Iridium complex-catalyzed allylic amination of allylic esters

Article abstract of DOI:10.1021/ja0112036

Iridium complex-catalyzed allylic amination of allylic carbonates was studied. The solvent strongly affected the catalytic activity. The use of a polar solvent such as EtOH is essential for obtaining the products in high yield. The reaction of (E)-3-substituted-2-propenyl carbonate and 1-substituted-2-propenyl carbonate with pyrrolidine in the presence of a catalytic amount of [Ir(COD)Cl]₂ and P(OPh)₃ (P/Ir=2) gave a branch amine with up to 99% selectivity. Both secondary and primary amines could be used for this reaction. When a primary amine was used, selective monoallylation occurred. No diallylation product was obtained. The reaction of 1,1-disubstituted-2-propenyl acetate with amines exclusively gave an α,α-disubstituted allylic amine. This reaction provides an alternative route to the addition of an organometallic reagent to ketimines for the preparation of such amines. The reaction of (Z)-3-substituted-2-propenyl carbonate with amines gave (Z)-linear amines with up to 100% selectivity. In all cases, no (E)-linear amine was obtained. The selectivities described here have not been achieved in similar palladium complex-catalyzed reactions.

Full text of DOI:10.1021/ja0112036

J. Am. Chem. Soc. 2001, 123, 9525-9534
9525
Iridium Complex-Catalyzed Allylic Amination of Allylic Esters
Ryo Takeuchi,* Naoki Ue, Keisuke Tanabe, Kengo Yamashita, and Norihito Shiga
Contribution from the Department of Chemistry, Graduate School of Integrated Science,
Yokohama City UniVersity, 22-2 Seto, Kanazawa-ku, Yokohama 236-0027, Japan
ReceiVed May 15, 2001
Abstract: Iridium complex-catalyzed allylic amination of allylic carbonates was studied. The solvent strongly
affected the catalytic activity. The use of a polar solvent such as EtOH is essential for obtaining the products
in high yield. The reaction of (E)-3-substituted-2-propenyl carbonate and 1-substituted-2-propenyl carbonate
with pyrrolidine in the presence of a catalytic amount of [Ir(COD)Cl]2 and P(OPh)3 (P/Ir ) 2) gave a branch
amine with up to 99% selectivity. Both secondary and primary amines could be used for this reaction. When
a primary amine was used, selective monoallylation occurred. No diallylation product was obtained. The reaction
of 1,1-disubstituted-2-propenyl acetate with amines exclusively gave an R,R-disubstituted allylic amine. This
reaction provides an alternative route to the addition of an organometallic reagent to ketimines for the preparation
of such amines. The reaction of (Z)-3-substituted-2-propenyl carbonate with amines gave (Z)-linear amines
with up to 100% selectivity. In all cases, no (E)-linear amine was obtained. The selectivities described here
have not been achieved in similar palladium complex-catalyzed reactions.
Introduction
Palladium complexes are general and versatile catalysts for
allylic amination.6,7 When a π-allyl palladium intermediate is
terminally monosubstituted, the amine generally attacks at the
unsubstituted allylic terminus to give an (E)-linear allylic amine
(Scheme 1).8 Recently, ruthenium,9a,b rhodium,9c,d iron,9e and
nickel9f,g complexes have served as catalysts for allylic amina-
There have been dramatic improvements recently in methods
for organic synthesis. Many of these improvements have been
achieved by the catalytic and stoichiometric application of
transition metal complexes.1 These can be used to catalyze
several selective transformations that would be either difficult
or impossible by conventional methodologies. Transition metal
complex-catalyzed carbon-nitrogen bond formation is particu-
larly important for the synthesis of nitrogen-containing natural
products. Of the methods recently reported, the palladium
complex-catalyzed amination of arenes2 has become an indis-
pensable tool for the synthesis of aminoarenes and N-hetero-
cycles, which are difficult to prepare by traditional methods.
Another important variant for transition metal complex-
catalyzed carbon-nitrogen bond formation is allylic amination.3
Nucleophilic attack by an amine to a π-allyl intermediate
generated from an allylic substrate gives an allylic amine, which
is an important synthetic intermediate.4 For example, oxidation
of the carbon-carbon double bond gives R- or â-amino acids.5
(4) (a) Johnson, T. A.; Curtis, M. D.; Beak, P. J. Am. Chem. Soc. 2001,
123, 1004. (b) Jun, C.-H.; Lee, H.; Park, J.-B.; Lee, D.-Y. Org. Lett. 1999,
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Tetrahedron Lett. 1998, 39, 1489. (f) Gatti, R. G. P.; Larsson, A. L. E.;
Ba¨ckvall, J.-E. J. Chem. Soc., Perkin Trans. 1 1997, 577. (g) Larsson, A.
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S.; Touzin, A.-M. Tetrahedron Lett. 1993, 34, 1159. (m) Tsuda, T.; Kiyoi,
T.; Saegusa, T. J. Org. Chem. 1990, 55, 3388. (n) Trost, B. M.; Scanlan,
T. S. J. Am. Chem. Soc. 1989, 111, 4988. (o) Tsuda, T.; Horii, Y.;
Nakagawa, Y.; Ishida, T.; Saegusa, T. J. Org. Chem. 1989, 54, 977. (p)
Nikaido, M.; Aslanian, R.; Scavo, F.; Helquist, P.; A° kermark, B.; Ba¨ckvall,
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E.; Zetterberg, K.; A° kermark, B. Organometallics 1983, 2, 1625. (r)
Keinan, E.; Roth, Z. J. Org. Chem. 1983, 48, 1769. (s) Godleski, S. A.;
Heacock, D. J.; Meinhart, J. D.; Wallendeal, S. V. J. Org. Chem. 1983, 48,
2101. (t) A° kermark, B.; A° kermark, G.; Hegedus, L. S.; Zetterberg, K. J.
Am. Chem. Soc. 1981, 103, 3037. (u) Trost, B. M.; Keinan, E. J. Org. Chem.
1980, 45, 2741. (v) Stakem, F. G.; Heck, R. F. J. Org. Chem. 1980, 45,
3584.
* To whom correspondence should be addressed. E-mail: rtakeuch@
yokohama-cu.ac.jp.
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University Science Books: Mill Valley, 1999. (c) Transition Metal
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10.1021/ja0112036 CCC: $20.00 © 2001 American Chemical Society
Published on Web 09/11/2001

9526 J. Am. Chem. Soc., Vol. 123, No. 39, 2001
Takeuchi et al.
Table 1. Solvent Effect on the Reaction of 1a with 2aa
entry solvent ET(30)b conditions yieldc/% ratiod 3a/4a (E/Z)
Scheme 1
1
2
3
4
5
6
7
8
9
EtOH
51.9
55.4
48.4
42.4
46.3
45.6
40.7
37.4
36.0
32.1
38.1
34.3
50 °C 3 h
50 °C 3 h
50 °C 3 h
reflux 17 h
50 °C 12 h
50 °C 7 h
reflux 22 h
50 °C 23 h
50 °C 22 h
50 °C 23 h
reflux 22 h
reflux 16 h
95
84
99
71
89
83
90
25
39
34
45
58
95/5 (100/0)
92/8 (100/0)
83/17 (100/0)
96/4 (100/0)
68/32 (100/0)
89/11 (100/0)
80/20 (100/0)
89/11 (100/0)
91/9 (100/0)
80/20 (100/0)
91/9 (100/0)
85/15 (100/0)
MeOH
i-PrOH
acetone
MeNO2
MeCN
CH2Cl2
THF
dioxane
10 Et3N
11 AcOEt
12 benzene
a A mixture of 1a (2 mmol), piperidine (2a) (6 mmol), [Ir(COD)Cl]2
(0.04 mmol), P(OPh)3 (0.16 mmol), and solvent (4.4 mL) was stirred
under argon. b Reference 12. c Isolated yield. d Ratios determined by
GLC and NMR.
tion. The selectivity of allylic amination changes with the use
of other transition metal complexes.
We first reported that an iridium complex was an efficient
catalyst for allylic alkylation.10 The regio- and stereoselectivities
of iridium complex-catalyzed allylic alkylation are quite different
from those of palladium complex-catalyzed allylic alkylation,
and therefore, an iridium catalyst provides a useful complement
to a palladium catalyst. We report here the details of the
extension of this chemistry to the iridium complex-catalyzed
allylic amination of allylic esters.
stereo-, and enantioselectivity of allylic substitution through the
selection of a central metal or the design of a ligand has been
extensively studied. The solvent should strongly influence such
selectivities by stabilizing π-allyl metal intermediates or the
transition state of the reaction.11 We observed that the solvent
strongly affects iridium complex-catalyzed allylic amination.
The results are summarized in Table 1. The reaction of (E)-3-
phenyl-2-propenyl carbonate (1a) with 3 equiv of piperidine
(2a) in the presence of a catalytic amount of [Ir(COD)Cl]2 (Ir
atom 4 mol %) and P(OPh)3 (P/Ir ) 2) gave 3a and (E)-4a (eq
Results
Allylic Amination of (E)-3-Aryl-2-propenyl Carbonates
and 1-Aryl-2-propenyl Carbonates. Fine tuning of the regio-,
(7) For enantioselective allylic amination, see: (a) Reference 5. (b) Evans,
D. A.; Campos, K. R.; Tedrow, J. S.; Michael, F. E.; Gange´, M. R. J. Am.
Chem. Soc. 2000, 122, 7905. (c) Selvakumar, K.; Valentini, M.; Wo¨rle,
M.; Pregosin, P. S.; Albinati, A. Organometallics 1999, 18, 1207. (d)
Constantieux, T.; Brunel, J.-M.; Labende, A.; Buono, G. Synlett 1998, 49.
(e) Burckhardt, U.; Baumann, M.; Trabesinger, G.; Gramlich, V.; Togni,
A. Organometallics 1997, 16, 5252. (f) Sudo, A.; Saigo, K. J. Org. Chem.
1997, 62, 5508. (g) Togni, A.; Burckhardt, U.; Gramlich, V.; Pregosin, P.
S.; Salzmann, R. J. Am. Chem. Soc. 1996, 118, 1031. (h) Blo¨chl, P. E.;
Togni, A. Organometallics 1996, 15, 4125. (i) von Matt, P.; Loiseleur, O.;
Koch, G.; Pfaltz, A.; Lefeber, C.; Feucht, T.; Helmchen, G. Tetrahedron:
Asymmetry 1994, 5, 573.
(8) (a) Katritzky, A. R.; Yao, J.; Denisko, O. V. J. Org. Chem. 2000,
65, 8063. (b) Delbecq, F.; Lapouge, C. Organometallics 2000, 19, 2716.
(c) Kuhn, O.; Mayr, H. Angew. Chem., Int. Ed. Engl. 1999, 38, 343. (d)
Yang, S.-C.; Hung, C.-W. J. Org. Chem. 1999, 64, 5000. (e) Yang, S.-C.;
Chung, W.-H. Tetrahedron Lett. 1999, 40, 953. (f) Katritzky, A. R.; Yao,
J.; Qi, M. J. Org. Chem. 1998, 63, 5232. (g) Santos, D. S.; Tong, Y.;
Quignard, F.; Choplin, A.; Sinou, D.; Dutasta, J. P. Organometallics 1998,
17, 78. (h) Kling, R.; Sinou, D.; Pozzi, G.; Choplin, A.; Quignard, F.; Busch,
S.; Kainz, S.; Koch, D.; Leitner, W. Tetrahedron Lett. 1998, 39, 9439. (i)
Bergbreiter, D. E.; Liu, Y.-S. Tetrahedron Lett. 1997, 38, 7843. (j) Audoire-
Lemaire, S.; Savignac, M.; Pourcelot, G.; Geneˆt, J.-P.; Bernard, J.-M. J.
