Aminohydroxylation of olefins with iminopyridinium ylides by dual Ir photocatalysis and Sc(OTf)3catalysis

Article abstract of DOI:10.1016/j.tet.2016.05.045

We have developed a new strategy for catalytic aminohydroxylation of olefins with an N-protected iminopyridinium ylide as the amine source. Iminopyridinium ylides N-protected with TFAc (trifluoroacetyl), Boc (tert-butoxycarbonyl), Troc (2,2,2-trichloroethoxycarbonyl), and Alloc (allyloxycarbonyl) groups serve as N-centered radical precursors when combined with fac-[Ir(ppy)₃] photocatalysis and Sc(OTf)₃catalysis. The dual Ir photoredox/Sc(OTf)₃catalysis proves to be effective for aminohydroxylation of olefins under mild reaction conditions to provide 2-aminoalcohol derivatives bearing a primary amino group.

Full text of DOI:10.1016/j.tet.2016.05.045

Accepted Manuscript
Aminohydroxylation of olefins with iminopyridinium ylides by dual Ir photocatalysis
and Sc(OTf) catalysis
3
Kazuki Miyazawa, Takashi Koike, Munetaka Akita
PII:
S0040-4020(16)30444-6
10.1016/j.tet.2016.05.045
TET 27772
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 5 April 2016
Accepted Date: 16 May 2016
Please cite this article as: Miyazawa K, Koike T, Akita M, Aminohydroxylation of olefins with
iminopyridinium ylides by dual Ir photocatalysis and Sc(OTf) catalysis, Tetrahedron (2016), doi:
3
10.1016/j.tet.2016.05.045.
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Aminohydroxylation of olefins with
iminopyridinium ylides by dual Ir
photocatalysis and Sc(OTf)3 catalysis
Leave this area blank for abstract info.
Kazuki Miyazawa, Takashi Koike,* and Munetaka Akita*
R1-27, 4259 Nagatsuta-cho, Midori-ku, Yokohama 226-8503, Japan
regiospecific aminohydroxylation
H2O
OH
H
N
removable
protective
group
photoredox
catalysis
Sc(OTf)3
catalysis
R2
R1
PG
R1
PG:
R2
N
N
PG
16 examples
visible light

ACCEPTED MANUSCRIPT
Tetrahedron
journal homepage: www.elsevier.com
Aminohydroxylation of olefins with iminopyridinium ylides by dual Ir photocatalysis
and Sc(OTf)3 catalysis
Kazuki Miyazawa,a Takashi Koike,a and Munetaka Akitaa
aLaboratory for Chemistry and Life Science, Institute of Innovative Research, Tokyo Institute of Technology, R1-27, 4259 Nagatsuta-cho, Midori-ku, Yokohama
226-8503, Japan
ARTICLE INFO
ABSTRACT
Article history:
Received
Received in revised form
Accepted
We have developed a new strategy for catalytic aminohydroxylation of olefins with an N-
protected iminopyridinium ylide as the amine source. Iminopyridinium ylides N-protected with
TFAc (trifluoroacetyl), Boc (tert-butoxycarbonyl), Troc (2,2,2-trichloroethoxycarbonyl), and
Alloc (allyloxycarbonyl) groups serve as N-centered radical precursors when combined with
fac-[Ir(ppy)3] photocatalysis and Sc(OTf)3 catalysis. The dual Ir photoredox/Sc(OTf)3 catalysis
proves to be effective for aminohydroxylation of olefins under mild reaction conditions to
provide 2-aminoalcohol derivatives bearing a primary amino group.
Available online
Keywords:
Photoredox catalysis
Lewis acid catalysis
Aminohydroxylation
Nitrogen-centered radical
2009 Elsevier Ltd. All rights reserved
.
1. Introduction
aminopyridinium reagents (1) have redox potentials enough to
undergo single electron transfer from the photoexcited catalyst,
(ii) the reverse electron transfer process, i.e., a back electron
transfer process, is suppressed to some extent, and (iii) the
generated N-centered radicals are reactive enough to add to
olefins.
Photoredox catalysis with, for example, well-known
[Ru(bpy)3]2+ and fac-[Ir(ppy)3] has emerged as a useful strategy
for radical reactions for the past several years.1 In particular, a
variety of reactions involving carbon-centered radicals have been
highlighted. Recently, photoredox-catalyzed reactions of
nitrogen-centered radicals have also attracted a considerable
interest of synthetic chemists.2 Nitrogen atom-containing
molecules are frequently found in biologically active natural
products and drugs. Various types of reactions via nitrogen-
centered radical species such as hydrogen atom abstraction3 and
radical amination of arenes4 and olefins5 are important for
construction of carbon–nitrogen bonds. Previously, we reported
on photoredox-catalyzed aminohydroxylation of olefins with N-
(a) previous work
OH
H
Ir photocat.
N
R2
NHTs
N
Ts
BF4
+
R1
R1
acetone/H2O
visible light
R2
1a
via NHTs
(b) this work
Lewis acid cat. (M)
OH
R2
N
Ir photocat.
R2
NHPG
N
PG
+
R1
R1
acetone/H2O
visible light
2
Ts-protected 1-aminopyridinium salt (1a) (Ts
=
p-
via N(M)PG
toluenesulfonyl) used as a nitrogen-centered radical precursor
(Scheme 1(a)).2n The protocol leads to efficient and regiospecific
synthesis of 2-aminoalcohols under mild reaction conditions, but
the Ts group is not always easily removed from the
PG: readily removable protective group (TFAc, Bz, Boc, Troc and Alloc)
Scheme 1. Photoredox-catalyzed aminohydroxylation of
olefins.
corresponding
2-aminoalcohol
scaffolds.
While
1-
aminopyridinium precursors with readily removable protective
groups such as TFAc (1b) (TFAc = trifluoroacetyl) group were
available, the photocatalytic aminohydroxylation with 1b turned
out to be sluggish. We envisaged that efficient
aminohydroxylation is viable if (i) N-protected 1-
———
More recently, it has been reported that highly programmed
cooperative
photoredox/Lewis
acid
catalysis
induces
transformations, which cannot be achieved by each
component.1g,6 We expected that, by the use of Lewis acid
catalyst in place of proton, Brønsted acid, as the iminopyridinium
Corresponding author. Tel.: +81-45-924-5229; fax: +81-45-924-5230; e-mail: koike.t.ad@m.titech.ac.jp (T. Koike)
Corresponding author. Tel.: +81-45-924-5230; fax: +81-45-924-5230; e-mail: makita@res.titech.ac.jp (M. Akita)

2
Tetrahedron
ACCEPTED MANUSCRIPT
ylide (2) activator, the reactivity of the resultant ylide-Lewis
[Ir(ppy)3] turned out to be the best (entries 7 and 8). Furthermore,
acid adduct will be tuned as desired (Scheme 1(b)). Herein we
will report that dual action of photoredox catalysis and Lewis
acid catalysis to N-protected iminopyridinium ylides (2) bearing
readily removable protective groups (PG) such as TFAc, Bz
addition of an extra amount of 3a with respect to 2b improved
the efficiency (entries 9 and 10). To be noted is that the present
reaction did not proceed at all either in the absence of the
photocatalyst or in the dark (entries 11 and 12).
(benzoyl),
Boc
(tert-butoxycarbonyl),
Troc
(2,2,2-
2.2. Scope of the present aminohydroxylation
trichloroethoxycarbonyl), and Alloc (allyloxycarbonyl) promotes
aminohydroxylation of olefins to furnish N-protected 2-
aminoalcohol.
With the optimal reaction conditions in hand, we investigated
the scope of the present dual catalytic aminohydroxylation.
2. Results and discussion
2.2.1. Scope for olefin
Sc(OTf)3 (20 mol%)
OH
R2
2.1. Optimization of catalytic aminohydroxylation of styrene
(3a) with N-TFAc-protected iminopyridinium ylide (2b)
H
N
O
fac-[Ir(ppy)3] (1 mol%)
N
+
N
O
R3
R1
acetone/H2O (9/1)
rt, 8 h
R1
CF3
1:2
R2 CF3
4bx
3x
2b
425 nm blue LEDs
Table 1. Optimization of photocatalytic aminohydroxylation
of styrene (3a).
