 2.90–2.69 (m, 4 H), 2.44–1.87 (m, 4 H), 1.96 (s, 3 H),
1.86–1.59 (m, 8 H).
13C NMR (75 MHz, CDCl3): δ = 168.1 (Cq), 145.6 (CAr), 145.0 (CAr),
141.7 (CAr), 138.6 (CAr), 136.6 (CAr), 134.4 (CAr), 134.1 (CAr), 131.9 (CAr),
130.7 (CAr), 129.4 (2 CAr), 129.3 (CAr), 128.8 (CAr), 127.9 (2 CAr), 127.5 (2
CAr), 119.2 (CAr), 29.6 and 28.6 (2 CH2), 27.5 and 27.3 (2 CH2), 24.6
(CH3), 23.3 and 23.2 (2 CH2), 22.8 and 22.6 (2 CH2).
HRMS (ES+): m/z [M + Na]+ calcd for C22H16INONa: 460.0169; found:
460.0170.
3-(1-Hydroxynaphthalen-2-yl)propanoic Acid (1)
This compound was prepared according to the procedure reported by
Kita et al. with slight modifications:4a To a stirred suspension of 3,4-
dihydro-2H-benzo[h]chromen-2-one (1 g, 5 mmol) in anhyd THF (36
mL) was added dropwise 1 M aq LiOH solution (17.9 mL), during
which the solution progressively turned green. After complete addi-
tion, the resulting brown solution was stirred vigorously at r.t. over-
night. The pH was then adjusted to 3 with 2 M aq HCl. The mixture
was diluted with EtOAc, the biphasic solution was transferred to a
separatory funnel, the layers were separated, and the aqueous layer
was extracted with EtOAc (3 ×). The combined organic extracts were
washed with brine, and dried (Na2SO4). The inorganic salts were re-
moved by filtration, and the organic layer was concentrated under re-
duced pressure with silica gel to afford a crude residue that was puri-
fied by chromatography (silica gel, heptane–EtOAc, gradient from
80:20 to 30:70) to afford the product as a white solid; yield: 992 mg
(83%); mp 105–107 °C.
HRMS (ES+): m/z [M + Na]+ calcd for C28H28INONa: 544.1108; found:
544.1104.
(R)-N-(2′-Amino-1,1′-binaphthalen-2-yl)acetamide (11)
Commercial (R)-BINAM 5 was mono-acylated according to the proce-
dure reported by Shi et al. with slight modifications:17 To a stirred
suspension of (R)-BINAM (284 mg, 1.0 mmol) and glacial AcOH (600
μL, 10 equiv) in CH2Cl2 (10 mL), cooled to 5 °C with an ice/water bath,
was added Ac2O (104 μL, 1.1 mmol, 1.1 equiv) dropwise. The ice bath
was removed and the solution was stirred overnight at r.t. The result-
ing mixture was then cooled with an ice/water bath and carefully
quenched by slow addition of 2 M aq NaOH under vigorous stirring to
reach pH 7. The resulting biphasic solution was transferred to a sepa-
ratory funnel, and the layers were separated. The aqueous layer was
extracted with CH2Cl2 (3 ×). Combined organic extracts were washed
with H2O and brine, and dried (Na2SO4). The inorganic salts were re-
moved by filtration, and the organic layer was concentrated under re-
duced pressure with silica gel to afford a crude residue that was puri-
fied by chromatography (silica gel, heptane–EtOAc, gradient from
80:20 to 50:50) to afford the product as a white solid; yield: 220 mg
(63%).
IR (neat): 3100, 1681, 1082, 808 cm–1
.
1H NMR (300 MHz, CDCl3): δ = 8.25–8.22 (m, 1 H), 7.76–7.71 (m, 1 H),
7.47–7.42 (m, 2 H), 7.39 (d, J = 8.5 Hz, 1 H), 7.17 (d, J = 8.5 Hz, 1 H),
3.04 (t, J = 7.0 Hz, 2 H), 2.87 (t, J = 7.0 Hz, 2 H).
13C NMR (75 MHz, acetone-d6): δ = 176.6 (Cq), 150.5 (Cq), 134.6 (CAr),
126.4 (CAr), 128.2 (CAr), 126.7 (CAr), 126.3 (CAr), 125.7 (CAr), 122.7 (CAr),
122.1 (CAr), 120.7 (CAr), 35.1 (CH2), 25.7 (CH2).