Mol. Catal. A 1997, 116, 247. (k) Masuyama, Y.; Kagawa, M.; Kurusu, Y.
Chem. Lett. 1995, 1121. (l) Blart, E.; Geneˆt, J. P.; Safi, M.; Savignac, M.;
Sinou, D. Tetrahedron 1994, 50, 505. (m) Hayashi, T.; Kishi, K.; Yamamoto,
A.; Ito, Y. Tetrahedron Lett. 1990, 31, 1743. (n) Bergbreiter, D. E.;
Weatherford, D. A. J. Org. Chem. 1989, 54, 2726. (o) Connell, R. D.; Rein,
T.; A° kermark, B.; Helquist, P. J. Org. Chem. 1988, 53, 3845. (p) A° kermark,
B.; Vitagliano, A. Organometallics, 1985, 4, 1275. (q) Trost, B. M.; Keinan,
E. J. Org. Chem. 1979, 44, 3451. (r) Takahashi, K.; Miyake, A.; Hata, G.
Bull. Chem. Soc. Jpn. 1972, 45, 230.
(9) For Ru, see: (a) Morisaki, Y.; Kondo, T.; Mitsudo, T. Organome-
tallics 1999, 18, 4742. (b) Kondo, T.; Ono, H.; Satake, N.; Mitsudo, T.;
Watanabe, Y. Organometallics 1995, 14, 1945. For Rh, see: (c) Evans, P.
A.; Robinson, J. E.; Nelson, J. D. J. Am. Chem. Soc. 1999, 121, 6761. (d)
Evans, P. A.; Robinson, J. E. Org. Lett. 1999, 1, 1929. For Fe, see: (e)
Enders, E.; Finkam, M. Synlett 1993, 401. For Ni, see: (f) Bricout, H.;
Carpentier, J.-F.; Mortreux, A. Tetrahedron 1998, 54, 1073. (g) Bricout,
H.; Carpentier, J.-F.; Mortreux, A. J. Chem. Soc., Chem. Commun. 1995,
1863.
1). EtOH and MeOH gave good results (entries 1 and 2). Branch
amine 3a was obtained in high yield with high selectivity. The
reaction under refluxing acetone gave the products in decreased
yield (entry 4). Although THF is a common solvent for
palladium complex-catalyzed allylic substitution, reactions in
THF or dioxane gave products in low yields (entries 8 and 9).
The ET(30) value is a well-known measure of solvent polarity.12
Solvents with ET(30) values above 40 gave the products in good
yield (entries 1-7). A polar solvent clearly enhances the reaction
of 1a with piperidine (2a). It is important to note that no (Z)-
4a was obtained in any of the cases.
The effect of the ratio of P(OPh)3 to Ir on the reaction was
examined by reacting 1a with piperidine (2a). The results are
summarized in Table 2. Reactions at P/Ir ratios of 1 and 2 gave
3a in high selectivity (entries 2 and 3). A different selectivity
was observed at a P/Ir ratio of 3. Linear amine (E)-4a was
obtained as a major product in 89% selectivity (entry 4). On
the basis of our previous study,10b,d a catalytically active species
is considered to be a monophosphite species. The reaction with
a P/Ir ratio of 3 would form a bisphosphite species as a major
catalytically active species. Increasing the steric bulkiness of
(10) (a) Takeuchi, R.; Kashio, M. Angew. Chem., Int. Ed. Engl. 1997,
36, 263. (b) Takeuchi, R.; Kashio, M. J. Am. Chem. Soc. 1998, 120, 8647.
(c) Takeuchi, R.; Tanabe, K. Angew. Chem., Int. Ed. Engl. 2000, 39, 1975.
(d) Takeuchi, R. Polyhedron 2000, 19, 557.
(11) Solvents affected the regio- and enantioselectivity of palladium
complex-catalyzed allylic substitution. See: Trost, B. M.; Toste, F. D. J.
Am. Chem. Soc. 1999, 121, 4545.
(12) Reichardt, C. Chem. ReV. 1994, 94, 2319.

Iridium Complex-Catalyzed Allylic Amination
J. Am. Chem. Soc., Vol. 123, No. 39, 2001 9527
Table 2. Effect of the Ratio of P/Ira
Scheme 2
entry
P/Ir
time/h
yieldb/%
ratioc 3a/4a (E/Z)
1
2
3
4
0
1
2
3
3
2
2
9
78
89
84
75
77/23 (100/0)
92/8 (100/0)
92/8 (100/0)
11/89 (100/0)
a A mixture of 1a (2 mmol), piperidine (2a) (6 mmol), [Ir(COD)Cl]2
(0.04 mmol), P(OPh)3, and EtOH (4.4 mL) was stirred under refluxing
conditions. b Isolated yield. c Determined by GLC and NMR.
Table 3. Reaction of 1a with 2a
yieldb/
%
ratioc
3/4 (E/Z)
entry
amine 2
time/h product
1
2
3
4
5
6
7
2b, pyrrolidine
2c, morpholine
2d, cyclopentylamine
2e, n-butylamine
2f, diethylamine
2g, tert-butylamine
2h, benzylamine
3
2
2
5
3
2
7
3b, 4b
3c, 4c
3d, 4d
3e, 4e
3f, 4f
3g, 4g
3h, 4h
95
92
93
79
75
92
89
96/4 (100/0)
92/8 (100/0)
96/4 (100/0)
95/5 (100/0)
65/35 (100/0)
81/19 (100/0)
96/4 (100/0)
strongly suggest the intermediacy of a π-allyl iridium complex.
a A mixture of 1a (2 mmol), amine (2) (6 mmol), [Ir(COD)Cl]2 (0.04
mmol), P(OPh)3 (0.16 mmol), and EtOH (4.4 mL) was stirred under
reflux. b Isolated yield. c Ratios determined by GLC and NMR.
this species would lead an amine to the unsubstituted allylic
terminus to give linear amine (E)-4a.
Carbonate 1a reacted with 3 equiv of amine (2) under
refluxing EtOH to give 3 and (E)-4 as an inseparable mixture.
The results are summarized in Table 3. In all cases, no (Z)-4
was obtained. Both secondary and primary amines could be
used. The yields were generally good, but the selectivities
depended on the amine used. The reactions of 1a with
pyrrolidine (2b), morpholine (2c), cyclopentylamine (2d),
n-butylamine (2e), and benzylamine (2h) gave 3b-e,h in
selectivities of 92-96% (entries 1-4 and 7). Reactions with
primary amines (2d,e,g,h) gave monoallylation products exclu-
sively. It is well-known that palladium complex-catalyzed allylic
amination with a primary amine gives a monoallylation product
and a considerable amount of a diallylation product.8e,f,l,q For
example, the reaction of 1b with 2 equiv of n-butylamine (2e)
has been reported to give a monoallylation product in 80% yield
and a diallylation product in 11% yield.8l An iridium complex
has an advantage over a palladium complex with regard to the
control of monoallylation and diallylation, in that no diallylation
product was obtained. Diethylamine (2f) gave a lower selectivity
for 3 than cyclic secondary amines (2a-c). The selectivity of
3f was 65% (entry 5). The basicities of these amines are almost
the same (piperidine, pKa ) 11.1; N,N′-diethylamine, pKa )
10.8).13 The difference in selectivity is likely due to the steric
effect of amines. The cone angle is generally used to measure
the steric bulk of a ligand. The cone angle of diethylamine (125°)
is slightly larger than that of piperidine (121°).14 To examine
whether this small difference in the cone angle affects the
regioselectivity, we examined the reaction with tert-butylamine
(2g), which has a cone angle of 123°.14 The reaction with tert-
butylamine (2g) gave an 81:19 mixture of 3g and (E)-4g in 92%
yield (entry 6). The selectivity of 3 decreased as the steric bulk
of the amine increased (piperidine > tert-butylamine > diethy-
lamine).
Iridium complex-catalyzed allylic alkylations of (E)-3-mono-
substituted-2-propenyl acetates and 1-monosubstituted-2-pro-
penyl acetates gave the same product distribution.10 This allylic
amination gave a slightly different product distribution. Carbon-
ate 5a gave a higher selectivity of 3 than 1a. Considering that
the SN2 substitution of the σ-allyl iridium intermediate with an
amine is a minor reaction path reasonably explained this
difference. A plausible mechanism is outlined in Scheme 2. The
major reaction path of both reactions gives 3 and a small amount
of 4. The minor reaction path of the reaction of 1a and 5a gives
a different product. SN2 substitution of σ-allyl iridium inter-
mediate 6 with an amine gives 4, whereas the same reaction of
8 with an amine gives 3. As a consequence, the reaction of 5a
is more selective for 3 than that of 1a.
1-Phenyl-2-propenyl carbonate (5a), which is a regioisomeric
carbonate of 1a, reacted with both a secondary amine and a
primary amine to give branch amine 3 (eq 2). These results
(13) Lange’s Handbook of Chemistry, 13th ed.; Dean, J. A., Ed.;
McGraw-Hill: New York, 1985; section 5.
(14) For cone angle of amines, see: Seligson, A. L.; Trogler, W. C. J.
Am. Chem. Soc. 1991, 113, 2520.

9528 J. Am. Chem. Soc., Vol. 123, No. 39, 2001
Table 4. Reaction of 9 and 10 with 2aa
Takeuchi et al.
reaction of 1a with 3 equiv of piperidine (2a) was complete
under refluxing EtOH for 2 h. On the other hand, the reac-
tion of 1b with piperidine (2a) under the same reaction
conditions was complete in 9 h to give a 90:10 mixture of 3a
and (E)-4a in 80% yield. 1-Phenyl-2-propenyl acetate (5b),
which is a regioisomeric acetate of 1b, showed a reactivity
comparable to that of carbonate 1a. Acetate 5b reacted with
piperidine (2a) under refluxing EtOH for 3 h to give a 98:2
mixture of 3a and (E)-4a in 88% yield.16 This result prompted
us to examine the allylic amination of 1,1-disubstituted-2-
propenyl acetate (16) (eq 5). Allylic amination at the disubsti-
tuted allylic terminus would give an R,R-disubstituted allylic
amine. A general route to such amines is the addition of
organometallic reagents to ketimines and their iminium salts.17
However, when ketimines have an R-hydrogen, the addition of
organometallic reagents to an imine carbon is problematic,
because R-deprotonation competes with the addition reaction.18
A more widely applicable method for the synthesis of an R,R-
disubstituted allylic amine is needed. Regioselective allylic
amination at the disubstituted allylic terminus should be a useful
alternative route.
yieldb/ ratioc 11/12
%
entry
1
substrate
9a, Ar )
time/h products
(E/Z)
2
3
3
6
2
6
11a, 12a
11a, 12a
11b, 12b
11b, 12b
11c, 12c
11c, 12c
80
94/6 (100/0)
4-methylphenyl
10a, Ar )
4-methylphenyl
9b, Ar )
4-fluorophenyl
10b, Ar )
4-fluorophenyl
2
3
85
91
83
89
80
99/1 (100/0)
95/5 (100/0)
99/1 (100/0)
95/5 (100/0)
97/3 (100/0)
4
5
9c, Ar )
2-thienyl
10c, Ar )
2-thienyl
6
a A mixture of 9 or 10 (2 mmol), piperidine (2a) (6 mmol),
[Ir(COD)Cl]2 (0.04 mmol), P(OPh)3 (0.16 mmol), and EtOH (4.4 mL)
was stirred under reflux. b Isolated yield. c Ratios determined by GLC
and NMR.
Allylic amination of (E)-3-aryl-2-propenyl carbonate (9) and
1-aryl-2-propenyl carbonate (10) was examined (eq 3). The
results are summarized in Table 4. The nature of the aryl group
did not affect the yield and the selectivity.