Lewis acid (20 mol%)
photocat. (2 mol%)
OD
OH
H
OH
OH
D
H
H
N
O
N
O
N
O
N
O
N
O
N
+
Ph
Ph
Ph
acetone-d6/D2O, rt
425 nm blue LEDs
CF3
1:2
CF3
CF3
CF3
CF3
3a
Me
MeO
2b
4ba
4ba: 59%
4bb: 59%
4bc: 63%
OH
OH
OH
H
H
H
N
O
N
O
N
O
tBu
N
N
OTf
N
N
IrIII
N
H
N
CF3
CF3
CF3
N
N
N
N
O
F
Cl
Br
RuII
N
IrIII
N
N
N
N
CF3
4bd: 62%
4be: 42%
4bf: 54%
tBu
OH
OH
OH
H
1b
H
H
N
Me
Ph
N
O
CF3
O
N
O
[Ru(bpy)3]2+
fac-[Ir(ppy)3]
[Ir(ppy)2(dtbbpy)]+
O
CF3
N
CF3
O
Entry Amine Photocat.
source
Additive
Reaction Yield
time/h of
4bg: 65%
4bh: 21%a,b
4bi: 85%a
4ba/%a
OH
H
OH
H
OH
H
1
2
3
4
5
6
7
8
9b
1b
2b
2b
2b
2b
2b
2b
2b
2b
fac-[Ir(ppy)3]
fac-[Ir(ppy)3]
fac-[Ir(ppy)3]
fac-[Ir(ppy)3]
fac-[Ir(ppy)3]
fac-[Ir(ppy)3]
[Ru(bpy)3](PF6)2
–
24
8
7
N
CF3
N
O
N
O
–
0
Me
O
CF3
CF3
Sc(OTf)3
Y(OTf)3
La(OTf)3
Zn(OTf)2
Sc(OTf)3
8
74
72
36
49
trace
8
4bj: 30%, 2.5:1 dra
4bk: 38%, 2.5:1 dr
4bl: 36%a,b
8
For detailed reaction conditions, see the experimental section.
Diastereomer ratios (dr) were determined by 1H NMR spectra of
crude reaction mixtures. Isolated yields are shown. aReaction
time was 24 h. b2 mol% of fac-[Ir(ppy)3] was used.
8
8
8
Fig. 1. The scope of olefins for the present aminohydroxy-
[Ir(ppy)2(dtbbpy)](PF6) Sc(OTf)3
8
lation.
fac-[Ir(ppy)3]
fac-[Ir(ppy)3]
–
Sc(OTf)3
Sc(OTf)3
Sc(OTf)3
Sc(OTf)3
8
41
63
0
10c 2b
11 2b
12d 2b
8
Styrenes bearing an electron-donating group (Me (3b) and
OMe (3c)) and an electron-withdrawing group (F (3d), Cl (3e),
and Br (3f)) on the benzene ring, and α-methylstyrene (3g)
afforded the corresponding products (4ba–bg) in 42–65%
isolated yields. In addition, methylenedioxy (3h) and pyridyl (3i)
groups were tolerated with the present reaction system (4bh:
21%, 4bi: 85%), but the reaction of 5-ethenyl-1,3-benzodioxole
(2h) was very slow. Furthermore, reactions of internal olefins
such as β-methylstyrene (3j) and 1,2-dihydronaphthalene (3k)
also produced aminoalcohols in 30% (4bj) and 38% yields (4bk)7,
respectively. An aliphatic olefin, methylenecyclopentane (3l),
could also be applied to the present aminohydroxylation (4bl:
36% yield), but a considerable amount of N-(cyclopent-1-en-
ylmethyl)-2,2,2-trifluoroacetamide (5bl) was also formed as a
by-product (Scheme 2).
24
24
fac-[Ir(ppy)3]
0
a
For reaction conditions, see the experimental section. Yields
1
were determined by H NMR spectroscopy using SiEt4 as an
internal standard. bThe ratio of 2b to 3a was 1:1. cThe ratio of 2b
to 3a was 2:1.dIn the dark.
We commenced examination of the reaction conditions for the
photocatalytic aminohydroxylation of styrene (3a) with N-TFAc-
protected aminopyridinium salt (1b) in the presence of a
photocatalyst, fac-[Ir(ppy)3] (2 mol%), following our previous
report.2n As we mentioned above, the reaction was sluggish
(entry 1 in Table 1). When N-TFAc-protected iminopyridinium
ylide (2b), which is a synthetic intermediate for 1b, was used in
place of 1b, again the reaction did not proceed at all (entry 2). To
our delight, addition of a catalytic amount of Sc(OTf)3 (20 mol%)
to 2b dramatically enhanced the yield of 2-aminoalcohol 4ba
(74% NMR yield) (entry 3). Investigation with other Lewis acid
catalysts proved that Sc(OTf)3 is the best option from a viewpoint
of efficiency and yield (entries 4–6). For the photocatalyst, fac-
OH
Sc(OTf)3 (20 mol%)
H
H
fac-[Ir(ppy)3] (2 mol%)
N
O
N
O
+
+
2b
3l
acetone/H2O (9/1)
rt, 24 h
425 nm blue LEDs
1:2
CF3
CF3
4bl
36%
isolated yield
5bl
23%
isolated yield
Scheme 2. Reaction of methylenecyclopentane (3l) with 2b.

mol% of Sc(OTf)3 (δH 8.33 (p)→8.42; 8.02 (m)→8.09). The
ACCEPTED MANUSCRIPT
2.2.2. Scope for the protective group on the
nitrogen atom
photoexcited Ir catalyst (Ered = –2.14 V vs. [Cp2Fe]) turned out to
be strong enough to reduce 2b (E2b = –2.11 V vs. [Cp2Fe] in
acetone; irreversible) and Sc(OTf)3 (ESc1/2 = –0.50 V vs. [Cp2Fe]
in acetone; reversible), while addition of Sc(OTf)3 to 2b did not
cause appearance of a distinct wave but broadening of the waves
for 2b and Sc(OTf)3 and appearance of a weak reduction wave
(around –1.65 V), which is indicative of formation of a new
chemical species. Finally, the photoexcited Ir catalyst was not
quenched by styrene 3a but by the additives in the order of 2b +
We supposed that the protective group on the nitrogen atom
plays a key role in determination of the reactivity of the N-
centered radical, i.e., efficient addition or hydrogen abstraction,
as well as the deprotection process after the aminohydroxylation.
Thus, we examined the scope for the protective groups (Fig. 2.).
Sc(OTf)3 (20 mol%)
fac-[Ir(ppy)3] (1 mol%)
OH
N
H
N
PG
+
Ph
Sc(OTf)3 > 2b > Sc(OTf)3. These observations suggest
N
acetone/H2O (9/1)
rt, 8 h
425 nm blue LEDs
Ph
PG
1:2
occurrence of an equilibrium for formation of some adduct
between 2b and Sc(OTf)3 but the generated adduct has remained
to be further characterized.
4xa
2x
3a
N
O
N
O
N
O
N
O
N
N
N
N
2.5. Control experiments for mechanistic aspects
OtBu
Ph
O
CCl3
O
2c
2d
4da: 58%
2e
4ea: 54%
2f
2.5.1. Reaction of 1-phenyl-2-(1-phenylethenyl)-
cyclopropane (3m)
4ca: 45%a
4fa: 43%
We examined the photocatalytic reaction of 1-phenyl-2-(1-
phenylethenyl)-cyclopropane (3m) with N-TFAc-protected
iminopyridinium ylide (2b) under the optimal photocatalytic
conditions (Scheme 4). As a result, aminohydroxylation was
accompanied by the ring-opening process of the cyclopropane
moiety to afford the linear aminoalcohol 4bm in a 56% isolated
yield (E/Z = 1:1). This result suggests that a radical intermediate
is involved in the present photocatalytic system.