[α]D25 +27.0 (c 1.0, CHCl3).
HRMS (ES+): m/z [M + Na]+ calcd for C13H12O3Na: 239.0679; found:
239.0684.
IR (neat): 3400, 1676, 1595, 1499, 1445, 1270, 1040, 965, 670 cm–1
.
1H NMR(300 MHz, CDCl3): δ = 8.58 (d, J = 8.5 Hz, 1 H), 8.00 (d, J = 9.0
Hz, 1 H), 7.91 (d, J = 8.0 Hz, 1 H), 7.87 (d, J = 9.0 Hz, 1 H), 7.83 (d,
J = 8.0 Hz, 1 H), 7.41 (t, J = 7.5 Hz, 1 H), 7.31–7.18 (m, 4 H), 7.15 (d,
J = 8.5 Hz, 1 H), 7.05 (br s, 1 H), 6.93 (d, J = 8.5 Hz, 1 H), 4.17 (br s, 2 H),
1.85 (s, 3 H).
13C NMR (75 MHz, CDCl3): δ = 168.7 (Cq), 142.7 (Cq), 135.1 (Cq), 133.6
(Cq), 130.4 (4 CAr), 129.3 (2 CAr), 128.2 (2 CAr), 127.3 (2 CAr), 126.8 (CAr),
125.4 (CAr), 125.1 (CAr), 123.7 (CAr), 122.8 (CAr), 120.9 (CAr), 118.1 (CAr),
24.8 (CH3).
1′H,3H-Spiro[furan-2,2′-naphthalene]-1′,5(4H)-dione (2); General
Procedure
To a stirred suspension of the iodoarene 4 (0.1 equiv, 5 μmol) in an-
hyd CHCl3 (1 mL) was added wet mCPBA (77%, 14.5 mg, 65 μmol, 1.3
equiv). The solution was cooled to 0 °C with a cooler, and stirred for
10 min. Then, 3-(1-hydroxynaphthalen-2-yl)propanoic acid (1, 10.8
mg, 50 μmol, 1 equiv,) was added, and glassware was rinsed with
CHCl3 (1 mL); the solution was stirred at 0 °C for several hours, moni-
toring the reaction by TLC. When the reaction was complete, the mix-
ture was carefully poured into sat. NaHCO3 solution and diluted with
CH2Cl2. The resulting biphasic solution was transferred into a separa-
tory funnel and the layers were separated. The aqueous layer was ex-
tracted with CH2Cl2 (3 ×). The combined organic extracts were
washed with NaHCO3 and brine, and dried (Na2SO4). The inorganic
salts were removed by filtration, and the organic layer was concen-
trated under reduced pressure to afford a crude residue that was puri-
HRMS(ES+): m/z [M + Na]+ calcd for C22H18N2ONa: 349.1311; found:
349.1311.
(R)-N-(2′-Iodo-1,1′-binaphthalen-2-yl)acetamide (4h)
Following the typical procedure for 4a using (R)-N-(2′-amino-1,1′-
binaphthalen-2-yl)acetamide 11 (300 mg, 500 μmol) afforded the
product as a white solid; yield: 117 mg (51%).
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2016, 48, 302–312

311
M. Bekkaye, G. Masson
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Synthesis
fied by chromatography (silica gel, heptane–EtOAc, gradient from
95:5 to 80:20) to afford the product as a white solid, see Table 2; mp
103–105 °C.
(3) For seminal electrochemical oxidations of iodoarenes, see:
(a) Fuchigami, T.; Fujita, T. J. Org. Chem. 1994, 59, 7190.
(b) Fujita, T.; Fuchigami, T. Tetrahedron Lett. 1996, 37, 4725.
Seminal oxidations of iodoarenes using chemical oxidants, see:
(c) McKillop, A.; Kemp, D. Tetrahedron 1989, 45, 3299.
(d) Kazmierczak, P.; Skulski, L.; Kraszkiewicz, L. Molecules 2001,
6, 881. (e) Zielinska, A.; Skulski, L. Molecules 2002, 7, 806.
(f) Sharefkin, J. G.; Saltzman, H. Org. Synth. 1963, 43, 62.