Allylic Amination of (E)-2-Alkenyl Carbonates. Allylic
amination of (E)-2-alkenyl carbonate ((E)-13) was less regi-
oselective for the branch amine (14) than that of (E)-3-aryl-2-
propenyl carbonate (eq 4). The results are summarized in Table
5. The yields of the products were generally good. The choice
Allylic amination of 1,1-disubstituted-2-propenyl acetates (16)
was examined. The results are summarized in Table 6. 1-Methyl-
1-(n-pentyl)-2-propenyl acetate (16a) smoothly reacted with
piperidine (2a) under refluxing EtOH for 4 h to give 17aa as a
single product in 76% yield (entry 1). The reaction occurred
with perfect regioselectivity at the disubstituted allylic terminus.
No 18aa was obtained. The use of EtOH was essential for this
reaction. The same reaction under refluxing dioxane for 24 h
gave no amination product, with the recovery of 16a in a
quantitative yield. Similarly, acetate 16a reacted with pyrroli-
dine (2b) and aniline (2i) to give 17ab and 17ai exclusively
in yields of 70 and 77%, respectively (entries 2 and 4). The
reaction of 16a with n-butylamine (2e) gave 17ae exclusively,
in a somewhat decreased yield compared to the yields of
17aa, 17ab, and 17ai (entry 3). Linalyl acetate (16b) reacted
with piperidine (2a) to give 17b exclusively in 76% yield (entry
4). Pd(PPh3)4-catalyzed allylic amination of 1,1-disubstituted
allylic nitro compounds with piperidine (2a) has been re-
ported to give both an (E)-linear allylic amine and an R,R-
of catalyst and solvent was important for obtaining a branch
amine in high selectivity. The reaction of (E)-13a with pyrro-
lidine (2b) using [Ir(COD)OMe]2 under refluxing acetone gave
14ab in 85% selectivity (entry 2). MeCN was also a good
solvent and gave 14ab in 84% selectivity (entry 3). Because
piperidine (2a) is more sterically demanding than pyrrolidine
(2b),14 the reaction with piperidine (2a) decreased the selectivity
of the branch amine (14aa) slightly (entry 4). Cyclopentylamine
(2d), n-butylamine (2e), and aniline (2i) gave better selectivity
of the branch amine than pyrrolidine (2b). Branch amines 14ad,
14ae, and 14ai were obtained in selectivies of 92-95% (entries
5-7). It is noteworthy that the diallylation of a primary amine
was not observed.
Oxidative addition of (E)-2-alkenyl carbonate gives a 1-alkyl
π-allyl iridium intermediate. Because an alkyl group is more
electron-donating than an aryl group,15 an allylic terminus
substituted with an alkyl group is less electron-deficient than
that substituted with an aryl group. Thus, the amination of a
1-alkyl π-allyl iridium intermediate is less regioselective for
the branch amine than that of a 1-aryl π-allyl iridium intermedi-
ate.
(16) The steric effect of the alkene in the allylic system affects the
coordination of a transition metal complex prior to oxidative addition.
Because of this effect, acetate 5b, a terminal alkene, is more reactive than
acetate 1b, an internal alkene.
(17) (a) Cogan, D. A.; Ellman, J. A. J. Am. Chem. Soc. 1999, 121, 268.
(b) Spero, D. M.; Kapadia, S. R. J. Org. Chem. 1997, 62, 5537. (c) Ciganek,
E. J. Org. Chem. 1992, 57, 4521.
(18) (a) Whitesell, J. K.; Whitesell, M. A. J. Org. Chem. 1977, 42, 377.
(b) Stork, G.; Dowd, S. R. J. Am. Chem. Soc. 1963, 85, 2178. (c) In the
reaction of the N-cyclohexylimine of 2-methylcyclohexanone with n-
butyllithium, it has been reported that selective R-deprotonation occurs.
See: Hosomi, A.; Araki, Y.; Sakurai, H. J. Am. Chem. Soc. 1982, 104,
2081.
Allylic Amination of 1,1-Disubstituted-2-propenyl Ac-
etates. Acetate 1b was less reactive than carbonate 1a. The
(15) The group electronegativity of an aryl group is bigger than that of
an alkyl group. See: Inamoto, N.; Masuda, S. Chem. Lett. 1982, 1003.

Iridium Complex-Catalyzed Allylic Amination
J. Am. Chem. Soc., Vol. 123, No. 39, 2001 9529
Table 5. Reaction of 13 with 2a
entry
substrate
amine
catalyst
solvent
EtOH
conditions
reflux 3 h
product
yieldb/% ratioc 14/15 (E/Z)
1
2
3
13a, R ) n-hexyl
13a, R ) n-hexyl
13a, R ) n-hexyl
13a, R ) n-hexyl
13a, R ) n-hexyl
13a, R ) n-hexyl
13a, R ) n-hexyl
13b, R ) n-octyl
2b, pyrrolidine
2b, pyrrolidine
2b, pyrrolidine
2a, piperidine
2d, cyclopentylamine [Ir(COD)OMe]2 MeCN
2e, n-butylamine
2i, aniline
[Ir(COD)Cl]2
14ab, 15ab
14ab, 15ab
14ab, 15ab
85
94
86
87
76
70
95
92
85
96
65/35 (100/0)
85/15 (100/0)
84/16 (100/0)
81/19 (100/0)
92/8 (100/0)
95/5 (100/0)
93/7 (100/0)
86/14 (100/0)
84/16 (100/0)
91/9 (100/0)
[Ir(COD)OMe]2 acetone reflux 2 h
[Ir(COD)OMe]2 MeCN reflux 4 h
[Ir(COD)OMe]2 acetone reflux 3 h
4
14aa, 15aa
5d
6d
7e
8
reflux 24 h 14ad, 15ad
reflux 24 h 14ae, 15ae
reflux 2 h
reflux 3 h
[Ir(COD)OMe]2 MeCN
[Ir(COD)OMe]2 EtOH
[Ir(COD)OMe]2 MeCN
[Ir(COD)OMe]2 acetone reflux 3 h
[Ir(COD)OMe]2 EtOH
14ai, 15ai
14bb, 15bb
14cb, 15cb
2b, pyrrolidine
9
13c, R ) cyclohexyl 2b, pyrrolidine
13c, R ) cyclohexyl 2i, aniline
10f
reflux 47 h 14ci, 15ci
a A mixture of 13 (2 mmol), 2 (6 mmol), Ir complex (0.04 mmol), P(OPh)3 (0.16 mmol), and solvent (4.4 mL) was stirred under argon. b Isolated
yield. c Ratios determined by GLC and NMR. d Compound 2 (12 mmol), [Ir(COD)OMe]2 (0.08 mmol), P(OPh)3 (0.32 mmol), solvent (4.0 mL).
e Aniline (2i) (3 mmol), [Ir(COD)OMe]2 (0.02 mmol), P(OPh)3 (0.08 mmol), EtOH (4.0 mL). f Aniline (2i) (4 mmol).
Table 6. Reaction of 16 with 2a
entry
substrate
amine
time/h
yieldb/%
product
ratioc
1
2
3
4
5
16a, R1 ) n-pentyl, R2 ) Me
16a, R1 ) n-pentyl, R2 ) Me
16a, R1 ) n-pentyl, R2 ) Me
16a, R1 ) n-pentyl, R2 ) Me
16b, R1 ) Me2CdCHCH2CH2, R2 ) Me
2a, piperidine
2b, pyrrolidine
2e, n-butylamine
2i, aniline
4
4
16
11
4
76
70
59
77
76
17aa, 18aa
17ab, 18ab
17ae, 18ae
17ai, 18ai
17b, 18b
100/0
100/0
100/0
100/0
100/0
2a, piperidine
a A mixture of 16 (2 mmol), amine (2) (6 mmol), [Ir(COD)Cl]2 (0.04 mmol), P(OPh)3 (0.16 mmol) and EtOH (4.4 mL) was stirred under reflux.
b Isolated yield. c Determined by GLC and NMR.
Table 7. Solvent Effect on the Reaction of (Z)-13a with 2aa
disubstituted allylic amine.19 The selectivity of an R,R-disub-
ratioc(Z)-15aa/
(E)-15aa/14aa
stituted allylic amine was moderate. Only iridium complex-
entry
solvent
conditions
yieldb/%
catalyzed allylic amination gave an R,R-disubstituted allylic
amine as a single product.
1
2
3d
4
5
6
7
MeNO2
MeNO2
MeNO2
EtOH
acetone
THF
reflux 3 h
50 °C 16 h
50 °C 16 h
reflux 2 h
reflux 47 h
reflux 24 h
reflux 24 h
91
87
73
93
82
14
65
91/0/9
94/0/6
93/0/7
88/0/12
91/0/9
92/0/8
93/0/7
Allylic Amination of (Z)-2-Alkenyl Carbonates.20 Allylic
amination of (Z)-2-alkenyl carbonate ((Z)-13a) was examined
(eq 6). Palladium complex-catalyzed allylic amination of (Z)-
2-alkenyl acetate gave (E)-linear allylic amine,8q because the
anti π-allyl palladium intermediate easily isomerized to a syn
π-allyl palladium intermediate21 prior to nucleophilic attack by
an amine. The retention of Z stereochemistry in the palladium
complex-catalyzed allylic substitution of (Z)-2-alkenyl esters has
been difficult to achieve. Limited examples have been reported,22
and these have had to be carried out at -78 °C to retain Z
stereochemistry. We previously reported that iridium complex-
catalyzed allylic alkylation of (Z)-2-hexenyl acetate gave a (Z)-
linear product in 70% selectivity.10b Extending this methodology,
we have achieved the first complete retention of Z stereochem-
istry in allylic amination. The reaction of (Z)-2-nonenyl carbon-
ate ((Z)-13a) with piperidine (2a) was carried out in various
solvents. The results are summarized in Table 7. The solvent
of choice was MeNO2. The reaction under refluxing MeNO2
gave products in 91% yield (entry 1). The selectivity of (Z)-
15aa was 91%. No (E)-15aa was obtained. The reaction at 50
°C increased the selectivity of (Z)-15aa up to 94% (entry 2).
Decreasing the amount of piperidine (2a) decreased the yield
of the products (entry 3). The use of EtOH gave products in
93% yield, but the selectivity of (Z)-15aa decreased to 88%
CH2Cl2
a A mixture of (Z)-13a (2 mmol), piperidine (2a) (10 mmol),
[Ir(COD)Cl]2 (0.04 mmol), P(OPh)3 (0.16 mmol), and solvent (4.1 mL)
was stirred under argon. b Isolated yield. c Determined by GLC and
NMR. d Piperidine (2a) (6 mmol).
(entry 4). The reaction in acetone required a longer reaction
time (entry 5). THF and CH2Cl2 were less efficient than MeNO2
(entries 6 and 7).
(19) (a) Tamura, R.; Hegedus, L. S. J. Am. Chem. Soc. 1982, 104, 3727.
(b) Tamura, R.; Kai, Y.; Kakihana, M.; Hayashi, K.; Tsuji, M.; Nakamura,
T.; Oda, D. J. Org. Chem. 1986, 51, 4375.
(20) A preliminary work described here, see: Takeuchi, R.; Shiga, N.
Org. Lett. 1999, 1, 265.
(21) (a) Sjo¨gren, M.; Hansson, S.; Norrby, P.; A° kermark, B.; Cucciolito,
M. E.; Vitagliano, A. Organometallics 1992, 11, 3954. (b) A° kermark,
B.; Hansson, S.; Vitagliano, A. J. Am. Chem. Soc. 1990, 112, 4587.