For the reaction conditions, see the experimental section.
aReaction time was 24 h.
Fig. 2. The scope for the protective groups on the nitrogen
atom.
Common amide and carbamate groups can be incorporated
into the iminopyridinium ylide scaffolds. The N-Bz-protected
reagent (2c) was less effective (24 h) and afforded the
corresponding product (4ca) in a moderate yield (45%). It was
found that N-Boc- (2d), N-Troc- (2e), and N-Alloc-protected
reagents (2f) served in a manner similar to reagent 2b (4da: 58%,
4ea: 54% and 4fa: 43%, 8 h). Thus, in addition to the N-Ts-
protected alcohols reported previously,2n 2-aminoalcohols N-
protected with various groups have become available.
Sc(OTf)3 (20 mol%)
fac-[Ir(ppy)3] (1 mol%)
1.0 equiv. 2b
Ph
H
Ph
N
O
Ph
CF3
acetone/H2O (9/1), RT, 24 h
425 nm blue LEDs
Ph
3m
2.0 equiv.
OH
4bm: 56% yield, E:Z=1:1
Scheme 4. Aminohydroxylation through the ring-opening
process.
2.3. Deprotection of the N-protected aminoalcohol products
The obtained amide and carbamate derivatives 4 can be
converted to free primary amines 6 by further treatment.8 For
example, the TFAc derivative 4ba was deprotected under basic
conditions, i.e. by treatment with K2CO3, to afford 2-amino-1-
phenylethanol 6a in a 29% yield.8c On the other hand, the N-Boc-
derivative 4da was deprotected under acidic conditions, i.e. by
exposure to ethereal HCl solution, to furnish 6a•HCl in a 66%
isolated yield.8e Thus free β-hydroxylated primary amines 6 can
be synthesized from olefins 3 by the present photoredox-
catalyzed aminohydroxylation followed by deprotection under
conditions appropriate for the functional groups in the molecule.
2.5.2. Examination of radical propagation
Next, we conducted the photocatalytic reaction with repeating
turning on-off of visible light irradiation (Fig. 3). It was observed
that the reaction progressed steadily during irradiation with blue
LED but did not proceed at all in the dark, suggesting that radical
chain mechanism is not a main process of the present
photocatalytic aminohydroxylation.
Scheme 3. Deprotection of the N-protected aminoalcohol
products.
2.4. Effect of Sc(OTf)3 on the present photocatalytic
aminohydroxylation
The effect of the scandium catalyst on the present dual
catalysis was examined for 2b by means of NMR, CV, and Stern-
Volmer plots (see the Supporting Information), and the following
observations were noted. The 1H NMR signals for the pyridinium
part of 2b were shifted to the lower field upon addition of 20
Fig. 3. Photocatalytic reaction with repeating turning on-off
of visible light irradiation.

4
Tetrahedron
2.5.3 A plausible reaction mechanism
measurements were recorded on a Hokutodende-nkou HZ-5000
ACCEPTED MANUSCRIPT
analyzer (observed in 2 mM acetone; [NBu4]PF6 = 0.1 M;
cat. Sc(OTf)3
R2
OH
R2
R1
Ag/AgCl
=
electrode; reported with respect to the
N
cat. fac-[Ir(ppy)3]
NHPG
+
N
PG
[FeCp2]/[FeCp2]+ couple). Emission spectra were recorded on a
HITACHI F7000 spectrophotometer. Single crystal X-ray
diffraction measurement was made on a Bruker SMART APEX
II ULTRA.
R3
acetone/H2O
visible light
R1
R3
2
3
4
Sc
Sc
Sc
Sc
*IrIII
reductant
IrIII
N
N
N
PG
PG
SET photoredox processes
7
H2O
IrIV
4.2. Synthesis of iminopyridinium ylides 2
Sc
oxidant
R2
R1
R2
R1
N
3
N(Sc)PG
N(Sc)PG
N(Sc)PG
4.2.1. N-Benzoyliminopyridinium ylide 2c
8
py
R3
9
R3
To a dry CH3CN (40 mL) solution of 1-aminopyridinium
iodide (1.12 g, 5.02 mmol) was added 4-dimethylaminopyridine
(DMAP) (59.9 mg, 0.490 mmol), potassium carbonate (2.08 g,
15.0 mmol), and benzoylchloride (724.4 mg, 5.15 mmol). Then,
the reaction mixture was stirred for 7 h at rt. The suspension was
concentrated in vacuo. The product was extracted with CH2Cl2
and filtered to remove inorganic impurities. After volatiles were
removed under reduced pressure, the crude product was purified
by flash column chromatography on Fuji Silysia silica gel
10
11
Scheme 5. A plausible reaction mechanism
On the basis of the experimental results obtained and our
previous reports, a plausible reaction mechanism is shown in
Scheme 5. First, 2 is activated by Sc(OTf)3 to form adduct 7. The
photoexcited Ir species (*IrIII) undergoes SET to 7 to give the
radical 8 and converts to the highly oxidized Ir species IrIV.
Radical 8 fragmentates into N-centered radical 9 and pyridine.
The N-centered radical 9 adds to olefin 3 to yield radical
intermediate 10, which is oxidized by the IrIV species to afford
carbocationic intermediate 11 and regenerate the ground state IrIII
species. Finally, nucleophilic attack of water to carbocationic
intermediate 11 furnishes aminohydroxylated product 4 and
regenerates the scandium catalyst.
FL100D
(CH2Cl2/MeOH
=
20/1)
to
afford
N-
benzoyliminopyridinium ylide (2c) as a white solid (668 mg,
3.37 mmol, 67% yield). The spectral data was identical with the
reported literatures11. 1H NMR (400 MHz, CDCl3) δ 8.85 (m, 2H;
NC5H2HH2), 8.16 (m, 2H; C6H2H3), 7.92 (m, 1H; NC5H2HH2),
7.68 (m, 2H; NC5H2HH2), 7.42 (m, 3H; C6H2H3).
4.2.2. N-(tert-Butoxycarbonyl)iminopyridinium
ylide 2d
3. Conclusion
Under N2 at 0 ºC, to a dry-CH3CN (100 mL) solution of 1-
aminopyridinium iodide (5.0103 g, 22.6 mmol) was added
triethylamine (6.3 mL, 45 mmol), DMAP (276 mg, 2.26 mmol),
and di-tert-butoxy dicarbonate (5.07 g, 23.3 mmol). The cooling
bath was removed and the reaction mixture was stirred for 6 h at
rt. Then, potassium carbonate (9.32 g, 67.5 mmol) was added and
the reaction mixture was stirred for additional 2 h at rt. The
suspension was concentrated in vacuo. The product was extracted
with CH2Cl2 and filtered to remove inorganic impurities. After
volatiles were removed under reduced pressure, the crude product
was purified by flash column chromatography on Fuji Silysia
silica gel FL60D (CH2Cl2/MeOH = 20/1) and recrystallized from
CH2Cl2 and hexane to afford the first, second and third crops of
We have developed a new strategy for introduction of a
variety of protected amino functional group to olefin by the dual
Ir
photoredox/Sc(OTf)3
catalysis.
Well-designed
iminopyridinium ylide can serve as an efficient N-centered
radical precursor when combined with Sc(OTf)3 and fac-
[Ir(ppy)3] catalysis under visible light irradiation. Sc(OTf)3 may
decease the reductive potential of N-protected iminopyridinium
ylide to promote formation of N-centered radical species. The
present photocatalytic system enables regiospecific synthesis of
various aminoalcohol bearing a range of N-protected amino
group. Further exploration of catalytic amination of organic
suvstrates with iminopyridinium ylide by the dual
photoredox/Lewis acid catalysis is underway in our laboratory.
1
2d as a white solid (total, 3.86 g, 19.9 mmol, 88% yield). H
NMR (400 MHz, CDCl3) δ 8.83 (m, 2H; C5H2HH2N), 7.71 (m,
1H; C5H2HH2N), 7.51 (m, 2H; C5H2HH2N), 1.50 (s, 9H;
C(CH3)3). 13C NMR (125 MHz, CDCl3) δ 163.4, 142.3, 134.6,
125.8, 77.9, 28.9. HRMS (ESI-TOF) calculated for
[C10H14N2O2+Na] requires 217.0947, found 217.0948.