(g) Zielinska, A.; Skulski, L. Molecules 2005, 10, 190. (h) Ochiai,
M.; Takeuchi, Y.; Katayama, T.; Sueda, T.; Miyamoto, K. J. Am.
Chem. Soc. 2005, 127, 12244. (i) Hossain, M. D.; Kitamura, T.
J. Org. Chem. 2005, 70, 6984. (j) Hossain, M. D.; Kitamura, T. Bull.
Chem. Soc. Jpn. 2006, 79, 142.
(4) (a) Dohi, T.; Maruyama, A.; Takenaga, N.; Senami, K.;
Minamitsuji, Y.; Fujioka, H.; Caemmerer, S. B.; Kita, Y. Angew.
Chem. Int. Ed. 2008, 47, 3787. (b) Dohi, T.; Takenaga, N.; Nakae,
T.; Toyoda, Y.; Yamasaki, M.; Shiro, M.; Fujioka, H.; Maruyama,
A.; Kita, Y. J. Am. Chem. Soc. 2013, 135, 4558. (c) Uyanik, M.;
Yasui, T.; Ishihara, K. Angew. Chem. Int. Ed. 2010, 49, 2175.
(d) Uyanik, M.; Yasui, T.; Ishihara, K. Tetrahedron 2010, 66, 5841.
(e) Murray, S. J.; Ibrahim, H. Chem. Commun. 2015, 51, 2376.
(f) Uyanik, M.; Sasakura, N.; Kaneko, E.; Ohori, K.; Ishihara, K.
Chem. Lett. 2015, 44, 179.
HPLC (Daicel Chiralpak OD-H, hexane–i-PrOH, 85:15, flow rate 1.0
mL/min, 230 nm): tR = 16.30, 21.51 min.
IR (neat): 1788, 1693, 1597, 1481, 1454, 1323, 1296, 1178, 1123,
1032, 930, 787 cm–1
.
1H NMR (300 MHz, CDCl3): δ = 8.02 (d, J = 8.0 Hz, 1 H), 7.63 (t, J = 7.5
Hz, 1 H), 7.41 (t, J = 7.5 Hz, 1 H), 7.26 (d, J = 7.5 Hz, 1 H), 6.66 (d,
J = 10.0 Hz, 1 H), 6.20 (d, J = 10.0 Hz, 1 H), 2.98–2.85 and 2.65–2.55
and 2.47–2.39 and 2.25–2.13 (m, 4 H).
13C NMR (75 MHz, CDCl3): δ = 196.5 (Cq), 176.5 (Cq), 136.7 (CAr), 135.6
(CAr), 132.1 (CAr), 128.8 (CAr), 127.9 (CAr), 127.8 (CAr), 127.5 (CAr), 127.1
(CAr), 83.4 (Cq), 31.0 (CH2), 26.4 (CH2).
HRMS (ES+): m/z [M + H]+ calcd for C13H11O3: 215.0703; found:
215.0699.
Acknowledgment
We thank ICSN for financial support. M.B. thanks MESR for a doctoral
fellowship, University of Paris Sud. Ethan Wappes is gratefully ac-
knowledged for reading the manuscript and for constructive com-
ments. Audrey Dumoulin is gratefully acknowledged for measuring
optical rotations.
(5) (a) Guilbault, A.-A.; Basdevant, B.; Wanie, V.; Legault, C. Y. J. Org.
Chem. 2012, 77, 11283. (b) Volp, K. A.; Harned, A. M. Chem.
Commun. 2013, 49, 3001. (c) Brenet, S.; Berthiol, F.; Einhorn, J.
Eur. J. Org. Chem. 2013, 8094.
(6) Examples of chiral hypervalent iodide(III) compounds, see:
(a) Imamoto, T.; Koto, H. Chem. Lett. 1986, 15, 967.