(c) Faller, J. W.; Mattina, M. Inorg. Chem. 1972, 11, 1296. (d) Faller, J.
W.; Thomsen, M. E.; Mattina, M. J. J. Am. Chem. Soc. 1971, 93,
2642.
(22) (a) Kazmaier, U.; Zumpe, F. L. Angew. Chem., Int. Ed. Engl. 2000,
39, 802. (b) Hutzinger, M. W.; Oehlschlager, A. C. J. Org. Chem. 1991,
56, 2918.
The reaction of (Z)-13a with various amines (2) in MeNO2
was examined. The results are summarized in Table 8. Allylic
amines (Z)-15aa-ac,ae,af were obtained in selectivities of
79-97%. No (E)-isomer was obtained in any of the cases.
The structure of the amine strongly affected the yield of the
products. The reaction of (Z)-13a with a secondary amine gave
the corresponding product in good yield (entries 1-3 and 5).
In contrast to the results obtained with secondary amines, the
reaction of (Z)-13a with n-butylamine (2e) had a decreased yield

9530 J. Am. Chem. Soc., Vol. 123, No. 39, 2001
Table 8. Reaction of (Z)-13 with 2a
Takeuchi et al.
entry
substrate
amine
conditions
product
yield/%b
ratioc(Z)-15/(E)-15/ 14
1
2
(Z)-13a, R ) n-hexyl
(Z)-13a, R ) n-hexyl
(Z)-13a, R ) n-hexyl
(Z)-13a, R ) n-hexyl
(Z)-13a, R ) n-hexyl
(Z)-13b, R ) n-octyl
(Z)-13d, R ) Ph(CH2)3
(Z)-13e, R ) H2CdCH(CH2)4
(Z)-13f, R ) n-BuEtCHCH2
(Z)-13g, R ) n-BuOCH2
2a, piperidine
2b, pyrrolidine
2c, morpholine
2e, n-butylamine
2f, diethylamine
2a, piperidine
2a, piperidine
2a, piperidine
2a, piperidine
2a, piperidine
50 °C 16 h
50 °C 3 h
50 °C 25 h
50 °C 20 h
50 °C 21 h
50 °C 22 h
50 °C 18 h
50 °C 3 h
50 °C 5 h
50 °C 7 h
15aa, 14aa
15ab, 14ab
15ac, 14ac
15ae, 14ae
15af, 14af
15ba, 14ba
15d, 14d
15e, 14e
15f, 14f
15g, 14g
87
80
80
56
69
86
89
89
70
95
94/0/6
94/0/6
88/0/12
79/0/21
97/0/3
94/0/6
92/0/8
100/0/0
100/0/0
99/0/1
3
4d
5
6
7
8e
9e
10
a A mixture of (Z)-13 (2 mmol), amine (2) (10 mmol), [Ir(COD)Cl]2 (0.04 mmol), P(OPh)3 (0.16 mmol), and MeNO2 (4.1 mL) was stirred under
argon. b Isolated yield. c Determined by GLC and NMR. d [Ir(COD)Cl]2 (0.08 mmol), P(OPh)3 (0.32 mmol). e Piperidine (2a) (5 mL) was used as
a solvent.
(entry 4). A rather bulky amine is necessary to obtain (Z)-15 in
high yield.23
neutral π-allyl intermediate, the reaction in a polar solvent
increases the yield of an amination product. If this hypothesis
is correct, methoxide will be formed by the dissociation from a
neutral π-allyl Ir intermediate. Thus, allylic alkylation with
diethyl malonate25 in EtOH may give an alkylation product
without using a base. To probe this hypothesis, we examined
the reaction of 1a with diethyl malonate in the presence of a
catalytic amount of [Ir(COD)Cl]2 and P(OPh)3 (Ir atom 4 mol
%, P/Ir ) 2) under refluxing EtOH for 24 h. No alkylation
product was obtained. The starting material was recovered in
quantitative yield. This result strongly suggests that a π-allyl Ir
intermediate is neutral and does not dissociate methoxide.
As shown in Table 8, (Z)-13b,d-g were successfully reacted
with piperidine to give (Z)-15ba,d-g with selectivities of 92-
100% (entries 6-10). No (E)-isomer was obtained. Terminal
alkene and alkoxy functionalities were tolerated in the allylic
amination (entries 8 and 10). Allylic amine (Z)-15g was obtained
with 99% selectivity (entry 10).
Discussion
Regioselectivity. The electron-withdrawing property of P(OPh)3
plays a crucial role in the high selectivity of a branch amine.
On the basis of a previous study,10b,d a π-allyl iridium interme-
diate is considered to be a monophosphite species in which
P(OPh)3 coordinates with the metal trans to the substituted allylic
terminus. The carbonium ion character of the substituted allylic
terminus enhanced by the electron-withdrawing property of
P(OPh)3 directs an amine to this position to give a branch amine.
Allylic amination of (Z)-2-alkenyl carbonate gave a (Z)-linear
amine. When an amine approached the substituted allylic ter-
minus of an anti π-allyl iridium intermediate, the substituent
and iridium moiety are close together to increase the steric
repulsion (Scheme 3). Thus, the transition state of the amination
at the substituted allylic terminus of an anti π-allyl iridium
intermediate is less stable than that of a syn π-allyl iridium
intermediate. Therefore, amination of an anti π-allyl iridium
intermediate preferentially occurs at the unsubstituted allylic
terminus to give a (Z)-linear allylic amine.
When the substrate and nucleophile in an SN2 reaction are
both neutral, the charge density in the transition state is greater
than that of the initial reactants. A polar solvent can stabilize
the transition state to enhance an SN2 reaction.26 It is well-known
that oxidative addition to a low-valent transition metal complex
proceeds via an SN2-type mechanism.27 Oxidative addition to
an Ir (+1) complex in a polar solvent has been reported to be
enhanced by stabilization of the transition state.28 Because of
this solvent effect, oxidative addition in this reaction might be
enhanced. Furthermore, a polar solvent plays an important role
in the nucleophilic attack by an amine to a π-allyl Ir intermedi-
ate. As described above, a π-allyl Ir intermediate generated in
this reaction is a neutral species. The transition state of the
nucleophilic attack is more polar than the initial reactants. As
a consequence, the nucleophilic attack by an amine to a π-allyl
Ir intermediate is also enhanced by a polar solvent. Thus, this
allylic amination in a polar solvent is enhanced to give an
amination product in high yield.
Scheme 3
Comparison with Ruthenium, Rhodium, and Nickel
Complex-Catalyzed Allylic Amination. A ruthenium complex
Mechanistic Consideration of the Solvent Effect. In this
allylic amination, the use of a polar solvent such as EtOH is
essential to obtain a product in high yield. This effect of a polar
solvent may be explained as follows. A neutral π-allyl Ir
intermediate formed by oxidative addition of an allylic carbonate
can dissociate methoxide with the aid of a polar solvent to give
a cationic π-allyl Ir intermediate (eq 7).24 Because a cationic
π-allyl intermediate is more reactive to a nucleophile than a
(25) Pd complex-catalyzed allylic alkylation under neutral conditions is
well-known. See: (a) Tsuji, J.; Shimizu, I.; Minami, I.; Ohashi, T.; Sugiura,
T.; Takahashi, K. J. Org. Chem. 1985, 50, 1523. (b) Tsuji, J.; Minami, I.
Acc. Chem. Res. 1987, 20, 140.
(26) Reichardt, C. SolVents and SolVent Effects in Organic Chemistry,
2nd ed.; VCH: Weinheim, Germany, 1988; p 137.
(27) (a) Collman, J. P.; Hegedus, L. S.; Norton, J. R.; Finke, R. G.
Principles and Applications of Organotransition Metal Chemistry, 2nd ed.;
University Science Books: Mill Valley, 1987; p 306. (b) Crabtree, R. H.
The Organometallic Chemistry of the Transition Metals, 3rd ed.; Wiley:
New York, 2001; p 156. (c) Atwood, J. D. Inorganic and Organometallic
Reaction Mechanisms, 2nd ed.; Wiley-VCH: 1997; p 158.
(28) (a) Wilson, M. R.; Liu, H.; Prock, A.; Giering, W. P. Organome-
tallics 1993, 12, 2044. (b) Chock, P. B.; Halpern, J. J. Am. Chem. Soc.
1966, 88, 3511.
(23) The decrease in the yield of (Z)-15 may be ascribed to the side
reaction where carbonate (Z)-13a undergoes nucleophilic attack of an amine
to the carbonyl carbon.
(24) It has been reported that a cationic rhodium complex was formed
in a polar solvent such as alcohol or MeNO2 by the dissociation of an anionic
ligand from a neutral rhodium complex. See: Shapley, J. R.; Schrock, R.
R.; Osborn, J. A. J. Am. Chem. Soc. 1969, 91, 2816.

Iridium Complex-Catalyzed Allylic Amination
J. Am. Chem. Soc., Vol. 123, No. 39, 2001 9531
noacetate (8.968 g, 40 mmol) was added an ethanol (20 mL) solution
of sodium ethoxide (prepared from 60 mmol of Na) at -30 °C. The
reaction mixture was stirred for 4 h at room temperature. Water was
added, and the mixture was extracted with ether. The ether solution
was dried over MgSO4 and evaporated in vacuo. Distillation of the
residue gave ethyl 3-(4-methylphenyl)-2-propenoate (6.088 g, 32 mmol).
To 0.95 M diisobutylaluminum hydride in n-hexane (68 mL) was added
dropwise 3-(4-methylphenyl)-2-propenoate (6.088 g, 32 mmol). The
mixture was stirred at -78 °C for 2 h. The cooling bath was removed,
and the mixture was allowed to warm to room temperature. The mixture
was poured into water, and the aqueous layer was extracted with ether.
The combined organic layers were dried with MgSO4. The solvent was
evaporated in vacuo. Column chromatography (n-hexane/AcOEt ) 90/
10) of the residue gave (E)-3-(4-methylphenyl)-2-propen-1-ol, yield
has been reported to give a branch amine predominantly.
Ruthenium complex-catalyzed allylic amination of (E)-1a with
piperidine (2a) gave 3a in 84% selectivity.9b Similarly, rhodium
complex-catalyzed allylic amination of 1-(n-propyl)-2-propenyl
carbonate gave a branch amine in high selectivity.9c,d In the
rhodium case, lithium N-tosyl amide was used as a nucleophile
to obtain products in high yield. The use of an amine gives a
modest yield of products. Although the ruthenium complex and
the rhodium complex favor the formation of a branch amine,
the iridium complex shows branch amine selectivity better or
comparable to those of the ruthenium complex and the rhodium
complex. On the other hand, the regioselectivity of nickel
complex-catalyzed allylic amination is similar to that of
palladium complex-catalyzed allylic amination. A nickel com-
plex has been reported to give a linear amine predominantly.9f
In conclusion, we have realized highly selective allylic
amination by using an iridium complex as a catalyst. The
selectivities described here have not been achieved in previous
studies with palladium. Iridium complex-catalyzed allylic ami-
nation represents a new method for the synthesis of various
allylic amines.
1
4.078 g (86%). H NMR (400 MHz, CDCl3) δ 2.18 (br, 1H), 2.32 (s,
3H), 4.26 (dd, J ) 5.8, 1.4 Hz, 2H), 6.27 (dt, J ) 15.9, 5.8 Hz, 1H),
6.54 (d, J ) 15.9 Hz, 1H), 7.09 (d, J ) 8.0 Hz, 2H), 7.25 (d, J ) 8.0
Hz, 2H); 13C NMR (100 MHz, CDCl3) δ 21.1, 63.6, 126.3 (2C), 127.4,
129.2 (2C), 131.0, 133.8, 137.4.
