N-Heterocyclization of naphthylamines with 1,2- And 1,3-Diols catalyzed by an iridium Chloride/BINAP system

Article abstract of DOI:10.1021/jo801966u

Benzoquinoline derivatives were successfully synthesized by iridium-catalyzed N-heterocyclization of naphthylamines with diols. For instance, the reaction of 1-naphthylamine with 1,3-propanediol catalyzed by IrCl₃ combined with BINAP as a ligand produced 7,8-benzoquinoline in quantitative yield. The VV-heterocyclization reaction was found to be markedly influenced by the ligands employed. Benzoindoles were also synthesized by the same strategy from napthylamines with 1,2-diols. A reaction mechanism for the N-heterocyclization of naphthylamines with 1,3-diols by IrCl₃ was proposed.

Full text of DOI:10.1021/jo801966u

N-Heterocyclization of Naphthylamines with 1,2- and 1,3-Diols
Catalyzed by an Iridium Chloride/BINAP System
Hiroomi Aramoto, Yasushi Obora, and Yasutaka Ishii*
Department of Chemistry and Materials Engineering, Faculty of Chemistry, Materials and Bioengineering
& High Technology Research Center, Kansai UniVersity, Suita, Osaka 564-8680, Japan
ishii@ipcku.kansai-u.ac.jp
ReceiVed September 5, 2008
Benzoquinoline derivatives were successfully synthesized by iridium-catalyzed N-heterocyclization of
naphthylamines with diols. For instance, the reaction of 1-naphthylamine with 1,3-propanediol catalyzed
by IrCl3 combined with BINAP as a ligand produced 7,8-benzoquinoline in quantitative yield. The
N-heterocyclization reaction was found to be markedly influenced by the ligands employed. Benzoindoles
were also synthesized by the same strategy from napthylamines with 1,2-diols. A reaction mechanism
for the N-heterocyclization of naphthylamines with 1,3-diols by IrCl3 was proposed.
Introduction
catalytic cyclization of naphthylamines and diols is restricted
to 7,8-benzoquinoline synthesis from naphthylamine and 1,3-
propanediol by RuCl3 catalyst.3b
We have now found that benzoquinoline and benzoindole
derivatives can be efficiently synthesized in high yields by the
direct catalytic cyclization of naphthylamines with 1,3- and 1,2-
diols, respectively, by IrCl3 under the influence of a suitable
phosphine ligand.
Indole and quinoline derivatives are a very important class
of compounds for the production of pharmaceuticals, herbicides,
dyes, etc.1 There have been several classical methods for the
synthesis of these compounds from various starting materials,2
but it is desired to improve the efficiency of the reaction and to
start the reaction from easily available starting materials. The
Ru-catalyzed N-heterocylization of anilines with diols leading
to indoles and quinolines is developed by Tsuji and Watanabe
et al.3a,b Thereafter, the RuCl3/SnCl2 system is used in the indole
synthesis from aniline and ethylene glycols3c or trialkanol-
amines.3d Recently, we reported the Ir-catalyzed quinoline
synthesis from 2-aminobenzyl alcohols and ketones without any
solvent under relatively mild conditions (at 100 °C for 3 h).4
Similar Ir-catalyzed quinoline synthesis from anilines and two
different aldehydes is also reported.5 On the other hand, much
effort has been spent on the development of a synthetic method
for benzoindole and benzoquinoline derivatives,6 but to our the
best knowledge, the synthesis of these compounds by the direct
In this paper, we would like to report a facile Ir-catalyzed
synthesis of a wide variety of benzoquinoline and benzoindole
derivatives from naphthylamines and diols.
Results and Discussion
To confirm an optimum reaction condition, the reaction of
1-naphtylamine (1a) with 1,3-propanediol (2a) was chosen as
a model reaction and carried out under various conditions. A
typical reaction is performed as follows: a mixture of 1a (5
mmol) and 2a (2 mmol) in the presence of IrCl3 ·3H2O (0.10
mmol), ligand (0.15 mmol), and Na2CO3 (0.16 mmol) was
allowed to react under air at refluxing temperature (169 °C) of
mesitylene for 15 h (standard conditions) (Table 1).
(1) Sundbelg, R. J. In Kirk-Othmer Encyclopedia of Chemical Technology;
Kroschwitz, J. I., Howe-Grand, M., Eds.; Wiley: New York, 1995; Vol. 14, p
161.