(b) Hatzigrigoriou, E.; Varvoglis, A.; Bakola-Christianopoulou,
M. J. Org. Chem 1990, 55, 315. (c) Ray, D. G.; Koser, G. F. J. Am.
Chem. Soc. 1990, 112, 5672. (d) Ochiai, M.; Takaoka, Y.; Masaki,
Y.; Nagao, Y.; Shiro, M. J. Am. Chem. Soc. 1990, 112, 5677. (e) Ray,
D. G.; Koser, G. F. J. Org. Chem. 1992, 57, 1607. (f) Rabah, G. A.;
Koser, G. F. Tetrahedron Lett. 1996, 37, 6453. (g) Wirth, T.; Hirt,
U. H. Tetrahedron: Asymmetry 1997, 8, 23. (h) Hirt, U. H.;
Spingler, B.; Wirth, T. J. Org. Chem. 1998, 63, 7674. (i) Tohma, H.;
Takizawa, S.; Watanabe, H.; Kita, Y. Tetrahedron Lett. 1998, 39,
4547. (j) Ochiai, M.; Kitagawa, Y.; Takayama, N.; Takaoka, Y.;
Shiro, M. J. Am. Chem. Soc. 1999, 121, 9233. (k) Tohma, H.;
Takizawa, S.; Watanabe, H.; Fukuoka, Y.; Maegawa, T.; Kita, Y.
J. Org. Chem. 1999, 64, 3519. (l) Tohma, H.; Takizawa, S.;
Morioka, H.; Maegawa, T.; Kita, Y. Chem. Pharm. Bull. 2000, 48,
445. (m) Hirt, U. H.; Schuster, M. F. H.; French, A. N.; Wiest, O.
G.; Wirth, T. Eur. J. Org. Chem. 2001, 1569. (n) Altermann, S. M.;
Richardson, R. D.; Page, T. K.; Schmidt, R. K.; Holland, E.;
Mohammed, U.; Paradine, S. M.; French, A. N.; Richter, C.; Bahar,
A. M.; Witulski, B.; Wirth, T. Eur. J. Org. Chem. 2008, 5315.
(o) Fujita, M.; Wakita, M.; Sugimura, T. Chem. Commun. 2011,
47, 3983. (p) Fujita, M.; Mori, K.; Shimogaki, M.; Sugimura, T.
Org. Lett. 2012, 14, 1294. (q) Farid, U.; Wirth, T. Angew. Chem.
Int. Ed. 2012, 51, 3462. (r) Farid, U.; Malmedy, F.; Claveau, R.;
Albers, L.; Wirth, T. Angew. Chem. Int. Ed. 2013, 52, 7018.
(s) Takesue, T.; Fujita, M.; Sugimura, T.; Akutsu, H. Org. Lett.
2014, 16, 4634.
Supporting Information
Supporting information for this article is available online at
http://dx.doi.org/10.1055/s-0035-1560512.
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References
(1) For reviews, see: (a) Ortiz, F. L.; Iglesias, M. J.; Fernández, I.;
Sánchez, C. M. A.; Ruiz Gómez, G. Chem. Rev. 2007, 107, 1580.
(b) Quideau, S.; Pouységu, L.; Deffieux, D. Synlett 2008, 467.
(c) Hudlicky, T.; Reed, J. W. Synlett 2009, 685. (d) Roche, S. P.;
Porco, J. A. Angew. Chem. Int. Ed. 2011, 50, 4068. (e) Zhuo, C.-X.;
Zhang, W.; You, S.-L. Angew. Chem. Int. Ed. 2012, 51, 12662.
(f) Ciufolini, M. A. Can. J. Chem. 2014, 92, 186. (g) Harned, A. M.
Tetrahedron Lett. 2014, 55, 4681. (h) Maertens, G.; L’Homme, C.;
Canesi, S. Front. Chem. 2015, 2, 115.
(2) For reviews on hypervalent iodine chemistry, see: (a) Ciufolini,
M. A.; Braun, N. A.; Canesi, S.; Ousmer, M.; Chang, J.; Chai, D.
Synthesis 2007, 3759. (b) Zhdankin, V. V.; Stang, P. J. Chem. Rev.
2008, 108, 5299. (c) Ochiai, M.; Miyamoto, K. Eur. J. Org. Chem.
2008, 4229. (d) Dohi, T.; Kita, Y. Chem. Commun. 2009, 2073.
(e) Uyanik, M.; Ishihara, K. Chem. Commun. 2009, 2086.
(f) Ngatimin, M.; Lupton, D. W. Aust. J. Chem. 2010, 63, 653.