(E)-3-(4-Fluorophenyl)-2-propen-1-ol was prepared similarly to
give (E)-3-(4-methylphenyl)-2-propen-1-ol from 4-fluorobenzaldehyde
1
and triethyl phosphonoacetate. H NMR (400 MHz, CDCl3) δ 2.43
(br, 1H), 4.28 (d, J ) 5.6 Hz, 2H), 6.24 (dt, J ) 15.9, 5.6 Hz, 1H),
6.54 (d, J ) 15.9 Hz, 1H), 6.98 (t, J ) 8.7 Hz, 2H), 7.30 (dd, J ) 8.7,
5.4 Hz, 2H); 13C NMR (100 MHz, CDCl3) δ 63.3, 115.4 (d, JC-F
)
Experimental Section
21.6 Hz, 2C), 127.9 (d, JC-F ) 8.0 Hz, 2C), 128.2 (d, JC-F ) 1.7 Hz),
129.8, 132.8 (d, JC-F ) 3.2 Hz), 162.2 (d, JC-F ) 246.8 Hz).
(E)-3-(2-Thienyl)-2-propen-1-ol was prepared similarly to give (E)-
3-(4-methylphenyl)-2-propen-1-ol from 2-thiophenaldehyde and triethyl
Materials. All reagents and solvents were dried and purified before
use by the usual procedures. Allylic esters were prepared by the reaction
of the corresponding alcohols with acetyl chloride, acetic anhydride,
or methyl chloroformate. Linalyl acetate was purchased. (E)-3-Phenyl-
2-propen-1-ol, (E)-2-nonen-1-ol, (E)-2-undecen-1-ol, (Z)-2-nonen-1-
ol, and (Z)-2-buten-1,4-diol were purchased. 1-Phenyl-2-propen-1-ol,
1-(4-methylphenyl)-2-propen-1-ol, 1-(4-fluorophenyl)-2-propen-1-ol,
and 1-(2-thienyl)-2-propen-1-ol were prepared by the reaction of
vinylmagnesium bromide with the corresponding aldehyde. 3-Methyl-
1-octen-3-ol was prepared by the reaction of vinylmagnesium bromide
with 2-heptanone. (Z)-2-Nonen-1-ol, (Z)-2-undecen-1-ol, (Z)-6-phenyl-
2-hexen-1-ol, (Z)-2,8-nonadien-1-ol, (Z)-5-ethyl-2-nonen-1-ol, and (Z)-
3-phenyl-2-propen-1-ol were prepared by the hydrogenation of the
corresponding 2-alkyn-1-ol. (Z)-2-Nonyn-1-ol, (Z)-2-undecyn-1-ol, and
(Z)-6-phenyl-2-hexyn-1-ol were prepared by the reaction of 1-alky-
nyllithium with paraformaldehyde.29 (Z)-2-Nonyn-8-en-1-ol and (Z)-
5-ethyl-2-nonyn-1-ol were prepared by the reaction of dilithiated
propargyl alcohol with the corresponding alkyl bromide in liquid
ammonia.30 (Z)-4-Butoxy-2-buten-1-ol was prepared by the reaction
of monosodio-(Z)-2-buten-1,4-diol with 1-iodobutane. [Ir(COD)Cl]2,31
[Ir(COD)2]BF4,32 and [Ir(COD)OMe]233 were prepared according to the
published method. Lindlar catalyst was purchased from Wako chemi-
cals. Amines, 4-methylbenzaldehyde, 4-fluorobenzaldehyde, 2-thiophe-
naldehyde, cyclohexanecarboxaldehyde, triethyl phosphonoacetate, and
DIBALH (diisobutylaluminum hydride) were purchased.
1
phosphonoacetate. H NMR (400 MHz, CDCl3) δ 2.65 (br, 1H), 4.21
(d, J ) 5.7 Hz, 2H), 6.15 (dt, J ) 15.7, 5.7 Hz, 1H), 6.69 (d, J ) 15.7
Hz, 1H), 6.91-6.94 (m, 2H), 7.12-7.13 (m, 1H); 13C NMR (100 MHz,
CDCl3) δ 63.0, 124.0, 124.2, 125.6, 127.2, 128.1, 141.7.
(E)-3-Cyclohexyl-2-propen-1-ol. To a solution of NaH (1.056 g,
44 mmol) in dimethoxyethane (80 mL) was added triethyl phospho-
noacetate (10.761 g, 48 mmol) dropwise at 0 °C. The mixture was
stirred at 0 °C for 30 min, and the mixture was gradually warmed to
room temperature. Cyclohexanecarboxaldehyde (4.487 g, 40 mmol) was
added, and the resulting mixture was stirred at room temperature for 3
h. Water was added, and the mixture was extracted with ether. The
ether solution was dried with MgSO4 and evaporated in vacuo. Column
chromatography (n-hexane/AcOEt ) 98/2) of the residue gave ethyl
(E)-3-cyclohexyl-2-propenoate, yield 5.249 g (72%). Medium-pressure
column chromatography of this mixture gave pure (E)-3-cyclohexyl-
2-propenoate. Reduction of (E)-3-cyclohexyl-2-propenoate by DIBALH
1
gave (E)-3-cyclohexyl-2-propen-1-ol. H NMR (400 MHz, CDCl3) δ
1.02-1.32 (m, 5H), 1.62-1.79 (m, 6H), 1.93-2.00 (m, 1H), 4.07 (d,
J ) 5.0 Hz, 2H), 5.57 (dt, J ) 15.6, 5.0 Hz, 1H), 5.64 (dd, J ) 15.6,
5.7 Hz, 1H); 13C NMR (100 MHz, CDCl3) δ 25.9 (2C), 26.1, 32.7
(2C), 40.2, 63.8, 126.3, 139.0.
Allylic Amination of Allylic Esters. A typical procedure is described
(Table 1, entry 1). A mixture of methyl (E)-3-phenyl-2-propenyl
carbonate, 1a, (384 mg, 2.0 mmol), triphenyl phosphite (49.6 mg, 0.16
mmol), [Ir(COD)Cl]2 (26.9 mg, 0.04 mmol), piperidine (511 mg, 6.0
mmol), and EtOH (4.4 mL) was stirred under refluxing EtOH for 2 h
under an Ar atmosphere. The progress of the reaction was monitored
by GLC. After 1a was consumed, the reaction mixture was diluted
with ether. The ethereal solution was extracted with 6 M HCl. Combined
acidic layers were neutralized with NaOH and extracted with ether.
The organic layer was dried with MgSO4 and filtered. After evaporation
of the solvent, the residue was purified by column chromatography
(n-hexane/ethyl acetate (70/30)) to give 3a and (E)-4a (338 mg; yield
84%).
1
General Methods. H NMR and 13C NMR spectra were measured
on a JEOL EX-270 spectrometer or a Bruker AVANCE-400 spec-
trometer using Me4Si as an internal standard. Samples were dissolved
in CDCl3 or benzene-d6 solutions. GC analyses were performed on a
Shimadzu GC-14A by using 3 mm × 2 m glass columns packed with
either 5% PEG-HT on 60/80 mesh chromosorb w AW-DMCS, 5%
PEG-HT + 1% KOH on 60/80 mesh uniport HP, or 5% OV-17 on
60/80 mesh chromosorb w AW-DMCS. Column chromatography was
carried out on 70-230 mesh silica gel (Merck, Silica Gel 60). Elemental
analyses were performed at the Microanalytical Center of Kyoto
University.
(E)-3-(4-Methylphenyl)-2-propen-1-ol. To a THF (60 mL) solution
of 4-methylbenzaldehyde (4.806 g, 40 mmol) and triethyl phospho-
1-[(E)-3-Phenyl-2-propenyl]pyrrolidine ((E)-4b). Compound (E)-
4b could not be isolated in a pure form. Partial 1H NMR spectra were
(29) Brandsma, L. PreparatiVe Acetylenic Chemistry, 2nd ed.; Elsevier:
Amsterdam, 1988; p 81.
(30) Ref 29, p 57.
(31) Crabtree, R. H.; Quirk, J. M.; Felkin, H.; Fillebeen-Khan, T. Synth.
React. Inorg. Met.-Org. Chem. 1982, 12, 407.
(32) Schenck, T. G.; Downs, J. M.; Milne, C. R. C.; Mackenzie, P.;
Boucher, H.; Whealan, J.; Bosnich, B. Inorg. Chem. 1985, 24, 2334.
(33) Uson, R.; Oro, L. A.; Cabeza, J. A. Inorg. Synth. 1985, 23, 128.
1
obtained from the mixture of 3b. H NMR (400 MHz, CDCl3) δ 3.27
(d, J ) 6.7 Hz, 2H), 6.33 (dt, J ) 15.8, 6.7 Hz, 1H), 6.54 (d, J ) 15.8
Hz, 1H).
N-(1-Phenyl-2-propenyl)cyclopentylamine (3d). 1H NMR (400
MHz, CDCl3) δ 1.24-1.88 (m, 9H), 3.03 (quintet, J ) 7.0 Hz, 1H),
4.24 (d, J ) 7.1 Hz, 1H), 5.08 (dd, J ) 10.2, 1.1 Hz, 1H), 5.18 (dd, J

9532 J. Am. Chem. Soc., Vol. 123, No. 39, 2001
Takeuchi et al.
1
) 17.2, 1.1 Hz, 1H), 5.93 (ddd, J ) 17.2, 10.2, 7.1 Hz, 1H), 7.22-
7.33 (m, 5H); 13C NMR (100 MHz, CDCl3) δ 23.9 (2C), 33.2, 33.4,
57.1, 64.5, 114.6, 127.0, 127.3 (2C), 128.4 (2C), 141.5, 143.3. Anal.
Calcd for C14H19N: C, 83.53; H, 9.51; N, 6.96. Found: C, 83.23; H,
9.41; N, 6.93.
spectra were obtained from the mixture of 11b. H NMR (400 MHz,
CDCl3) δ 6.21 (dt, J ) 15.8, 6.8 Hz, 1H), 6.45 (d, J ) 15.8 Hz, 1H).
1-[1-(2-Thienyl)-2-propenyl]piperidine (11c). 1H NMR (400 MHz,
CDCl3) δ 1.38-1.44 (m, 2H), 1.56 (quintet, J ) 5.6 Hz, 4H), 2.38
(quintet, J ) 5.6 Hz, 2H), 2.49 (quintet, J ) 5.6 Hz, 2H), 4.10 (d, J )
8.3 Hz, 1H), 5.20 (dd, J ) 10.5, 0.9 Hz, 1H), 5.21 (dd, J ) 16.7, 0.9
Hz, 1H), 5.99 (ddd, J ) 16.7, 10.5, 8.3 Hz, 1H), 6.86 (dd, J ) 3.5, 0.9
Hz, 1H), 6.93 (dd, J ) 5.1, 3.5 Hz, 1H), 7.21 (dd, J ) 5.1, 0.9 Hz,
1H); 13C NMR (100 MHz, CDCl3) δ 24.6, 26.2 (2C), 51.5 (2C), 69.5,
117.2, 124.4, 124.5, 126.3, 137.9, 146.5. Anal. Calcd for C12H17NS:
C, 69.51; H, 8.26; N, 6.76; S, 15.47. Found: C, 69.46; H, 8.13; N,
6.65; S, 15.69.
N-[(E)-3-(2-Thienyl)-2-propenyl]piperidine ((E)-12c). Compound
(E)-12c could not be isolated in a pure form. Partial H NMR spectra
were obtained from the mixture of 11c. H NMR (400 MHz, CDCl3)
δ 3.07 (d, J ) 6.9 Hz, 2H), 6.13 (dt, J ) 15.6, 6.9 Hz, 1H), 6.61 (d,
J ) 15.6 Hz, 1H).