(2) (a) Robinson, B. Chem. ReV. 1963, 63, 373. (b) Augustine, R. L.;
Gustavesen, A. J.; Wanat, S. F.; Pattison, I. C.; Houghton, K. S.; Koleter, G. J.
Org. Chem. 1973, 38, 3004.
(3) (a) Tsuji, Y.; Huh, K.-T.; Watanabe, Y. Tetrahedron Lett. 1986, 277,
377. (b) Tsuji, Y.; Huh, K.-T.; Watanabe, Y. J. Org. Chem. 1987, 52, 1673. (c)
Cho, C. S.; Lee, J. W.; Lee, D. Y.; Shim, S. C.; Kim, T. J. Chem. Commun.
1996, 2115. (d) Cho, C. S.; Lim, H. K.; Shim, S. C.; Kim, T. J.; Choi, H.-J.
Chem. Commun. 1998, 995.
The effect of ligand on the cyclization of 1a with 2a by
IrCl3 ·3H2O was first examined. The reaction was found to be
markedly influenced by the ligands employed. No reaction was
induced in the absence of any ligand (entry 1). When a
(6) (a) Fu¨rstner, A.; Mamane, V. J. Org. Chem. 2002, 67, 6264. (b) Bartoli,
G.; Palmieri, G.; Bosco, M.; Dalpozzo, R. Tetrahedron Lett. 1989, 30, 2129. (c)
Baudin, J.-B.; Julia, S. A.; Ruel, O. Tetrahedron 1987, 43, 881. (d) Hamada,
Y.; Takeuchi, I. J. Org. Chem. 1977, 42, 4209.
(4) Taguchi, K.; Sakaguchi, S.; Ishii, Y. Tetrahedron Lett. 2005, 46, 4539.
(5) Igarashi, T.; Inada, T.; Sekioka, T.; Nakajima, T.; Shimizu, I. Chem. Lett.
2005, 106.
628 J. Org. Chem. 2009, 74, 628–633
10.1021/jo801966u CCC: $40.75 2009 American Chemical Society
Published on Web 11/26/2008

N-Heterocyclization of Naphthylamines
TABLE 1. Reaction of 1-Naphtylamine (1a) with 1,3-Propanediol
(2a) by Ir-Catalyst under Various Conditionsa
entry
ligand
temp/°C
yield of 3aa/%b
1
2
3
4
-
169
169
169
169
169
169
169
150
169
169
169
-
PPh3
44
P(nOct)3
dppe
dppp
BINAP
BINAP
BINAP
BINAP
BINAP
BINAP
66
14
13
99 (96)
58
3
79
55
-
5
6
FIGURE 1. Time-dependence curve for the formation of 3aa under
N2, air, and O2 atmosphere (under the reaction conditions as shown in
entry 6, Table 1).
7c
8
9d
10e
11f
air or N2, which shows that the oxidation step is involved as an
important step in the present cyclization as discussed later. In
previous papers, we reported several Ir-catalyzed reactions of
alcohols including the dehydrogenation to aldehydes as a key
step, i.e., the alkylation of ketones with alcohols and diols,7
the Guerbet reaction of alcohols,8 and the dimerization reaction9
of primary alcohols to esters. Among these three reactions, O2
is needed to promote the reaction of primary alcohols to esters.
In this reaction, since the hydrogenation step by an Ir-hydride
generated by the hydrogen transfer from alcohols to Ir catalyst
is not involved, it is necessary to remove the hydride from the
Ir-hydride with O2 to regenerate the Ir-catalyst. These observa-
tions indicate that O2 is not necessary in the Ir-catalyzed
reactions including the hydrogenation step with the Ir-hydride
generated in the reaction course.
On the basis of these results, the reaction of 1a with several
diols was examined under the standard conditions (Table 2).