(g) Liang, H.; Ciufolini, M. A. Angew. Chem. Int. Ed. 2011, 50,
11849. (h) Kita, Y.; Dohi, T.; Morimoto, K. J. Synth. Org. Chem.,
Jpn. 2011, 69, 1241. (i) Fernández González, D.; Benfatti, F.;
Waser, J. ChemCatChem 2012, 4, 955. (j) Yusubov, M. S.;
Zhdankin, V. V. Curr. Org. Synth. 2012, 9, 247. (k) Farid, U.;
Wirth, T. In Asymmetric Synthesis II; Christmann, M.; Bräse, S.,
Eds.; Wiley-VCH: Weinheim, 2012, 197. (l) Brown, M.; Farid, U.;
Wirth, T. Synlett 2013, 24, 424. (m) Parra, A.; Reboredo, S. Chem.
Eur. J. 2013, 19, 17244. (n) Singh, F. V.; Wirth, T. Chem. Asian J.
2014, 9, 950. (o) Kumar, R.; Wirth, T. Top. Curr. Chem. 2015, doi:
10.1007/128_2015_639.
(7) (a) Lebée, C.; Kataja, A. O.; Blanchard, F.; Masson, G. Chem. Eur. J.
2015, 21, 8399. (b) Dumoulin, A.; Lalli, C.; Retailleau, P.;
Masson, G. Chem. Commun. 2015, 51, 5383. (c) Lalli, C.;
Dumoulin, A.; Lebée, C.; Drouet, F.; Guérineau, V.; Touboul, D.;
Gandon, V.; Zhu, J.; Masson, G. Chem. Eur. J. 2015, 21, 1704.
(d) Dagousset, G.; Erb, W.; Zhu, J.; Masson, G. Org. Lett. 2014, 16,
2554. (e) He, L.; Laurent, G.; Retailleau, P.; Folléas, B.; Brayer, J.-
L.; Masson, G. Angew. Chem. Int. Ed. 2013, 52, 11088. (f) Courant,
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2016, 48, 302–312

312
M. Bekkaye, G. Masson
Paper
Synthesis
T.; Kumarn, S.; He, L.; Retailleau, P.; Masson, G. Adv. Synth. Catal.
2013, 355, 836. (g) He, L.; Bekkaye, M.; Retailleau, P.; Masson, G.
Org. Lett. 2012, 14, 3158. (h) Dagousset, G.; Zhu, J.; Masson, G.
J. Am. Chem. Soc. 2011, 133, 14804. (i) Liu, H.; Dagousset, G.;
Masson, G.; Retailleau, P.; Zhu, J. J. Am. Chem. Soc. 2009, 131,
4598.
(15) (a) Kranz, M.; Clark, T.; v. R. Schleyer, P. J. Org. Chem. 1993, 58,
3317. (b) Brath, H.; Dubovská, M.; Juríček, M.; Kasák, P.; Putala,
M. Collect. Czech. Chem. Commun. 2004, 69, 1517. (c) Brown, K.
J.; Berry, M. S.; Waterman, K. C.; Lingenfelter, D.; Murdoch, J. R.
J. Am. Chem. Soc. 1984, 106, 4717. (d) Mešková, M.; Putala, M.
Tetrahedron Lett. 2011, 52, 5379. (e) Kasak, P.; Brath, H.;
Krascsenicsová-Polaková, K.; Kicková, A.; Moldovan, N.; Putala,
M. Collect. Czech. Chem. Commun. 2007, 72, 1139.
(16) Usanov, D. L.; Yamamoto, H. Angew. Chem. Int. Ed. 2010, 49,
8169.
(17) We obtained a mixture of non-reacted and over-acylated mate-
rials as major products. See also: Wang, C.-J.; Shi, M. Eur. J. Org.
Chem. 2003, 2823.
(18) (a) Tohma, H.; Maruyama, A.; Maeda, A.; Maegawa, T.; Dohi, T.;
Shiro, M.; Morita, T.; Kita, Y. Angew. Chem. Int. Ed. 2004, 43,
3595. (b) Dohi, T.; Maruyama, A.; Yoshimura, M.; Morimoto, K.;
Tohma, H.; Shiro, M.; Kita, Y. Chem. Commun. 2005, 2205.