4. Experimental
4.1. General
fac-[Ir(ppy)3],9b [Ru(bpy)3](PF6)2,9a [Ir(ppy)2(dtbbpy)](PF6),9c
2b2n, 3h10, 3i2n and 3m2nwere prepared according to the literature
procedures. Olefins 3a, 3b, 3c, 3d, 3e, 3f, 3g, 3j and 3k were
purchased from TCI and 3l was purchased from Aldrich.
Catalytic reactions were performed under an atmosphere of
nitrogen using standard Schlenk techniques unless otherwise
noted. Acetone was dried over K2CO3, distilled and stored under
nitrogen. Column chromatography was performed using Fuji
Silysia silica gel FL100D (neutral), FL60D or SCANVENGER
NH SILICA. Thin-layer chromatography was performed on TLC
plate with 60 F254 Merck. Visible light irradiation was performed
4.2.3. N-(2,2,2-Trichloroethoxycarbonyl)imino-
pyridinium ylide 2e
Under N2 at 0 ºC, to a dry-CH3CN (50 mL) solution of 1-
aminopyridinium iodide (1.12 g, 5.02 mmol) was added DMAP
(64.3 mg, 0.526 mmol), potassium carbonate (2.03 g 14.7 mmol),
and 2,2,2-trichloroethyl chloroformate (1.01 g, 4.76 mmol). The
cooling bath was removed and the reaction mixture was stirred
for 13 h at rt. The suspension was filtered and concentrated in
vacuo. The product was extracted with CH2Cl2 and filtered to
remove inorganic impurities. After volatiles were removed under
reduced pressure, the crude product was purified by flash column
chromatography on Fuji Silysia silica gel FL100D
(CH2Cl2/MeOH = 20/1) to afford 2e as a white solid (0.924 g,
with a Relyon LED lamp (3 W x 2: λ = 425 ± 15 nm). 1H and 13
C
NMR spectra were acquired on a Bruker AVANCE-400
spectrometer and a Bruker AVANCE-HD500 spectrometer at rt.
19F NMR chemical shifts were referenced to external CF3COOH
(–76.55 ppm). HRMS (ESI-TOF Mass) spectra were obtained
with a Bruker microTOF II spectrometer. Electrochemical
1
3
3.43 mmol, 72%). H NMR (400 MHz, CDCl3) δ 8.87 (d, J =

3
6.0 Hz, 2H; C5H2HH2N), 7.87 (t, J = 7.6 Hz, 1H; C5H2HH2N),
HOCHCHHNH), 3.38 (m, 1H; HOCHCHHNH), 2.23 (brs, 1H;
OH).
ACCEPTED MANUSCRIPT
7.64 (m, 2H; C5H2HH2N), 4.80 (s, 2H; CH2CCl3). 13C NMR (125
MHz, CDCl3) δ 162.0, 142.6, 136.3, 126.3, 96.8, 74.8. HRMS
(ESI-TOF) calculated for [C8H7Cl3N2O2+Na] requires 290.9465,
found 290.9465.
4.4.2. N-(2-Hydroxy-2-(4-methylphenyl)ethyl)-
2,2,2-trifluoroacetamide 4bb
The reaction of 2b (76.5 mg, 0.402 mmol), 4-methylstyrene
3b (94.9 mg, 0.803 mmol), Sc(OTf)3 (39.7 mg, 80.7 µmol), and
fac-[Ir(ppy)3] (2.6 mg, 3.97 µmol) following the general
procedures afforded 4bb (59.1 mg, 59% yield, reaction time = 8
h) as a colorless oil after purification by flash column
chromatography on Fuji Silysia SCAVENGER NH SILICA
(hexane : EtOAc = 5:1 ). 1H NMR (400 MHz, CDCl3) δ 7.25 (d,
3J = 8.0 Hz, 2H; C6H2H2), 7.20 (d, 3J = 8.0 Hz, 2H; C6H2H2), 6.75
(brs, 1H; NH), 4.85 (m, 1H; HOCHCHHNH), 3.80 (m, 1H;
HOCHCHHNH), 3.37 (m, 1H; HOCHCHHNH), 2.36 (s, 3H;
CH3C6H4), 2.14 (brs, 1H; OH). 13C NMR (125 MHz, CDCl3) δ
157.6 (q, 2J = 36.9 Hz), 138.6, 137.7, 129.6, 125.8, 116.0 (q, 1J =
285.9), 72.4, 46.7, 21.3. 19F NMR (376 MHz, CDCl3) δ –77.2.
HRMS (ESI-TOF) calculated for [C11H12F3NO2+Na] requires
270.0712, found 270.0712.
4.2.4. N-(Allyloxycarbonyl)iminopyridinium ylide 2f
To a dry-CH3CN (40 mL) solution of 1-aminopyridinium
iodide (1.12 g, 5.02 mmol) was added DMAP (60.5 mg, 0.493
mmol), potassium carbonate (2.12 g, 15.3 mmol), and allyl
chloroformate (587 mg, 4.86 mmol). The reaction mixture was
stirred for overnight at rt. The suspension was concentrated in
vacuo. The product was extracted with CH2Cl2 and filtered to
remove inorganic impurities. After volatiles were removed under
reduced pressure, the crude product was purified by flash column
chromatography on Fuji Silysia silica gel FL60D (Hexane/EtOAc
= 1/1 → CH2Cl2/MeOH = 20/1) to afford 2f as a dull red oil (377
1
mg, 2.12 mmol, 42% yield). H NMR (400 MHz, CDCl3) δ 8.86
3
3
(d, J = 6.0 Hz, 2H; C5HH2H2N), 7.80 (t, J = 7.6 Hz, 1H;
C5HH2H2N), 7.58 (m, 2H; C5HH2H2N), 6.03 (m, 1H;
CH2=CHCH2O), 5.28 (m, 2H; CH2=CHCH2O), 4.63 (m, 2H;
CH2=CHCH2O). 13C NMR (125 MHz, CDCl3) δ 163.4, 142.5,
135.4, 134.3, 126.0, 116.7, 65.3. HRMS (ESI-TOF) calculated
for [C9H10N2O2+Na] requires 201.0634, found 201.0637.
4.4.3. N-(2-Hydroxy-2-(4-methoxyphenyl)ethyl)-
2,2,2-trifluoroacetamide 4bc
The reaction of 2b (75.8 mg, 0.399 mmol), 4-methoxystyrene
3c (107.4 mg, 0.800 mmol), Sc(OTf)3 (40.1 mg, 81.5 µmol), and
fac-[Ir(ppy)3] (2.5 mg, 3.82 µmol) following the general
procedures afforded 4bc (66.6 mg, 63% yield, reaction time = 8
h) as a pale yellow solid after purification by flash column
chromatography on Fuji Silysia SCAVENGER NH SILICA
4.3. NMR experiments
To an acetone-d6 (0.45 mL)-D2O (0.05 mL) solution of olefin
3
(50.0 µmol) in an NMR tube was added 1-(2,2,2-
1
trifluoroacetylamino)pyridinium ylide 2b (50.0 µmol), fac-
[Ir(ppy)3] (1.00 µmol), and tetraethylsilane (an internal standard)
under N2. The mixture was degassed by three freeze-pump-thaw
cycles. The reaction was carried out at room temperature (in a
water bath) under irradiation by LED lamps (placed at a distance
of 2-3 cm from the blue LED lamps).