The reaction of 1a with ethylene glycol (2b) afforded 6,7-
benzoindole (3ab) in 47% isolated yield (entry 1). The cycliza-
tion of 1a with a secondary 1,2-diol like 2,3-butanediol (2c)
proceeded more selectively than that with primary 1,2-diol 2b
to give the corresponding benzoindole, 2,3-dimethyl-6,7-ben-
zoindole (3ac), in 96% isolated yield (entry 2). The reaction
with a cyclic diol like trans-1,2-cyclopentanediol (2d) or 1,2-
cyclohexanediol (2e) (cis-2e/trans-2e ) 64/36) afforded the
corresponding benzoindole derivatives, 3ad (84%) and 3ae
(88%), respectively (entries 3 and 4). Although the reactions
of 1a with pure cis-2e and trans-2e were examined, the reactivity
between cis-2e and trans-2e was found to be almost the same
(entries 5 and 6). In these reactions, the cyclization promoted
smoothly even by the use of PPh3 ligand in place of BINAP
ligand.
a See text. b GLC yields based on 2a used. The number in parentheses
shows isolated yield. c 1a (2 mmol) was used. d The reaction was
performed in the absence of Na2CO3. e Under N2. f [IrCl(cod)]2 (0.1
mmol) was used instead of IrCl3.
monodentate ligand like PPh3 or P(nOct)3 was added to the
catalytic system under standard conditions, 7,8-benzoquinoline
(3aa) was obtained in 44% or 66% yield, respectively (entries
1 and 2). Typical bidentate phosphine ligands such as 1,2-
bis(diphenylphosphino)ethane (dppe) and 1,3-bis(diphenylphos-
phino)propane (dppp) were less efficient than monodentate
ligands to lead to 3aa in low yields (entries 4 and 5). It was
found that rac-2,2′-bis(diphenylphosphino)-1,1′-binaphtyl (BI-
NAP) is a very efficient ligand for the IrCl3 ·3H2O catalyst to
form 3aa in almost quantitative yield (96% isolated yield) (entry
6). This method provides a simple efficient route to 3aa, since
the precedent Ru-catalyzed reaction gave 3aa in low yield
(37%).3b The reaction was strongly dependent on a starting
molar ratio of 1a to 2a, and the yield of 3aa was decreased
with decreasing the molar ratio of 1a to 2a. Thus, the yield of
3aa decreased to 58% in a stoichiometric reaction of 1a and 2a
(entry 7). When the reaction temperature was lowered from 169
to 150 °C, the reaction gave 3aa in poor yield (3%) (entry 8).
In this reaction, however, as the diol 2a was completely
consumed, the dehydrogenation of the diol 2a to an aldehyde
by the Ir complex seems to take place easily at this temperature.
Consequently, the cyclization step would call for higher
temperature than 150 °C. The reaction in the absence of Na2CO3
led to 3aa in slightly lower yield (79%) (entry 9). Hence the
base is not an essential component in this reaction. The reaction
under nitrogen atmosphere proceeded slowly to give 3aa in 55%
yield as discussed later (entry 10). [IrCl(cod)]2 complex was
inert in this reaction, although this complex serves as an efficient
catalyst for the alkylation reaction of methyl ketones with
primary alcohols (entry 11).7 Probably under such higher
temperature the complex may be decomposed to an inactive Ir
compound.
The N-heterocyclization of several substituted naphthylamines
with 1,2- and 1,3-diols was examined under optimized reaction
conditions (Table 3).
The reaction of 4-methyl-1-naphtylamine (1b) with 2a or 2c
afforded 6-methylbenzo[h]quinoline (3ba) (90%) or 2,3,5-
trimethyl-1H-benzo[g]indole (3bc) (88%) in high isolated yields,
respectively (entries 1 and 2). Similarly, 7-methoxy-1-naphtyl-
amine (1c) and 5-methoxy-1-naphtylamine (1d) reacted with
2a and 2c under these conditions to give the corresponding
cyclization products, 9-methoxy-benzo[h]quinoline (3ca) (72%),
To reveal the effect of oxygen on the present cyclization,
the reaction of 1a with 2a under O2 was compared with that
under air or N2 (Figure 1). It was found that the reaction under
O2 atmosphere promotes more rapidly than the reaction under
(8) Matsu-ura, T.; Sakaguchi, S.; Obora, Y.; Ishii, Y. J. Org. Chem. 2006,
(7) (a) Taguchi, K.; Nakagawa, H.; Hirabayashi, T.; Sakaguchi, S.; Ishii, Y.
J. Am. Chem. Soc. 2004, 126, 72. (b) Maeda, K.; Obora, Y.; Sakaguchi, S.;
Ishii, Y. Bull. Chem. Soc. Jpn. 2008, 81, 689.
71, 8306.
(9) Izumi, A.; Obora, Y.; Sakaguchi, S.; Ishii, Y. Tetrahedron Lett. 2006,
47, 9199.