(19) (a) Lewis, N.; Wallbank, P. Synthesis 1987, 1103. (b) Barret, R.;
Daudon, M. Tetrahedron Lett. 1990, 31, 4871. (c) Mal, D.; Roy, H.
N.; Hazra, N. K.; Adhikari, S. Tetrahedron 1997, 53, 2177.
(d) Quideau, S.; Looney, M. A.; Pouységu, L. Org. Lett. 1999, 1,
1651. (e) Quideau, S.; Pouységu, L.; Oxoby, M.; Looney, M. A.
Tetrahedron 2001, 57, 319. (f) Wood, J. L.; Graeber, J. K.;
Njardarson, J. T. Tetrahedron 2003, 59, 8855.
(20) Koser, G. F. Hypervalent Halogen Compounds, In The Chemistry of
Functional Groups, Supplement D; Patai, S.; Rappoport, Z., Eds.;
Wiley: Chichester, 1983, Chap. 18, 729.
(21) (a) Lee, C.-K.; Mak, T. C. W.; Li, W.-K.; Kirner, J. F. Acta Crystal-
logr., Sect. B 1977, 33, 1620. (b) Alcock, N. W.; Countryman, R.
M.; Esperás, S.; Sawyer, J. F. J. Chem. Soc., Dalton. Trans. 1979,
854.
(8) (a) Carboni, A.; Dagousset, G.; Magnier, E.; Masson, G. Org. Lett.
2014, 16, 1240. (b) Bekkaye, M.; Su, Y.; Masson, G. Eur. J. Org.
Chem. 2013, 3978. (c) Drouet, F.; Masson, G.; Zhu, J. Org. Lett.
2013, 15, 2854. (d) Drouet, F.; Fontaine, P.; Masson, G.; Zhu, J.
Synthesis 2009, 1370. (e) Fontaine, P.; Chiaroni, A.; Masson, G.;
Zhu, J. Org. Lett. 2008, 10, 1509.
(9) Richardson, R. D.; Page, T. K.; Altermann, S.; Paradine, S. M.;
French, A. N.; Wirth, T. Synlett 2007, 538.
(10) (a) Quideau, S.; Lyvinec, G.; Marguerit, M.; Bathany, K.; Ozanne-
Beaudenon, A.; Buffeteau, T.; Cavagnat, D.; Chénedé, A. Angew.
Chem. Int. Ed. 2009, 48, 4605. (b) Bosset, C.; Coffinier, R.;
Peixoto, P. A.; El Assal, M.; Miqueu, K.; Sotiropoulos, J.-M.;
Pouységu, L.; Quideau, S. Angew. Chem. Int. Ed. 2014, 53, 9860.
(11) Recently Wirth and co-workers reported the synthesis of chiral
diaryliodonium salts derived from BINI, see: Brown, M.;
Delorme, M.; Malmedy, F.; Malmgren, J.; Olofsson, B.; Wirth, T.
Synlett 2015, 26, 1573.
(12) (a) Li, T.; Tsuda, Y.; Minoura, K.; In, Y.; Ishida, T.; Lazarus, L. H.;
Okada, Y. Chem. Pharm. Bull. 2006, 54, 873. (b) Miles, K. C.; Le,
C.; Stambuli, J. P. Chem. Eur. J. 2014, 20, 11336. (c) Liu, T.-F.; Zou,
L.; Feng, D.; Chen, Y.-P.; Fordham, S.; Wang, X.; Liu, Y.; Zhou, H.-
C. J. Am. Chem. Soc. 2014, 136, 7813.
(13) (a) Guo, H.; Ding, K. Tetrahedron Lett. 2000, 41, 10061. (b) Kano,
T.; Tanaka, Y.; Osawa, K.; Yurino, T.; Maruoka, K. J. Org. Chem.
2008, 73, 7387.
(14) Also, see: Wang, Y.-M.; Kuzniewski, C. N.; Rauniyar, V.; Hoong,
C.; Toste, F. D. J. Am. Chem. Soc. 2011, 133, 12972.
(22) (a) Siebert, H.; Handrich, M. Z. Anorg. Allg. Chem. 1976, 426, 173.
(b) Gallos, J.; Varvoglis, A.; Alcock, N. W. J. Chem. Soc., Perkin
Trans. 1 1985, 757.
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