1-[1-(n-Hexyl)-2-propenyl]piperidine (14aa). 1H NMR (400 MHz,
CDCl3) δ 0.87 (t, J ) 7.0 Hz, 3H), 1.19-1.27 (m, 8H), 1.36-1.43 (m,
4H), 1.45-1.63 (m, 4H), 2.26-2.40 (m, 2H), 2.49-2.54 (m, 2H), 2.68
(td, J ) 8.9, 4.3 Hz, 1H), 5.02 (dd, J ) 16.5, 2.0 Hz, 1H), 5.13 (dd,
J ) 10.3, 2.0 Hz, 1H), 5.68 (ddd, J ) 16.5, 10.3, 8.9 Hz, 1H); 13C
NMR (100 MHz, CDCl3) δ 14.0, 22.6, 24.9, 26.4 (2C), 26.6, 29.4,
31.8, 31.9, 50.7 (2C), 69.2, 116.8, 138.1. Anal. Calcd for C14H27N: C,
80.31; H, 13.00; N, 6.69. Found: C, 80.02; H, 13.08; N, 6.60.
1-[(E)-2-Noneyl]piperidine ((E)-15aa). Compound (E)-15aa could
not be isolated in a pure form. Partial 1H NMR spectra were obtained
from the mixture of 14aa. 1H NMR (400 MHz, CDCl3) δ 2.97 (d, J )
5.9 Hz, 2H), 5.49 (dt, J ) 15.3, 6.3 Hz, 1H), 5.56 (dt, J ) 15.3, 5.9
Hz, 1H).
1-[(Z)-2-Nonenyl]piperidine ((Z)-15aa). 1H NMR (400 MHz, C6D6)
δ 1.00 (t, J ) 7.0 Hz, 3H), 1.30-1.51 (m, 10H), 1.66 (quintet, J ) 5.1
Hz, 4H), 2.19 (q, J ) 7.1 Hz, 2H), 2.48 (t, J ) 5.1 Hz, 4H), 3.09 (d,
J ) 6.7 Hz, 2H), 5.64 (dtt, J ) 11.0, 7.3, 1.6 Hz, 1H), 5.77 (dtt, J )
11.0, 6.7, 1.5 Hz, 1H); 13C NMR (100 MHz, CDCl3) δ 14.0, 22.6,
24.3, 26.0 (2C), 27.4, 28.9, 29.5, 31.7, 54.5 (2C), 55.8, 126.3, 132.7.
Anal. Calcd for C14H27N: C, 80.31; H, 13.00; N, 6.69. Found: C, 80.07;
H, 13.01; N, 6.65.
N-[(E)-3-Phenyl-2-propenyl]cyclopentylamine ((E)-4d): Com-
1
pound (E)-4d could not be isolated in a pure form. Partial H NMR
1
spectra were obtained from the mixture of 3d. H NMR (400 MHz,
CDCl3) δ 3.40 (dd, J ) 6.4, 1.4 Hz, 2H), 6.32 (dt, J ) 15.8, 6.4 Hz,
1H), 6.52 (d, J ) 15.8 Hz, 1H).
N-(1-Phenyl-2-propenyl)-n-butylamine (3e). 1H NMR (400 MHz,
CDCl3) δ 0.89 (t, J ) 7.3 Hz, 3H), 1.34 (sextet, J ) 7.3 Hz, 2H), 1.40
(br, 1H), 1.47 (quintet, J ) 7.3 Hz, 2H), 2.49 (dt, J ) 11.4, 7.3 Hz,
1H), 2.59 (dt, J ) 11.4, 7.3 Hz, 1H), 4.17 (d, J ) 7.1 Hz, 1H), 5.08
(dd, J ) 10.2, 1.5 Hz, 1H), 5.19 (dd, J ) 17.1, 1.5 Hz, 1H), 5.92 (ddd,
J ) 17.1, 10.2, 7.1 Hz, 1H), 7.21-7.37 (m, 5H); 13C NMR (100 MHz,
CDCl3) δ 14.4, 20.9, 32.8, 47.8, 66.7, 115.1, 127.5, 127.6 (2C), 128.9
(2C), 141.7, 143.6. Anal. Calcd for C13H19N: C, 82.48; H, 10.12; N,
7.40. Found: C, 82.19; H, 9.94; N, 7.26.
1
1
(1-Phenyl-2-propenyl)diethylamine (3f). 1H NMR (400 MHz,
CDCl3) δ 0.98 (t, J ) 7.1 Hz, 6H), 2.55 (q, J ) 7.1 Hz, 2H), 2.57 (q,
J ) 7.1 Hz, 2H), 4.13 (d, J ) 8.9 Hz, 1H), 5.12 (dd, J ) 10.1, 1.3 Hz,
1H), 5.18 (dd, J ) 17.1, 1.3 Hz, 1H), 5.95 (ddd, J ) 17.1, 10.1, 8.9
Hz, 1H), 7.19-7.39 (m, 5H); 13C NMR (100 MHz, CDCl3) δ 11.5
(2C), 42.8 (2C), 69.4, 116.0, 126.8, 127.8 (2C), 128.3 (2C), 139.5,
143.0. Anal. Calcd for C13H19N: C, 82.48; H, 10.12; N, 7.40. Found:
C, 82.36; H, 10.36; N, 7.23.
N-(1-Phenyl-2-propenyl)-t-butylamine (3g). 1H NMR (400 MHz,
CDCl3) δ 1.08 (s, 9H), 1.31 (s, 1H), 4.40 (d, J ) 6.9 Hz, 1H), 4.99 (dt,
J ) 10.1, 1.5 Hz, 1H), 5.10 (dt, J ) 17.1, 1.5 Hz, 1H), 5.98 (ddd, J )
17.1, 10.1, 6.9 Hz, 1H), 7.17-7.37 (m, 5H); 13C NMR (100 MHz,
CDCl3) δ 30.6 (3C), 52.0, 60.9, 114.0, 127.1, 127.7 (2C), 128.8 (2C),
144.1, 146.8. Anal. Calcd for C13H19N: C, 82.48; H, 10.12; N, 7.40.
Found: C, 82.34; H, 10.35; N, 7.30.
1
N-(1-Phenyl-2-propenyl)benzylamine (3h). H NMR (400 MHz,
CDCl3) δ 1.63 (s, 1H), 3.72 (d, J ) 4.1 Hz, 2H), 4.22 (d, J ) 7.1 Hz,
1H), 5.11 (dd, J ) 10.2, 1.5 Hz, 1H), 5.22 (dd, J ) 17.1, 1.5 Hz, 1H),
5.94 (ddd, J ) 17.1, 10.2, 7.1 Hz, 1H), 7.22-7.38 (m, 10H); 13C NMR
(100 MHz, CDCl3) δ 51.3, 65.1, 115.1, 126.9, 127.2, 127.3 (2C), 128.1
(2C), 128.4 (2C), 128.5 (2C), 140.5, 141.0, 142.8. Anal. Calcd for
C16H17N: C, 86.05; H, 7.67; N, 6.27. Found: C, 85.79; H, 7.50; N,
6.26.
1-[1-(n-Hexyl)-2-propenyl]pyrrolidine (14ab). 1H NMR (400 MHz,
C6D6) δ 1.00 (t, J ) 6.8 Hz, 3H), 1.38-1.44 (m, 8H), 1.57-1.63 (m,
2H), 1.71-1.80 (m, 4H), 2.54-2.62 (m, 4H), 2.77 (td, J ) 8.9, 4.3
Hz, 1H), 5.14 (dd, J ) 10.2, 2.2 Hz, 1H), 5.17 (dd, J ) 17.2, 2.2 Hz,
1H), 5.88 (ddd, J ) 17.2, 10.2, 8.9 Hz, 1H); 13C NMR (100 MHz,
C6D6) δ 14.3, 23.1, 23.8 (2C), 26.1, 30.0, 32.3, 34.5, 51.4 (2C), 68.4,
115.6, 140.9. Anal. Calcd for C13H25N: C, 79.93; H, 12.90; N, 7.17.
Found: C, 79.78; H, 13.10; N, 7.00.
1-[(E)-2-Noneyl]pyrrolidine ((E)-15ab). Compound (E)-15ab could
not be isolated in a pure form. Partial H NMR spectra were obtained
from the mixture of 14ab. H NMR (400 MHz, C6D6) δ 3.17 (d, J )
5.9 Hz, 2H), 5.73 (dt, J ) 15.3, 6.3 Hz, 1H), 5.80 (dt, J ) 15.3, 5.9
N-[(E)-3-Phenyl-2-propenyl]benzylamine ((E)-4h). Compound (E)-
4h could not be isolated in a pure form. Partial 1H NMR spectra were
1
obtained from the mixture of 3h. H NMR (400 MHz, CDCl3) δ 6.31
(dt, J ) 15.9, 6.3 Hz, 1H), 6.53 (d, J ) 15.9 Hz, 1H).
1-[1-(4-Methylphenyl)-2-propenyl]piperidine (11a). 1H NMR (400
MHz, CDCl3) δ 1.37-1.43 (m, 2H), 1.54 (quintet, J ) 5.6 Hz, 4H),
2.26-2.40 (m, 7H), 3.61 (d, J ) 8.6 Hz, 1H), 5.05 (dd, J ) 10.1, 1.7
Hz, 1H), 5.15 (dd, J ) 17.1, 1.7 Hz, 1H), 5.94 (ddd, J ) 17.1, 10.1,
8.6 Hz, 1H), 7.10-7.23 (m, 4H); 13C NMR (100 MHz, CDCl3) δ 21.0,
24.7, 26.2 (2C), 52.4 (2C), 75.1, 115.5, 127.8 (2C), 129.1 (2C), 136.4,
139.4, 140.6. Anal. Calcd for C15H21N: C, 83.67; H, 9.83; N, 6.50.
Found: C, 83.49; H, 9.98; N, 6.22.
1
1
Hz, 1H).
1-[(Z)-2-Nonenyl]pyrrolidine ((Z)-15ab). 1H NMR (400 MHz,
C6D6) δ 1.00 (t, J ) 6.8 Hz, 3H), 1.31-1.51 (m, 8H), 1.71-1.77 (m,
4H), 2.20 (q, J ) 7.3 Hz, 2H), 2.54-2.63 (m, 4H), 3.26 (d, J ) 6.7
Hz, 2H), 5.62 (dtt, J ) 11.0, 7.3, 1.6 Hz, 1H), 5.83 (dtt, J ) 11.0, 6.7,
1.6 Hz, 1H); 13C NMR (100 MHz, CDCl3) δ 14.3, 23.0, 24.0 (2C),
27.9, 29.3, 30.0, 32.1, 52.9, 54.2 (2C), 128.4, 131.6. Anal. Calcd for
C13H25N: C, 79.93; H, 12.90; N, 7.17. Found: C, 80.01; H, 12.98; N,
7.14.
1-[(Z)-2-Nonenyl]morpholine ((Z)-15ac). 1H NMR (270 MHz,
CDCl3) δ 0.89 (t, J ) 6.9 Hz, 3H), 1.29-1.34 (m, 8H), 2.06 (q, J )
6.9 Hz, 2H), 2.44-2.55 (m, 4H), 3.01 (d, J ) 6.4 Hz, 2H), 3.72 (t, J
) 4.6 Hz, 4H), 5.44 (dt, J ) 11.2, 6.9 Hz, 1H), 5.58 (dt, J ) 11.2, 6.4
Hz, 1H); 13C NMR (100 MHz, CDCl3) δ 14.0, 22.6, 27.5, 28.9, 29.5,
31.7, 53.6 (2C), 55.5, 67.0 (2C), 125.3, 133.8. Anal. Calcd for C13H25-
NO: C, 73.88; H, 11.92; N, 6.63; O, 7.57. Found: C, 74.13; H, 12.08;
N, 6.80.