J. Org. Chem. Vol. 74, No. 2, 2009 629

Aramoto et al.
TABLE 2. Reaction of 1-Naphtylamine (1a) with Various Diols
(2a) with Ir-Catalysta
TABLE 3. Reaction of Various Naphtylamines (1) with 1,2- or
1,3-Diols (2) with Ir-Catalysta
a 1a (5 mmol) was allowed to react with 2 (2 mmol) in the presence
of IrCl3 ·3H2O (0.1 mmol, 5 mol % based on 2), ligand (0.15 mmol, 7.5
mol %), and Na2CO3 (0.16 mmol, 8 mol %) under air at refluxing
temperature (169 °C) in mesitylene (3 mL) for 15 h. b GLC yields based
on 2 used. The numbers in parentheses show isolated yields. c 1a (10
mmol) was used. d PPh3 (0.2 mmol, 10 mol % based on 2) was used
instead of BINAP.
8-methoxy-2,3-dimethyl-1H-benzo[g]indole (3cc) (78%), 7-meth-
oxy-benzo[h]quinoline (3da) (72%), and 6-methoxy-2,3-di-
methyl-1H-benzo[g]indole (3dc) (76%), respectively (entries
3-6). To obtain double N-heterocyclization product, 1,5-
diaminonaphthalene (1e) was allowed to react with 2a and 2c
under the same conditions; however, double-cyclization products
were not obtained, but monocyclization products, 7-amino-
benzo[h]quinoline (3ea) (59%) and 6-amino-2,3-dimethyl-1H-
benzo[g]indole (3ec) (52%), were formed from 2a and 2c,
respectively (entries 7 and 8).
In a previous paper, we reported the quinoline synthesis from
ketones and aminobenzyl alcohols by IrCl3.4 Recently, cyclic
amines were synthesized by the reaction of primary amines with
diols by Ir complex, and the reaction is shown to proceed via
the dehydrogenation of diols to aldehydes which then react with
amines to form Schiff-base imines followed by hydrogenation
by an Ir-hydride generated in the reaction course to give cyclic
amines in good yields.10 On the other hand, quinolines are
a 1a (5 mmol) was allowed to react with 2 (2 mmol) in the presence
of IrCl3 ·3H2O (0.1 mmol, 5 mol % based on 2), BINAP (0.15 mmol,
7.5 mol %), and Na2CO3 (0.16 mmol, 8 mol %) under O2 (1 atm) at
refluxing temperature (169 °C) in mesitylene (3 mL) for 15 h. b GLC
yields based on 2 used. The numbers in parentheses show isolated
yields.
synthesized from aniline and 1,3-diols by RuCl3 catalyst, and
3b
the reaction mechanism is studied in detail.
3-Anilino-1-
propanol (A), which is predictable as a precursor to a quinoline
(B), is prepared and the intra- and intermolecular cyclization
of A and of A with aniline (4), respectively, is studied in the
presence of RuCl3 ·nH2O combined with PPh3. They obtained
B in 73% yield by intermolecular cyclization, but not by
intramolecular cyclization, and concluded that B is formed
through the cyclization of N,N′-diphenylpropane-1,3-diamine (C)
derived from A and 4, since C, prepared independently, leads
to B and 4 (Scheme 1).
In our Ir-catalyzed benzoquinoline synthesis from 1a and 2a,
the reaction seems to proceed through a similar reaction pathway
(10) Fujita, K.; Fujii, T.; Yamaguchi, R. Org. Lett. 2004, 6, 3525.
630 J. Org. Chem. Vol. 74, No. 2, 2009

N-Heterocyclization of Naphthylamines
proposed by Watanabe.3b Thus, we prepared 3-(1-napthty-
lamino)-1-propanol (D) and tried the cyclization of D itself and
the reaction of D with 1a under the influence of IrCl3 ·3H2O
and BINAP (eqs 1 and 2). In contrast to the Ru-catalyzed
reaction where the intramolecular cyclization of A to B does
not occur, the Ir-catalyzed reaction of D produced 3aa in 43%
yield (eq 1). In addition, the reaction of D with 1a led to 3aa
in higher yield (72%), and 1a was recovered in 19% (eq 2).
together with aniline 4 (65%), and the yield of quinoline B was
very low (7%).