(hexane : EtOAc = 8:1 → 5:1 → 3:1). H NMR (400 MHz,
CDCl3) δ 7.28 (d, 3J = 8.4 Hz, 2H; C6H2H2), 6.91 (d, 3J = 8.8 Hz,
2H; C6H2H2), 6.74 (brs, 1H; NH), 4.83 (m, 1H; HOCHCHHNH),
3.81 (s, 3H; CH3OC6H4), 3.78 (m, 1H; HOCHCHHNH), 3.37 (m,
1H; HOCHCHHNH), 2.21 (brs, 1H; OH). 13C NMR (125 MHz,
2
CDCl3) δ 159.9, 157.5 (q, J = 36.9 Hz), 132.8, 127.2, 116.0 (q,
1J = 284.6 Hz), 114.4, 72.2, 55.5, 46.7. 19F NMR (376 Hz,
CDCl3)
δ
–77.2. HRMS (ESI-TOF) calculated for
4.4. General procedures for photocatalytic
amionohydroxylation of olefins with 1-(2,2,2-
trifluoroacetylamino)pyridinium ylide 2b
[C11H12F3NO3+Na] requires 286.0661, found 286.0662.
4.4.4. N-(2-Hydroxy-2-(4-fluorolphenyl)ethyl)-
2,2,2-trifluoroacetamide 4bd
To an acetone (3.6 mL)-H2O (0.4 mL) solution of olefin (3)
(0.80 mmol) in a 20 mL-Schlenk tube, 2b (0.40 mmol), fac-
[Ir(ppy)3] (4 µmol), and Sc(OTf)3 (80 µmol) were added under
N2. The mixture was degassed by three freeze-pump-thaw cycles.
The tube was placed at a 2-3 cm from blue LED lamps. The
resulting mixture was stirred at room temperature (in a water
bath) under visible light irradiation. Then, resulting mixture was
concentrated in vacuo to remove volatiles. The crude product was
purified by flash column chromatography on silica gel.
The reaction of 2b (76.3 mg, 0.401 mmol), 4-fluorostyrene 3d
(97.8 mg, 0.801 mmol), Sc(OTf)3 (38.4 mg, 78.0 µmol), and fac-
[Ir(ppy)3] (2.7 mg, 4.12 µmol) following the general procedures
afforded 4bd (62.9 mg, 62% yield, reaction time = 8 h) as a white
solid after purification by flash column chromatography on Fuji
Silysia SCAVENGER NH SILICA (hexane : EtOAc = 10:1 →
5:1 → 3:1). 1H NMR (400 MHz, CDCl3) δ 7.34 (m, 2H;
FC6H2H2), 7.07 (m, 2H; FC6H2H2), 6.80 (brs, 1H; NH), 4.88 (m,
1H; HOCHCHHNH), 3.78 (m, 1H; HOCHCHHNH), 3.35 (m,
1H; HOCHCHHNH), 2.45 (brs, 1H; OH). 13C NMR (125 MHz,
CDCl3) δ 162.8 (d, 1J = 245.5 Hz), 157.8 (q, 2J = 37.0 Hz), 136.5
4.4.1. N-(2-Hydroxy-2-phenylethyl)-2,2,2-
trifluoroacetylamide (4ba)
3
1
(4J = 3.1 Hz), 127.6 (d, J = 8.25 Hz), 115.9 (q, J = 285.6 Hz),
The reaction of 2b (75.9 mg, 0.399 mmol), styrene 3a (82.7
mg, 0.794 mmol), Sc(OTf)3 (38.9 mg, 79.0 µmol), and fac-
[Ir(ppy)3] (2.7 mg, 4.12 µmol) following the general procedures
afforded 4ba (56.7 mg, 61% yield, reaction time = 8 h) as a white
solid after purification by flash column chromatography on Fuji
Silysia SCAVENGER NH SILICA (hexane : EtOAc = 8:1 → 5:1
115.8 (d, 2J = 21.4 Hz), 71.9, 46.8. 19F NMR (376 MHz, CDCl3)
δ
–75.9, –113.3 (m). HRMS (ESI-TOF) calculated for
[C10H9F4NO2+Na] requires 274.0462, found 274.0462.
→ 3:1). Spectral data is in agreement with the reported data.12 1
H
4.4.5. N-(2-Hydroxy-2-(4-chlorolphenyl)ethyl)-
2,2,2-trifluoroacetamide 4be
The reaction of 2b (76.7 mg, 0.403 mmol), 4-chlorostyrene 3e
(110.7 mg, 0.799 mmol), Sc(OTf)3 (38.9 mg, 79.0 µmol), and
NMR (400 MHz, CDCl3) δ 7.42-7.34 (m, 5H; C6H5), 6.77 (brs,
1H; NH), 4.90 (m, 1H; HOCHCHHNH), 3.83 (m, 1H;

6
Tetrahedron
fac-[Ir(ppy)3] (2.6 mg, 3.97 µmol) following the general
HOCHCHHNH), 3.34 (m, 1H; HOCHCHHNH), 2.24 (brs, 1H;
ACCEPTED MANUSCRIPT
2
procedures afforded 4be (45.6 mg, 42% yield, reaction time = 8
h) as a colorless oil after purification by flash column
chromatography on Fuji Silysia SCAVENGER NH SILICA
(hexane : EtOAc = 20:1 → 5:1 ). 1H NMR (400 MHz, CDCl3) δ
7.37 (m, 2H; ClC6H2H2), 7.32 (m, 2H; ClC6H2H2), 6.73 (brs, 1H;
NH), 4.90 (m, 1H; HOCHCHHNH), 3.80 (m, 1H;
OH). 13C NMR (125 MHz, CDCl3) δ157.6 (q, J = 36.9 Hz),
1
148.2, 147.8, 134.7, 119.4, 116 (q, J = 285.8 Hz), 108.6, 106.3,
101.4, 72.3, 46.8. 19F NMR (376 MHz, CDCl3) δ–77.2. HRMS
(ESI-TOF) calculated for [C11H10F3NO4+Na] requires 300.0454,
found 300.0455.
2
3
HOCHCHHNH), 3.35 (ddd, J = 13.6 Hz, J = 8.4, 4.2 Hz, 1H;
HOCHCHHNH), 2.26 (brs, 1H; OH). 13C NMR (125 MHz,
4.4.9. N-(2-Hydroxy-2-phenyl-2-pyridylethyl)-2,2,2-
trifluoroacetamide 4bi
2
CDCl3) δ 157.8 (q, J = 37.1 Hz), 139.2, 134.4, 129.1, 127.2,
115.9 (q, J = 285.6 Hz), 71.9, 46.8. 19F NMR (376 MHz,
1
The reaction of 2b (76.3 mg, 0.401 mmol), 1-(2-pyridyl)-1-
phenylethene 3i (145.2 mg, 0.801 mmol), Sc(OTf)3 (40.3 mg,
81.9 µmol), and fac-[Ir(ppy)3] (2.7 mg, 4.12 µmol) following the
general procedures afforded 4bi (105.9 mg, 85% yield, reaction
time = 24 h) as a white solid after purification by flash column
chromatography on Fuji Silysia SCAVENGER NH SILICA
CDCl3)
δ
–77.2. HRMS (ESI-TOF) calculated for
[C10H9ClF3NO2+Na] requires 290.0166, found 290.0165.