1-[(E)-3-(4-Methylphenyl)-2-propenyl]piperidine ((E)-12a). Com-
1
pound (E)-12a could not be isolated in a pure form. Partial H NMR
1
spectra were obtained from the mixture of 11a. H NMR (400 MHz,
CDCl3) δ 3.10 (dd, J ) 6.7, 1.2 Hz, 2H), 6.24 (dt, J ) 15.8, 6.7 Hz,
1H), 6.46 (d, J ) 15.8 Hz, 1H).
1-[1-(4-Fluorophenyl)-2-propenyl]piperidine (11b). 1H NMR (400
MHz, CDCl3) δ 1.38-1.44 (m, 2H), 1.54 (quintet, J ) 5.5 Hz, 4H),
2.24-2.29 (m, 2H), 2.39-2.40 (m, 2H), 3.65 (d, J ) 8.6 Hz, 1H),
5.08 (dd, J ) 10.1, 1.7 Hz, 1H), 5.16 (dd, J ) 17.1, 1.7 Hz, 1H), 5.90
(ddd, J ) 17.1, 10.1, 8.6 Hz, 1H), 6.95-7.01 (m, 2H), 7.25-7.32 (m,
2H); 13C NMR (100 MHz, CDCl3) δ 24.6, 26.0 (2C), 52.3 (2C), 74.4,
115.1 (d, JC-F ) 21.0 Hz, 2C), 116.0, 129.3 (d, JC-F ) 7.8 Hz, 2C),
138.1 (d, JC-F ) 3.1 Hz), 140.1, 161.8 (d, JC-F ) 244.7 Hz). Anal.
Calcd for C14H18FN: C, 76.68; H, 8.27; F, 8.66; N, 6.39. Found: C,
76.66; H, 8.44; F, 8.95; N, 6.10.
1-(1-n-Hexyl-2-propenyl)morpholine (14ac). Compound 14ac could
not be isolated in a pure form. Partial 1H NMR spectra were obtained
from the mixture of (Z)-15ac. 1H NMR (270 MHz, CDCl3) δ 5.07 (dd,
N-[(E)-3-(4-Fluorophenyl)-2-propenyl]piperidine ((E)-12b). Com-
1
pound (E)-12b could not be isolated in a pure form. Partial H NMR

Iridium Complex-Catalyzed Allylic Amination
J. Am. Chem. Soc., Vol. 123, No. 39, 2001 9533
J ) 16.3, 2.0 Hz, 1H), 5.18 (dd, J ) 10.2, 2.0 Hz, 1H), 5.65 (ddd, J
) 16.3, 10.2, 7.9 Hz, 1H).
5.13 (dd, J ) 17.2, 2.2 Hz, 1H), 5.21 (dd, J ) 10.3, 2.2 Hz, 1H), 5.84
(ddd, J ) 17.2, 10.3, 6.9 Hz, 1H).
N-(1-n-Hexyl-2-propenyl)cyclopentylamine (14ad). 1H NMR (400
MHz, C6D6) δ 0.88 (t, J ) 7.1 Hz, 3H), 1.25-1.47 (m, 15 H), 1.62-
1.82 (m, 4H), 2.96-3.00 (m, 1H), 3.13 (quintet, J ) 6.5 Hz, 1H), 5.02
(dd, J ) 10.1, 2.0 Hz, 1H), 5.04 (dd, J ) 17.2, 2.0 Hz, 1H), 5.54 (ddd,
J ) 17.2, 10.1, 8.1 Hz, 1H); 13C NMR (100 MHz, C6D6) δ 14.3, 23.0,
24.3 (2C), 26.3, 29.8, 32.3, 33.3, 34.5, 36.8, 57.0, 60.6, 114.4, 143.1.
Anal. Calcd for C14H27N: C, 80.31; H, 13.00; N, 6.69. Found: C, 80.56;
H, 13.16; N, 6.51.
1-[1-(n-Octyl)-2-propenyl]pyrrolidine (14bb). 1H NMR (400 MHz,
C6D6) δ 0.86 (t, J ) 7.1 Hz, 3H), 1.24-1.26 (m, 12H), 1.40-1.49 (m,
2H), 1.56-1.69 (m, 4H), 2.41-2.48 (m, 4H), 2.64 (td, J ) 8.6, 4.4
Hz, 1H), 5.01 (dd, J ) 10.2, 2.1 Hz, 1H), 5.04 (dd, J ) 17.2, 2.1 Hz,
1H), 5.75 (ddd, J ) 17.2, 10.2, 8.6 Hz, 1H); 13C NMR (100 MHz,
C6D6) δ 14.3, 23.1, 23.8 (2C), 26.2, 29.8, 30.1, 30.4, 32.3, 34.6, 51.4
(2C), 68.4, 115.6, 140.9. Anal. Calcd for C15H29N: C, 80.65; H, 13.08;
N, 6.27. Found: C, 80.43; H, 13.36; N, 6.12.
N-[(E)-2-Nonenyl]cyclopentylamine ((E)-15ad). Compound (E)-
15ad could not be isolated in a pure form. Partial H NMR spectra
1-[(E)-2-Undecenyl]pyrrolidine ((E)-15bb). Compound (E)-15bb
1
1
could not be isolated in a pure form. Partial H NMR spectra were
were obtained from the mixture of 14ad. 1H NMR (400 MHz, CDCl3)
δ 5.52 (dt, J ) 15.3, 5.7 Hz, 1H), 5.58 (dt, J ) 15.3, 5.2 Hz, 1H).
N-(1-n-Hexyl-2-propenyl)-n-butylamine (14ae). 1H NMR (400
MHz, CDCl3) δ 0.88 (t, J ) 7.2 Hz, 6H), 1.25-1.45 (m, 15H), 2.44
(dt, J ) 11.2, 6.6 Hz, 1H), 2.63 (dt, J ) 11.2, 6.8 Hz, 1H), 2.91 (q, J
) 7.9 Hz, 1H), 5.03 (dd, J ) 10.2, 2.0 Hz, 1H), 5.06 (dd, J ) 17.2,
2.0 Hz, 1H), 5.58 (ddd, J ) 17.2, 10.2, 7.9 Hz, 1H); 13C NMR (100
MHz, CDCl3) δ 14.24, 14.28, 20.9, 23.0, 26.3, 29.9, 32.2, 33.1, 36.4,
47.3, 62.4, 114.7, 142.9. Anal. Calcd for C13H27N: C, 79.11; H, 13.79;
N, 7.10. Found: C, 78.96; H, 13.83; N, 7.09.
obtained from the mixture of 14bb. 1H NMR (400 MHz, C6D6) δ 3.03
(d, J ) 5.3 Hz, 2H), 5.59 (dt, J ) 15.4, 6.3 Hz, 1H), 5.66 (dt, J )
15.4, 5.3 Hz, 1H).
1-[1-Cyclohexyl-2-propenyl]pyrrolidine (14cb). 1H NMR (400
MHz, C6D6) δ 0.91-1.31 (m, 4H), 1.50-1.77 (m, 10H), 1.98-2.00
(m, 1H), 2.42-2.47 (m, 5H), 5.00 (dd, J ) 17.2, 2.3 Hz, 1H), 5.07
(dd, J ) 10.3, 2.3 Hz, 1H), 5.73 (ddd, J ) 17.2, 10.3, 9.3 Hz, 1H); 13
C
NMR (100 MHz, C6D6) δ 23.7 (2C), 27.0, 27.1, 27.4, 28.5, 31.4, 40.9,
51.1 (2C), 73.4, 116.7, 138.1. Anal. Calcd for C13H23N: C, 80.76; H,
11.99; N, 7.25. Found: C, 80.99; H, 12.23; N, 7.17.
N-[(E)-2-Nonenyl]-n-butylamine ((E)-15ae). Compound (E)-15ae
1-[(E)-3-Cyclohexyl-2-propenyl]pyrrolidine ((E)-15cb). Compound
(E)-15cb could not be isolated in a pure form. Partial 1H NMR spectra
were obtained from the mixture of 14cb. 1H NMR (400 MHz, C6D6) δ
3.06 (d, J ) 5.4 Hz, 2H), 5.58 (dd, J ) 15.8, 6.0 Hz, 1H), 5.65 (dt, J
) 15.8, 5.4 Hz, 1H).
1
could not be isolated in a pure form. Partial H NMR spectra were
1
obtained from the mixture of 14ae. H NMR (400 MHz, CDCl3) δ
3.18 (d, J ) 5.8 Hz, 2H), 5.51 (dt, J ) 15.4, 5.9 Hz, 1H), 5.58 (dt, J
) 15.4, 5.8 Hz, 1H).
N-[(Z)-2-Nonenyl]-n-butylamine ((Z)-15ae). 1H NMR (400 MHz,
C6D6) δ 0.97-1.03 (m, 6H), 1.36-1.53 (m, 13H), 2.17 (q, J ) 7.3
Hz, 2H), 2.65 (t, J ) 5.9 Hz, 2H), 3.37 (d, J ) 6.6 Hz, 2H), 5.60 (dt,
J ) 10.9, 7.3 Hz, 1H), 5.68 (dt, J ) 10.6, 6.6 Hz, 1H); 13C NMR (67.8
MHz, CDCl3) δ 13.9, 14.0, 20.5, 22.6, 27.4, 28.9, 29.6, 31.7, 32.2,
46.3, 49.2, 128.0, 131.9. Anal. Calcd for C13H27N: C, 79.11; H, 13.79;
N, 7.10. Found: C, 79.11; H, 14.03; N, 7.01.
1
N-(1-Cyclohexyl-2-propenyl)aniline (14ci). H NMR (400 MHz,
CDCl3) δ 1.01-1.30 (m, 5H), 1.46-1.51 (m, 1H), 1.66-1.86 (m, 5H),
3.62-3.65 (m, 2H), 5.13 (d, J ) 10.3, 1.6 Hz, 1H), 5.16 (dd, J )
17.0, 1.6 Hz, 1H), 5.71 (ddd, J ) 17.0, 10.3, 6.6 Hz, 1H), 6.56-6.66
(m, 3H), 7.10-7.15 (m, 2H); 13C NMR (100 MHz, CDCl3) δ 26.27,
26.33, 26.5, 29.3, 29.4, 42.7, 61.0, 113.2 (2C), 115.7, 116.9, 129.1
(2C), 138.3, 147.9. Anal. Calcd for C15H21N: C, 83.67; H, 9.83; N,
6.50. Found: C, 83.39; H, 10.03; N, 6.54.
1
N-[(Z)-2-Nonenyl]diethylamine ((Z)-15af). H NMR (400 MHz,
C6D6) δ 1.00 (t, J ) 7.1 Hz, 3H), 1.12 (t, J ) 7.1 Hz, 6H), 1.34-1.50
(m, 8H), 2.19 (q, J ) 7.1 Hz, 2H), 2.59 (q, J ) 7.1 Hz, 4H), 3.24 (d,
J ) 6.6 Hz, 2H), 5.63 (dtt, J ) 11.0, 7.1, 1.6 Hz, 1H), 5.75 (dtt, J )
11.0, 6.6, 1.5 Hz, 1H); 13C NMR (100 MHz, C6D6) δ 12.5 (2C), 14.2,
23.0, 27.9, 29.3, 30.1, 32.1, 47.2 (2C), 50.3, 128.4, 132.1. Anal. Calcd
for C13H27N: C, 79.11; H, 13.79; N, 7.10. Found: C, 79.14; H, 13.75;
N, 7.12.