We next investigated the reactivity and selectivity of the D
as an intermediate in the present reaction. Thus, the D was
reacted with 4 under these conditions, giving 3aa in 75% yield
as the sole N-heterocyclization product without formation of B
(eq 6). In this reaction, 4 was recovered in only 5%. On the
other hand, the reaction of A with 1a afforded the same
N-heterocyclization product 3aa in 46% yield together with 4
(39%), and 1a was recovered in 15% (eq 7). Furthermore, the
reaction of A with 1a was performed at 150 °C, and the yield
of cyclization product 3aa was only 2%, but the corresponding
diamine, F, was formed in 33% yield (eq 8).
These results may indicate that the cyclization step would
be a rate-determining step and the formation to the 3aa is a
kinetically and thermodynamically favored process. Further-
more, the fact that the product distribution of 3aa and 4 in eqs
6 and 7 was considerably different suggests that 3aa is not
formed via a common reaction intermediate, which implies that
both the aminoalcohol (D) and the diamines (E and F) can be
intermediates of the present cyclization reaction.
The product distribution derived from D itself was found to
be different from that derived from D and 1a. These results
suggest that a reaction mechanism for the formation of 3aa from
D (as shown in eq 1) seems to be different from that from D
and 1a (as shown in eq 2). Indeed, when the reaction of D with
1a was performed under low reaction temperature (150 °C),
the yield of 3aa was only 3%, but N,N′-di(naphthalene-1-
yl)propane-1,3-diamine (E) was obtained in 58% yield (eq 3).
This result suggested that diamine E would also be a probable
intermediate in the present reaction.
Thus, to obtain further information on the reaction path in
the present cyclization reaction, diamine E was prepared and
allowed to react under the same conditions to produce an
approximately equimolar amount of 3aa (76%) and 1a (83%)
(eq 4).
From these results, it is rather hazardous to predict a reaction
pathway in detail at the present stage, but the following two
possible reaction pathways may be proposed for the formation
of 3aa by the present Ir-catalyzed reaction (Schemes 2 and 3).
It is probable that the reaction is initiated by the Ir-catalyzed
dehydrogenation of diol 2a to aldehyde (F), which readily reacts
with 1a to give an imine intermediate (G) followed by
hydrogenation by the in situ generated Ir-hydride leading to D.
One plausible reaction pathway is that the resulting D reacts
In addition, to investigate the reactivity and selectivity of the
diamine intermediates, N-(naphthalene-1-yl)-N′-phenylpropane-
1,3-diamine (F) was prepared and allowed to react under these
reaction conditions (eq 5). As a result, a selective N-heterocy-
clization reaction took place to produce 3aa in 69% yield
J. Org. Chem. Vol. 74, No. 2, 2009 631

Aramoto et al.
SCHEME 1. Reported Reaction Mechanism for the Ru-Catalyzed Quinoline Synthesis3d
SCHEME 2. A Plausible Reaction Mechanism through Diamine Intermediate (E)
SCHEME 3. Another Plausible Reaction Pathway through Aminoalcohol Intermediate (D)
further with 1a after the formation of aldehyde H to give imine
I. The formation of 3aa from I may be explained by a similar
reaction path proposed by Watanabe et al. (Scheme 2).3b
However, another possible reaction pathway involving the direct
intramolecular cyclization of D to afford 3aa would also be
plausible (Scheme 3).
To obtain information about the role of O2 in the intramo-
lecular cyclization of D, the reaction of D under O2 was
compared with those under air and Ar. The yield of 3aa under
O2 (see eq 1), air, and Ar decreased in order of 43% (O2), 25%
(air), and 13% (Ar). The fact that the intramolecular cyclization
is accelerated under O2 indicates that the reaction step promoted
by O2 is included in the reaction course from D to 3aa and E.
In addition, the effect of O2 on the reaction of diamine E was
similarly examined. As a result, the yield of 3aa was 83% under
O2 (see, eq 3), 62% under air, and 43% under Ar. In the presence
of O2 in the reaction system, the Ir-hydride generated during
the reaction is trapped by O2 to regenerate Ir species liberating
H2O. Under the present higher temperature (169 °C) condition,
however, the resulting Ir-hydride seems to liberate hydrogen to
632 J. Org. Chem. Vol. 74, No. 2, 2009

N-Heterocyclization of Naphthylamines
7.49 (dd, J ) 19 Hz, 8 Hz, 2H), 7.84 (d, J ) 9 Hz, 1H), 8.34 (br,
1H); 13C NMR (400 MHz,CDCl3) δ 8.6 (CH3), 11.6 (CH3), 55.3
(CH3), 99.1 (CH), 108.9 (C), 114.4 (CH), 116.2 (CH), 119.5 (CH),
122.0 (C), 125.1 (C), 125.4 (C),128.9 (C), 129.0 (C), 130.5 (CH),
157.4 (C); GC-MS (EI) m/z (rel intensity) 225 (100) [M]+, 210
(15), 182 (31); HRMS (EI) m/z calcd for C15H15NO [M]+ 225.1154,
found 225.1148.
regenerate Ir species even in the absence of O2. It is probable
that the aromatization step is prompted by the existence of O2.