4.4.6. N-(2-Hydroxy-2-(4-bromophenyl)ethyl)-2,2,2-
trifluoroacetamide 4bf
The reaction of 2b (76.1 mg, 0.400 mmol), 4-bromostyrene 3f
(146.4 mg, 0.800 mmol), Sc(OTf)3 (39.2 mg, 79.7 µmol), and
fac-[Ir(ppy)3] (2.8 mg, 4.28 µmol) following the general
procedures afforded 4bf (67.3 mg, 54% yield, reaction time = 8
1
(hexane : EtOAc = 10:1→5:1). H NMR (400 MHz, CDCl3)
δ8.54 (m, 1H; C5HHH2N), 7.70 (m, 1H; C5HHH2N), 7.49 (d, 3J
= 7.2 Hz, 2H; C6H2H3), 7.41-7.25 (m, 5H; C5HHH2N and C6H2H3
were overlapped), 6.87 (brs, 1H; NH), 6.17 (brs, 1H; OH), 4.32
(dd, 2J = 13.6 Hz, 3J = 7.2 Hz, 1H; OHCCHHNH), (dd, 2J = 13.6
3
h) as
a
white solid after purification by flash column
Hz, J = 4.8 Hz, 1H; OHCCHHNH). 13C NMR (125 MHz,
2
chromatography on Fuji Silysia SCAVENGER NH SILICA
(hexane : EtOAc = 5:1→3:1). H NMR (400 MHz, CDCl3) δ
7.52 (d, J = 8.4 Hz, 2H; BrC6H2H2), 7.26 (d, J = 8.4 Hz, 2H;
BrC6H2H2), 6.73 (brs, 1H; NH), 4.88 (m, 1H; HOCHCHHNH),
3.80 (m, 1H; HOCHCHHNH), 3.35 (m,1H; HOCHCHHNH),
2.29 (brs, 1H; OH). 13C NMR (125 MHz, CDCl3) δ 157.7 (q, 2J =
CDCl3) δ 160.1, 157.4 (q, J = 37.0 Hz), 147.7, 142.7, 137.8,
1
1
128.8, 128.1, 125.8, 123.2, 120.9, 115.8 (q, J = 286.0 Hz), 77.1,
47.9. 19F NMR (376 MHz, CDCl3) δ –77.4. HRMS (ESI-TOF)
calculated for [C15H13F3N2O2+Na] requires 333.0821, found
333.0820.
3
3
1
37.0 Hz), 139.7, 132.1, 127.5, 122.6, 115.9 (q, J = 286.0 Hz),
72.0, 46.7. 19F NMR (376 MHz, CDCl3) δ –77.2. HRMS (ESI-
TOF) calculated for [C10H9BrF3NO2+Na] requires 333.9661,
found 333.9661.
4.4.10. N-(2-Hydroxy-1-methyl-2-phenylethyl)-
2,2,2-trifluoroacetamide 4bj
The reaction of 2b (75.9 mg, 0.399 mmol), trans-β-
methylstyrene 3j (94.3 mg, 0.798 mmol), Sc(OTf)3 (39.7 mg,
80.7 µmol), and fac-[Ir(ppy)3] (2.6 mg, 3.97 µmol) following the
general procedures afforded 4bj (30 mg, 30% yield, reaction time
= 24 h) as a white solid after purification by flash column
chromatography on Fuji Silysia silica gel FL60D (hexane :
4.4.7. N-(2-Hydroxy-2-phenylethyl)-2,2,2-
trifluoroacetamide 4bg
The reaction of 2b (76.2 mg, 0.401 mmol), α-methylstyrene
3g (94.8 mg, 0.802 mmol), Sc(OTf)3 (39.7 mg, 80.7 µmol), and
fac-[Ir(ppy)3] (2.6 mg, 3.97 µmol) following the general
procedures afforded 4bg (64.6 mg, 65% yield, reaction time = 8
1
EtOAc = 5:1). (1R*,2R*)-4bj (major isomer): H NMR (400
MHz, CDCl3) δ7.35 (m, 5H; C6H5), 6.55 (brs, 1H; NH), 4.75
(m, 1H; HOCHCHNH), 4.25 (m, 1H; HOCHCHNH), 2.24 (brs,
3
h) as
a
white solid after purification by flash column
1H; OH), 1.31 (d, J = 6.8 Hz, 3H; CHCH3). 13C NMR (125
2
chromatography on Fuji Silysia SCAVENGER NH SILICA
(hexane : EtOAc = 5:1). H NMR (400 MHz, CDCl3) δ7.45
MHz, CDCl3) δ 157.0 (q, J = 36.8 Hz), 140.7, 128.8, 128.7,
126.0, 115.9 (q, J = 286.3 Hz), 75.9, 51.7, 17.5. 19F NMR (376
1
1
(m, 2H; C6H2H2H), 7.39 (m, 2H; C6H2H2H), 7.31 (m, 1H;
MHz, CDCl3) δ –77.3. HRMS (ESI-TOF) calculated for
2
3
C6H2H2H), 6.60 (brs, 1H; NH), 3.75 (dd, J = 13.6 Hz, J = 6.4
[C11H12F3NO2+Na] requires 270.0712, found 270.0713.
2
3
1
Hz, 1H; OHCCHHNH), 3.53 (dd, J = 13.6 Hz, J = 5.2 Hz;
OHCCHHNH), 1.66 (brs, 1H; OH), 1.62 (brs, 3H; CH3C). 13C
NMR (125 MHz, CDCl3) δ 157.9 (q, 2J = 37.0 Hz), 144.4, 128.7,
127.7, 124.8, 115.9 (q, 1J = 285.7 Hz), 74.2, 50.5, 27.4. 19F NMR
(376 MHz, CDCl3) δ –77.2. HRMS (ESI-TOF) calculated for
[C11H10F3NO4+Na] requires 300.0454, found 300.0455.
(1R*,2S*)-4bj (minor isomer): H NMR (400 MHz, CDCl3, rt)
δ7.35 (m, 5H; C6H5), 6.67 (brs, 1H; NH), 4.94 (m, 1H;
HOCHCHNH), 4.31 (m, 1H; HOCHCHNH), 2.40 (brs, 1H; OH),
1.06 (d, 3J = 6.8 Hz, 3H; CHCH3). The spectral data of
(1R*,2S*)-4bj was identical with the reported data13.
4.4.11. N-(1-Hydroxy-1,2,3,4-tetrahydro-
naphthalen-2-yl)-2,2,2-trifluoroacetamide 4bk
4.4.8. N-(2-Hydroxy-2-(2,4-
methylenedioxyophenyl)ethyl-2,2,2-
trifluoroacetamide 4bh
The reaction of 2b (76.1 mg, 0.400 mmol), 1,2-
dihydronaphthalene 3k (104.7 mg, 0.804 mmol), Sc(OTf)3 (38.7
mg, 78.6 µmol), and fac-[Ir(ppy)3] (2.8 mg, 4.28 µmol) following
the general procedures afforded 4bk (a single diastereomer of
(1R*,2S*)-4bk fraction: 11.8 mg, 11% yield, diastereomers’
mixture fraction: 18.4 mg, 18% yield, and another single
diastereomer of (1R*,2R*)-4bk fraction: 8.6 mg, 8% yield, total
yiled: 38.8 mg, 37%, reaction time = 8 h) as each white solid
after purification by flash column chromatography on Fuji Silysia
silica gel FL60D (hexane : EtOAc = 10:1→5:1). Diastereomer
The reaction of 2b (76.2 mg, 0.401 mmol), 5-ethenyl-1,3-
benzodioxide 3h (117.9 mg, 0.796 mmol), Sc(OTf)3 (39.1 mg,
79.4 µmol), and fac-[Ir(ppy)3] (5.1 mg, 7.79 µmol) following the
general procedures afforded 4bh (23.3 mg, 21% yield, reaction
time = 24 h) as a pale yellow oil after purification by flash
column chromatography on Fuji Silysia silica gel (hexane :
EtOAc = 10:1→5:1). 1H NMR (400 MHz, CDCl3) δ 6.86 (s, 1H;
C6HHH), 6.81 (m, 2H; C6HHH), 6.74 (brs, 1H; NH), 5.98 (s, 2H;
OCH2O), 4.80 (m, 1H; HOCHCH2NH), 3.77 (m, 1H;
1
ratio (2.5:1) was determined by H NMR analysis of the crude

product before chromatography. The structure of the major
The reaction of N-tert-butoxycarbonyliminopyridinium ylide
2d (78.0 mg, 0.402 mmol), 3a (83.4 mg, 0.801 mmol), Sc(OTf)3
(39.7 mg, 80.7 µmol), and fac-[Ir(ppy)3] (2.6 mg, 3.97 µmol)
following the general procedures afforded 4da (55.2 mg, 58%
yield, reaction time = 8 h) as a white solid after purification by
flash column chromatography on Fuji Silysia SCAVENGER NH
SILICA (hexane : EtOAc = 5 : 1). The spectral data was identical
with the reported data15. 1H NMR (400 MHz, CDCl3) δ 7.35 (m,
4H; Ar), 7.28 (m, 1H; Ar), 4.92 (brs, 1H; NH), 4.83 (m, 1H;
HOCHCH2), 3.49 (m, 1H; HOCHCHHNH), 3.26 (m, 1H;
HOCHCHHNH), 3.01 (brs, 1H; OH), 1.45 (s, 9H; OC(CH3)3.