Thus, the cyclization of D to 3aa is thought to progress smoothly
under the influence of O2.
In conclusion, we have developed a facile approach to
benzoquinoline and benzoindole derivatives from naphtylamines
and 1,2- and 1,3-diols catalyzed by IrCl3 combined with BINAP
ligand. The reaction gave the desired products in good yields.
3da. 1H NMR (400 MHz,CDCl3) δ 4.02 (s, 3H), 7.07 (d, J ) 8
Hz, 1H), 7.48 (dd, J ) 8 Hz, 4 Hz, 1H), 7.62-7.66 (m, 2H), 8.14
(dd, J ) 8 Hz, 2 Hz, 1H), 8.28 (d, J ) 9 Hz, 1H), 8.88 (d, J ) 9
Hz, 1H), 8.98 (dd, J ) 4 Hz, 2 Hz, 1H); 13C NMR (400
MHz,CDCl3) δ 55.7 (CH3), 107.3 (CH), 116.4 (CH), 121.4 (CH),
121.8 (CH), 124.4 (CH), 124.8 (C), 126.5 (C), 127.2 (CH), 132.6
(C), 135.8 (CH), 146.2 (C), 148.7 (CH), 155.4 (C); GC-MS (EI)
m/z (rel intensity) 209 (100) [M]+, 194 (50), 166 (65); HRMS (EI)
m/z calcd for C14H11NO [M]+ 209.0841, found 209.0842.
Experimental Section
All starting materials except A,3d D,11 and E12 were com-
mercially available and used without any purification.
Compounds 3aa,3b 3ab,6a3ac,13 3ad,14 3ae,6a 3ba,15 3ca,16 and
3ea17 were reported previously. Compound F was prepared
according to a literature method.18
1
3dc. H NMR (400 MHz, CDCl3) δ 2.30 (s, 3H), 2.43 (s, 3H),
A Typical Reaction Procedure for the Formation of
7,8-Benzoquinoline Is As Follows (Table 1, entry 6). A mixture
of IrCl3 ·H2O (35 mg, 0.10 mmol), BINAP (93 mg, 0.15 mmol),
and Na2CO3 (17 mg, 0.16 mmol) was added to the mixture of 1a
(716 mg, 5 mmol) and 2a (152 mg, 2 mmol) in mesitylene (3 mL)
under open air. The reaction mixture was stirred at the refluxing
temperature of mesitylene (169 °C) for 15 h. The yield of the
product was estimated from the peak area based on the internal
standard technique using GC. The product (3aa) was isolated by
column chromatography (70-230 mesh Alumina, n-hexane/ethyl
acetate ) 15: 1) in 96% yield (344 mg).
4.02 (s, 3H), 6.77 (d, J ) 8 Hz, 1H), 7.40 (t, J ) 8 Hz, 1H), 7.50
(d, J ) 8 Hz, 1H), 7.60 (d, J ) 9 Hz, 1H), 7.94 (d, J ) 9 Hz, 1H),
8.32 (br, 1H); 13C NMR (400 MHz,CDCl3) δ 8.6 (CH3), 11.6 (CH3),
55.5 (CH3), 102.1 (CH), 108.8 (C), 111.8 (C), 113.3 (C), 117.7
(CH), 121.3 (CH), 122.2 (C), 125.3 (CH), 125.4 (C), 129.0 (C),
129.4 (C), 156.5 (CH3); GC-MS (EI) m/z (rel intensity) 225 (100)
[M]+, 210 (15), 182 (43); HRMS (EI) m/z calcd for C14H11NO [M]+
225.1154, found 225.1157.
1
3ec. H NMR (400 MHz, CDCl3) δ 2.22 (s, 3H), 2.37 (s, 3H),
4.11 (br, 2H), 7.18-7.24 (m, 2H), 7.30-7.33 (m, 1H), 7.38 (dd, J
) 9 Hz, 1 Hz, 1H), 7.51 (d, J ) 9 Hz, 1H), 8.29 (br, 1H); 13C
NMR (400 MHz, CDCl3) δ 8.6 (CH3), 11.6 (CH3), 108.0 (CH),
108.8 (C), 110.1 (CH), 112.3 (CH), 117.5 (CH), 119.2 (C), 122.1
(C), 124.9 (CH), 125.7 (C), 129.0 (C), 129.8 (C), 143.2 (C); GC-
MS (EI) m/z (rel intensity) 210 (100) [M]+, 195 (19); HRMS (EI)
m/z calcd for C14H14N2 [M]+ 210.1157, found 210.1158.
Reaction of 3-(1-Naphtylamino)propanol (D) in the
Presence of Ir-Catalyst (Eq 1). A mixture of IrCl3 ·H2O (18 mg,
0.05 mmol), BINAP (47 mg, 0.075 mmol), and Na2CO3 (9 mg,
0.08 mmol) was added to 3-(1-naphtylamino)-1-propanol (201 mg,
1 mmol) in mesitylene (1.5 mL) under O2 (1 atm). The reaction
mixture was stirred at the refluxing temperature of mesitylene (169
°C) for 15 h. GC analysis of the reaction mixture showed that 3aa
was formed in 43% yield.
1
F: H NMR (400 MHz, CDCl3) δ 1.81-1.87 (s, 2H), 3.12 (t, J
) 7 Hz, 2H), 3.20 (t, J ) 7 Hz, 2H), 3.92 (br, 2H), 6.45-6.49 (m,
3H), 6.61 (dq, J ) 11 Hz, 3 Hz, 1H), 7.09 (dt, J ) 19 Hz, 6 Hz,
3H), 7.21-7.33 (m, 3H), 7.60 (d, J ) 9 Hz, 1H), 7.67 (d, J ) 2
Hz, 1H); 13C NMR (400 MHz, CDCl3) δ 28.8 (CH2), 42.2 (CH2),
42.3 (CH2), 104.2 (CH), 112.9 (CH), 117.3 (CH), 117.5 (CH), 119.8
(CH), 123.4 (C), 124.6 (CH), 125.7 (CH), 126.5 (CH), 128.6 (CH),
129.2 (CH), 134.2 (C), 143.3 (C), 148.1 (C); GC-MS (EI) m/z (rel
intensity) 276 (100) [M]+, 156 (43), 143 (21); HRMS (EI) m/z calcd
for C19H20N2 [M]+ 276.1626, found 276.1625.
1
3bc. H NMR (400 MHz, CDCl3) δ 2.31 (s, 3H), 2.43 (s, 3H),
2.76 (s, 3H), 7.43-7.53 (m, 3H), 7.91(d, J ) 7 Hz, 1H), 8.07 (d,
J ) 8 Hz, 1H), 8.27 (br, 1H); 13C NMR (400 MHz, CDCl3) δ 8.6
(CH3), 11.6 (CH3), 20.0 (CH3), 108.5 (C), 118.9 (CH), 119.5 (CH),
121.5 (C), 122.9 (CH), 124.5 (C), 124.8 (CH), 125.2 (C), 125.3
(CH), 128.3 (C), 128.6 (C), 129.2 (C); GC-MS (EI) m/z (rel
intensity) 209 (100) [M]+, 194 (30); HRMS (EI) m/z calcd for
C15H15N [M]+ 209.1204, found 209.1199.
1
3cc. H NMR (400 MHz,CDCl3) δ 2.32 (s, 3H), 2.45 (s, 3H),
3.96 (s, 3H), 7.08 (tt, J ) 5 Hz, 2 Hz, 1H), 7.24 (d, J ) 2 Hz, 1H),
Acknowledgement. This work was supported by a Grant-
in-Aid for Scientific Research on Priority Areas “Advanced
Molecular Transformations of Carbon Resources” from the
Ministry of Education, Culture, Sports, Science and Technology,
Japan, and “High-Tech Research Center” Project for Private
Universities: matching fund subsidy from the Ministry of
Education, Culture, Sports, Science and Technology, 2005-2009.
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Supporting Information Available: Experimental procedure
and NMR spectral data of 3. This material is available free of
charge via the Internet at http://pubs.acs.org.
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