ACCEPTED MANUSCRIPT
diastereomer was confirmed by single-crystal X-ray analysis.
1
(1R*,2S*)-4bk(major isomer): H NMR (400 MHz, CDCl3)
δ
7.32 (m, 1H; C6HH2H), 7.27 (m, 2H; C6HH2H), 7.18 (m, 1H;
C6HH2H), 7.04 (brs, 1H; NH), 4.74 (d, 3J = 4.4 Hz, 1H;
HOCHCHNH), 4.24 (m, 1H; HOCHCHNH), 2.95 (m, 2H;
C6H4CH2), 2.01 (m, 2H; HNCHCH2CH2), 1.78 (brs, 1H; OH).
13C NMR (125 MHz, CDCl3) δ 156.9 (q, 2J = 36.6 Hz), 135.84,
135.77, 130.2, 129.3, 129.2, 126.9, 116.0(q, 1J = 286.3 Hz), 68.2,
50.4, 28.1, 23.1. 19F NMR (376 MHz, CDCl3) δ –77.2.
1
(1R*,2R*)-4bk(minor isomer): H NMR (400 MHz, CDCl3)
d
7.53 (m, 1H; C6HH2H), 7.27 (m, 2H; C6HH2H), 7.14 (m, 1H;
C6HH2H), 6.43 (brs, 1H; NH), 4.66 (d, 3J = 7.6 Hz, 1H;
HOCHCHNH), 4.15 (m, 1H; HOCHCHNH), 3.02 (m, 1H;
C6H4CHH), 2.88 (m, 1H; C6H4CHH). 2.31 (m, 1H;
HNCHCHHCH2), 2.23 (brs, 1H; OH), 1.91 (m, 1H;
HNCHCHHCH2). 13C NMR (125 MHz, CDCl3) δ 157.9 (q, 2J =
36.9 Hz), 136.5, 135.2, 128.8, 128.4, 127.9, 127.0, 115.9 (q, 1J =
286.3 Hz), 72.3, 54.0, 27.2, 26.0. 19F NMR (376 MHz, CDCl3) δ
–77.1. HRMS (ESI-TOF) calculated for [C12H12F3NO2+Na]
requires 282.0712, found 282.0712.
4.4.15. 2-(2,2,2-Trichloroethoxycarbonylamino)-1-
phenylethanol 4ea
The reaction of 1-2,2,2-trichloroethoxycarbonylimino-
pyridinium ylide 2e (108.2 mg, 0.401 mmol), 3a (83.3 mg, 0.800
mmol), Sc(OTf)3 (38.6 mg, 78.4 µmol), and fac-[Ir(ppy)3] (2.6
mg, 3.97 µmol) following the general procedures afforded 4ea
(67.3 mg, 54% yield, reaction time = 8 h) as a white solid after
purification by flash column chromatography on Fuji Silysia
SCAVENGER NH SILICA (hexane : EtOAc = 10:1→5:1→3:1).
1H NMR (400 MHz, CDCl3) δ 7.38-7.29 (m, 5H; Ar), 5.44 (brs,
1H; NH), 4.87 (m, 1H; HOCHCHHNH), 4.73 (s, 2H; CH2CCl3),
3.61 (m, 1H; HOCHCHHNH), 3.37 (m, 1H; HOCHCHHNH),
2.49 (brs, 1H; OH). 13C NMR (125 MHz, CDCl3) δ 155.3, 141.3,
128.8, 128.4, 126.0, 95.6, 74.8, 73.5, 48.6. HRMS (ESI-TOF)
calculated for [C11H12Cl3NO3+Na] requires 339.9775, found
339.9773.
4.4.12. N-((1-Hydroxycyclopentyl)methyl)-2,2,2-
trifluoroacetamide 4bl and N-(cyclopent-1-en-
ylmethyl)-2,2,2-trifluoroacetamide 5bl
The reaction of 2b (76.4 mg, 0.402 mmol),
methylenecyclopentane 3l (66.1 mg, 0.805 mmol), Sc(OTf)3
(39.5 mg, 80.3 µmol), and fac-[Ir(ppy)3] (5.2 mg, 7.94 µmol)
following the general procedures afforded 4bl (30.7 mg, 36%
yield, reaction time = 24 h) as a white solid and 5bl (18.2 mg,
23% yield) as a colorless oil after purification by flash column
chromatography on Fuji Silysia silica gel FL60D (hexane :
4.4.16. 2-(Allyloxycarbonylamino)-1-phenylethanol
4fa
1
EtOAc = 10:1→5:1). 4bl: H NMR (400 MHz, CDCl3) δ6.78
The reaction of N-allyloxycarbonyliminopyridinium ylide 2f
(71.3 mg, 0.400 mmol), 3a (83.6 mg, 80.3 mmol), Sc(OTf)3 (39.4
mg, 80.1 µmol), and fac-[Ir(ppy)3] (2.8 mg, 4.28 µmol) following
the general procedures afforded 4fa (37.8 mg, 43% yield,
reaction time = 8 h) as a white solid after purification by flash
column chromatography on Fuji Silysia SCAVENGER NH
3
(brs, 1H; NH), 3.47 (d, J = 5.6 Hz, 2H; HOCCH2NH), 1.82 (m,
2H; cyclopentyl), 1.70 (m, 6H; cyclopentyl). 1.61 (brs, 1H; OH).
2
13C NMR (125 MHz, CDCl3) δ157.9 (q, J = 37.0 Hz), 116.1
1
(q, J = 285.8 Hz), 81.8, 48.6, 38.2, 23.8. 19F NMR (376 MHz,
CDCl3)
δ
–77.2. HRMS (ESI-TOF) calculated for
1
1
[C8H12F3NO2+Na] requires 234.0712, found 234.0713. 5bl: H
NMR (400 MHz, CDCl3) δ 6.42 (brs, 1H; NH), 5.59 (t, J = 1.6
Hz, 1H; C=CHCH2), 4.02 (d, J = 5.6 Hz, 2H; CCH2NH), 2.34
SILICA (hexane : EtOAc = 5:1 → 3:1). H NMR (400 MHz,
3
CDCl3) δ 7.37 (m, 4H; Ar), 7.32 (m, 1H; Ar), 5.92 (m, 1H;
CH2=CHCH2O), 5.27 (m, 2H; CH2=CHCH2O), 5.13 (brs, 1H;
NH), 4.85 (m, 1H; HOCHCH2NH), 4.58 (m, 2H;
CH2=CHCH2O), 3.56 (m, 1H; HOCHCHHNH), 3.32 (m, 1H;
HOCHCHHNH), 2.71 (brs, 1H; OH). 13C NMR (125 MHz,
CDCl3) δ157.2, 141.7, 132.9, 128.7, 128.1, 126.0, 118.0, 73.8,
66.0, 48.6. HRMS (ESI-TOF) calculated for [C12H15F3NO3+Na]
requires 244.0944, found 244.0943.
3
(m, 2H; CHCH2CH2), 2.29 (m, 2H; CCH2CH2), 1.93 (m, 2H;
2
CCH2CH2CH2). 13C NMR (125 MHz, CDCl3) δ 157.2 (q, J =
36.6 Hz), 138.8, 127.8, 116.0 (q, 1J = 286.1 Hz), 40.3, 33.4, 32.4,
23.4. 19F NMR (376 MHz, CDCl3) δ –77.2. HRMS (ESI-TOF)
calculated for [C8H10F3NO+Na] requires 216.0607, found
216.0604.
4.4.13. N-(2-Hydroxy-2-phenylethyl)benzamide 4ca
4.4.17. N-(5-Hydroxyl-2,5-diphenylpent-2-enyl)-
The reaction of 1-benzoyliminopyridinium ylide 2c (79.5 mg,
0.401 mmol), styrene 3a (83.1 mg, 0.798 mmol), Sc(OTf)3 (38.9
mg, 79.0 µmol), and fac-[Ir(ppy)3] (2.6 mg, 3.97 µmol) following
the general procedures afforded 4ca (43.4 mg, 45% yield,
reaction time = 24 h) as a white solid after purification by flash
column chromatography on Fuji Silysia silica gel (hexane :
EtOAc = 5:1). The spectral data was identical with the reported
2,2,2-trifluoroacetamide 4bm
The reaction of 2b (76.3 mg, 0.401 mmol), 1-phenyl-2-(1-
phenylethenyl)cyclopropane 3m (176.1 mg, 0.799 mmol),
Sc(OTf)3 (39.4 mg, 80.1 µmol), and fac-[Ir(ppy)3] (2.8 mg, 4.28
µmol) following the general procedures afforded 4bm ((E)-4bm:
31.8 mg, 23% yield, (Z)-4bm: 46.7 mg, 33% yield, total yield:
78.5 mg, 56% yield, reaction time = 8 h) as a colorless oil after
purification by flash column chromatography on Fuji Silysia
SCAVENGER NH SILICA (hexane : EtOAc = 10:1 → 5:1). The
E/Z ratio was determined to be 1/1 form the crude reaction
1
3
data14. H NMR (400 MHz, CDCl3) δ 7.76 (d, J = 7.2 Hz, 2H;
C6H2H3), 7.75-7.29 (m, 8H; Ar), 6.56 (brs, 1H; NH), 4.98 (m,
1H; HOCHCH2NH), 3.94 (m, 1H; HOCHCHHNH), 3.54 (m, 1H;
HOCHCHHNH), 3.22 (brs, 1H; OH).
1
mixture using H NMR spectroscopy. The stereochemistry was
1
1
confirmed by H-1H NOESY NMR spectroscopy. (E)-4bm: H
NMR (400 MHz, CDCl3) δ 7.35 – 7.24 (m, 8H; Ar), 7.03 (m,
2H; Ar), 6.19 (brs, 1H; NH), 5.78 (t, 3J = 7.2 Hz, 1H; CCHCH2),
4.4.14. 2-(tert-Butoxycarbonylamino)-1-
phenylethanol 4da

8
Tetrahedron
3
4.74 (m, 1H; HOCHCH2), 4.19 (d, J = 6.0 Hz, 2H; HNCH2C),
According to the typical NMR experimental procedure (4.3.),
the photocatalytic aminohydroxylation of 3a (9.7 mg, 0.0510
mmol) with 2b (10.6 mg, 0.102 mmol), Sc(OTf)3 (4.9 mg, 9.96
µmol) and fac-[Ir(ppy)3] (0.8 mg, 1.22 µmol) was performed
under repeated turning on and off of light irradiation for the fixed
durations. The time profile is shown in Figure 3.
ACCEPTED MANUSCRIPT
2.47 (m, 2H; HOCHCH2CH), 1.87 (brs, 1H; OH). 13C NMR (125
MHz, CDCl3) δ 157.1 (q, J = 36.9 Hz), 143.8, 137.9, 137.3,
2
1
128.7, 128.6, 128.5, 127.9, 127.8, 126.7, 125.9, 115.9 (q, J =
286.4 Hz), 74.0, 46.8, 38.4. 19F NMR (376 MHz, CDCl3) δ –
77.3. HRMS (ESI-TOF) calculated for [C19H18F3NO2+Na]
requires 372.1182, found 372.1182. (Z)-4bm: 1H NMR (400
MHz, CDCl3) δ 7.63 (brs, 1H; NH), 7.34-7.28 (m, 10H; Ar), 6.08
3
(t, J = 7.2 Hz, 1H; CCHCH2), 4.93 (m, 1H; OHCHCH2), 4.44
Acknowledgments
2
3
2
(dd, J = 14.4 Hz, J = 6.4 Hz, 1H; HNCHHC), 4.29 (dd, J =
14.4 Hz, 3J = 4.0 Hz, 1H; NHCHHC), 2.72 (m, 2H;
HOCHCH2C), 2.45 (brs, 1H; OH). 13C NMR (125 MHz, CDCl3)
This work was supported by JSPS KAKENHI Grant Numbers
(26288045 and 15K13689).
2
δ 157.0 (q, J = 36.8 Hz), 143.7, 140.3, 137.6, 129.4, 128.8,
1
128.8, 128.1, 127.8, 126.0, 125.7, 116.1 (q, J = 286.1 Hz), 73.3,
38.7, 38.4. 19F NMR (376 MHz, CDCl3, rt) δ –77.1. HRMS
(ESI-TOF) calculated for [C19H18F3NO2+Na] requires 372.1182,
found 372.1182.
References and notes
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Ischay, J. Du.; Nat. Chem. 2010, 2, 527-532; (b) Narayanam, J. M.
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576.
4.5. Deprotection of 4ba and 4da
4.5.1. Deprotection of 4ba under basic conditions
This deprotection was conducted according to the modified
Nordlander’s method16a. A mixture of 4ba (63.0 mg, 0.270
mmol) and potassium carbonate (201 mg, 1.49 mmol) dissolved
in MeOH (10 mL)-H2O (0.6 mL) was reflux for 2 h. After
cooling to room temperature, the mixture was concentrated in
vacuo. Then, H2O was poured into the mixture and extracted with
CH2Cl2. The organic layer was washed with brine, dried over
Na2SO4 and filtered. The filtrate was concentrated in vacuo to
afford the 2-amino-1-phenylethanol (6a) (10.9 mg, 29% yield).
2.
For related reviews, see: (a) Hu, J.; Wang, J.; Nguyen, T. H.;
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The spectral data was identical with the reported data16b
NMR (400 MHz, CDCl3) δ 7.34 (m, 4H; Ar), 7.29 (m, 1H; Ar),
4.68 (dd, J = 8.0 Hz, J = 3.6 Hz, 1H; HOCH), 3.05 (dd, J =
12.8 Hz, 3J = 3.6 Hz, 1H; HNCHH), 2.85 (dd, 3J = 12.8 Hz, 3J =
8.0 Hz, 1H; HNCHH), 2.00 (brs, 3H; OH and NH2 are
overlapped).
.
1H
3
3
3
4.5.2. Deprotection of 4da under acidic conditions
To 4da (55.2 mg, 0.233 mmol) was added hydrogen chloride
(1.0 M in diethyl ether solution) under 0 ºC. The cooling bath
was removed and the reaction mixture was stirred for 4 h at rt.
Then, the mixture was concentrated in vacuo. The residue was
washed with CH2Cl2 and dried in vacuo to afford 6a•HCl (26.8
mg, 66% yield). The spectral data was identical with the reported
data17. 1H NMR (400 MHz, DMSO-d6) δ 8.15 (brs, 3H; NH3Cl),
7.38 (m, 4H; Ar), 7.31 (m, 1H; Ar), 6.08 (brs, 1H; OH), 4.84 (dd,
3J = 5.6 Hz, J = 3.2 Hz, 1H; HOCH), 3.00 (m, 1H; H3NCHH),
2.82 (m, 1H; H3NCHH).
3
4.6. Luminescence quenching experiments
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The emission from the photoexcited fac-[Ir(ppy)3] catalyst
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prescribed amount of the quencher under deaerated conditions
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4.7. Time profile for the photocatalytic aminohydroxylation

5.
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7.
Molecular structure of (1R*,2S*)-4bk is shown in Supporting
Information. CCDC 1470156 containing the supplementary
crystallographic data can be obtained free of charge from The
Cambridge
www.ccdc.cam.ac.uk/data_request/cif.
Crystallographic
Data
Center
via
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ACCEPTED MANUSCRIPT
Highlights
•
•
•
Regiospecific aminohydroxylation of alkenes by cooperative photoredox/Lewis acid catalysis was
developed.
Various N-protected iminopyridinium ylides serves as efficient nitrogen-centered radical precursors
under mild reaction conditions.
The present strategy leads to facile synthesis of aminoalcohols bearing the primary amino group
from alkenes.