N-((E)-3-Cyclohexyl-2-propenyl)aniline ((E)-15ci). Compound (E)-
15ci could not be isolated in a pure form. Partial 1H NMR spectra were
obtained from the mixture of 14ci. 1H NMR (400 MHz, CDCl3) δ 3.67
(d, J ) 5.8 Hz, 2H), 5.51 (dtd, J ) 15.5, 5.8, 1.0 Hz, 1H), 5.64 (dd,
J ) 15.5, 6.5 Hz, 1H).
1-[(Z)-6-Phenyl-2-hexenyl]piperidine ((Z)-15d). 1H NMR (400
MHz, C6D6) δ 1.32-1.38 (m, 2H), 1.54 (quintet, J ) 5.6 Hz, 4H),
1.60 (quintet, J ) 7.5 Hz, 2H), 2.03 (q, J ) 7.3 Hz, 2H), 2.32 (br,
4H), 2.49 (t, J ) 7.6 Hz, 2H), 2.91 (d, J ) 6.7 Hz, 2H), 5.49 (dtt, J )
11.0, 7.3, 1.6 Hz, 1H), 5.67 (dtt, J ) 11.0, 6.7, 1.6 Hz, 1H), 7.06-
7.20 (m, 5H); 13C NMR (100 MHz, CDCl3) δ 24.3, 25.9 (2C), 27.0,
31.2, 35.4, 54.5 (2C), 55.9, 125.7, 127.0, 128.2 (2C), 128.4 (2C), 132.2,
142.3. Anal. Calcd for C17H25N: C, 83.89; H, 10.35; N, 5.75. Found:
C, 83.64; H, 10.65; N, 5.67.
N-[1-(n-Hexyl)-2-propenyl]diethylamine (14af). Compound 14af
1
could not be isolated in a pure form. Partial H NMR spectra were
1
obtained from the mixture of (Z)-15af. H NMR (400 MHz, C6D6) δ
5.11 (dd, J ) 17.2, 2.1 Hz, 1H), 5.20 (dd, J ) 10.4, 2.2 Hz, 1H), 5.81
(ddd, J ) 17.2, 10.4, 6.9 Hz, 1H).
N-[1-(n-Hexyl)-2-propenyl]aniline (14ai). 1H NMR (400 MHz,
CDCl3) δ 0.88 (t, J ) 7.0 Hz, 3H), 1.28-1.45 (m, 8H), 1.54-1.60 (m,
2H), 3.59 (br, 1H), 3.78 (q, J ) 6.2 Hz, 1H), 5.10 (dd, J ) 10.3, 1.3
Hz, 1H), 5.19 (d, J ) 17.2, 1.3 Hz, 1H), 5.72 (ddd, J ) 17.2, 10.3, 6.2
Hz, 1H), 6.56-6.69 (m, 3H), 7.11-7.18 (m, 2H); 13C NMR (100 MHz,
CDCl3) δ 14.0, 22.6, 25.9, 29.2, 31.7, 35.9, 55.9, 113.3 (2C), 114.9,
117.1, 129.1 (2C), 140.2, 147.7. Anal. Calcd for C15H23N: C, 82.89;
H, 10.67; N, 6.44. Found: C, 82.63; H, 10.87; N, 6.27.
1-[1-(3-Phenylpropyl)-2-propenyl]piperidine (14d). Compound
14d could not be isolated in a pure form. Partial 1H NMR spectra were
1
obtained from the mixture of (Z)-15d. H NMR (400 MHz, C6D6) δ
4.96 (dd, J ) 17.2, 2.1 Hz, 1H), 5.07 (dd, J ) 10.3, 2.1 Hz, 1H).
1
1-[(Z)-2,8-Nonadienyl]piperidine ((Z)-15e). H NMR (400 MHz,
C6D6) δ 1.24-1.37 (m, 6H), 1.54 (quintet, J ) 5.7 Hz, 4H), 1.93-
2.04 (m, 4H), 2.34 (br, 4H), 2.95 (d, J ) 6.7 Hz, 2H), 4.97 (ddt, J )
10.2, 2.0, 1.0 Hz, 1H), 5.02 (dq, J ) 17.1, 2.0 Hz, 1H), 5.48 (dtt, J )
11.0, 7.3, 1.5 Hz, 1H), 5.65 (dtt, J ) 11.0, 6.7, 1.5 Hz, 1H), 5.75 (ddt,
J ) 17.1, 10.2, 6.7 Hz, 1H); 13C NMR (100 MHz, CDCl3) δ 24.4,
26.0 (2C), 27.3, 28.5, 29.0, 33.6, 54.5 (2C), 55.9, 114.3, 126.6, 132.5,
138.9. Anal. Calcd for C14H25N: C, 81.09; H, 12.15; N, 6.75. Found:
C, 80.83; H, 12.42; N, 6.74.
1-[(Z)-5-Ethyl-2-nonenyl]piperidine ((Z)-15f). 1H NMR (400 MHz,
C6D6) δ 0.99 (t, J ) 7.0 Hz, 3H), 1.02 (t, J ) 6.7 Hz, 3H), 1.38-1.47
(m, 11H), 1.66 (quintet, J ) 5.6 Hz, 4H), 2.18-2.20 (m, 2H), 2.49 (t,
J ) 5.2 Hz, 4H), 3.12 (d, J ) 6.7 Hz, 2H), 5.65 (dtt, J ) 11.1, 7.3, 1.6
Hz, 1H), 5.81 (dtt, J ) 11.1, 6.7, 1.5 Hz, 1H); 13C NMR (67.8 MHz,
CDCl3) δ 11.0, 14.1, 23.0, 24.4, 25.8, 26.0 (2C), 29.0, 31.1, 32.7, 39.5,
54.6 (2C), 56.1, 127.2, 131.4. Anal. Calcd for C16H31N: C, 80.94; H,
13.16; N, 5.90. Found: C, 80.99; H, 13.12; N, 5.84.
N-[(E)-2-Nonenyl]aniline ((E)-15ai). Compound (E)-15ai could not
be isolated in a pure form. Partial 1H NMR spectra were obtained from
1
the mixture of 14ai. H NMR (400 MHz, C6D6) δ 5.38 (dt, J ) 15.3,
5.7 Hz, 1H), 5.53 (dt, J ) 15.3, 6.7 Hz, 1H).
1-[(Z)-2-Undecenyl]piperidine ((Z)-15ba). 1H NMR (400 MHz,
C6D6) δ 1.0 (t, J ) 6.7 Hz, 3H), 1.39-1.48 (m, 14H), 1.66 (quintet, J
) 5.7 Hz, 4H), 2.20 (q, J ) 7.3 Hz, 2H), 2.48 (t, J ) 5.1 Hz, 4H),
3.10 (d, J ) 6.7 Hz, 2H), 5.64 (dtt, J ) 11.0, 7.3, 1.6 Hz, 1H), 5.77
(dtt, J ) 11.0, 6.7, 1.5 Hz, 1H); 13C NMR (67.8 MHz, CDCl3) δ 14.1,
22.6, 24.4, 26.0 (2C), 27.4, 29.3 (2C), 29.4, 29.5, 31.8, 54.5 (2C), 55.9,
126.3, 132.8. Anal. Calcd for C16H31N: C, 80.94; H, 13.16; N, 5.90.
Found: C, 80.81; H, 13.10; N, 5.74.
1-[1-(n-Octyl)-2-propenyl]piperidine (14ba). Compound 14ba
1
could not be isolated in a pure form. Partial H NMR spectra were
1
obtained from the mixture of (Z)-15ba. H NMR (400 MHz, C6D6) δ

9534 J. Am. Chem. Soc., Vol. 123, No. 39, 2001
Takeuchi et al.
1-[(Z)-4-(n-Butoxy)-2-butenyl]piperidine ((Z)-15g). 1H NMR (400
MHz, C6D6) δ 0.86 (t, J ) 7.3 Hz, 3H), 1.29-1.42 (m, 4H), 1.47-
1.58 (m, 6H), 2.28 (br, 4H), 2.88 (d, J ) 6.6 Hz, 2H), 3.32 (t, J ) 6.4
Hz, 2H), 4.00 (d, J ) 6.1 Hz, 2H), 5.68 (dtt, J ) 11.2, 6.6, 1.5 Hz,
1H), 5.78 (dtt, J ) 11.2, 6.1, 1.5 Hz, 1H); 13C NMR (100 MHz, C6D6)
δ 14.1, 19.8, 24.8, 26.4 (2C), 32.3, 54.8 (2C), 56.4, 66.9, 70.2, 129.3,
130.0. Anal. Calcd for C13H25NO: C, 73.88; H, 11.92; N, 6.63; O,
7.57. Found: C, 73.58; H, 11.91; N, 6.49.
20.6, 22.6, 23.1, 23.4, 32.5, 33.1, 40.5, 42.1, 56.8, 112.4, 145.7. Anal.
Calcd for C13H27N: C, 79.11; H, 13.79; N, 7.10. Found: C, 79.02; H,
13.86; N, 7.37.
N-[1-Methyl-1-(n-pentyl)-2-propenyl]aniline (17ai). 1H NMR (400
MHz, CDCl3) δ 0.87 (t, J ) 6.5 Hz, 3H), 1.21-1.37 (m, 9H), 1.43-
1.59 (m, 1H), 1.65-1.72 (m, 1H), 3.64 (br, 1H), 5.14 (dd, J ) 10.5,
1.1 Hz, 1H), 5.15 (dd, J ) 17.8, 1.1 Hz, 1H), 5.94 (dd, J ) 17.8, 10.5
Hz, 1H), 6.64-6.70 (m, 3H), 7.07-7.23 (m, 2H); 13C NMR (100 MHz,
CDCl3) δ 14.0, 22.6, 23.1, 24.4, 32.2, 41.6, 57.2, 113.4, 115.7 (2C),
117.3, 128.7 (2C), 145.5, 146.7. Anal. Calcd for C15H23N: C, 82.89;
H, 10.67; N, 6.44. Found: C, 82.60; H, 10.56; N, 6.36.
1-(n-Butoxylmethyl-2-propenyl)piperidine (14g). Compound 14g
1
could not be isolated in a pure form. Partial H NMR spectra were
1
obtained from the mixture of (Z)-15g. H NMR (400 MHz, C6D6) δ
5.16 (d, J ) 9.8 Hz, 1H), 5.18 (d, J ) 18.8 Hz, 1H), 5.88 (ddd, J )
18.8, 9.8, 7.3 Hz, 1H).
1-[1-Methyl-1-(3-methyl-2-butenyl)-2-propenyl]piperidine (17b).
1H NMR (400 MHz, CDCl3) δ 1.04 (s, 3H), 1.37-1.56 (m, 11H), 1.67
(s, 3H), 1.82-2.02 (m, 2H), 2.45 (br, 4H), 4.98 (dd, J ) 17.7, 1.5 Hz,
1H), 5.07-5.08 (m, 1H), 5.08 (dd, J ) 11.0, 1.5 Hz, 1H), 5.83 (dd, J
) 17.7, 11.0 Hz, 1H); 13C NMR (100 MHz, CDCl3) δ 16.5, 17.6, 22.6,
25.2, 25.7(2C), 27.0, 39.3, 47.1 (2C), 60.8, 112.9, 125.1, 131.0, 145.2.
Anal. Calcd for C15H27N: C, 81.38; H, 12.29; N, 6.33. Found: C, 81.32;
H, 12.43; N, 6.36.
1-[1-Methyl-1-(n-pentyl)-2-propenyl]piperidine (17aa). 1H NMR
(400 MHz, CDCl3) δ 0.87 (t, J ) 7.3 Hz, 3H), 1.01 (s, 3H), 1.20-
1.32 (m, 6H), 1.39-1.45 (m, 4H), 1.53 (quintet, J ) 5.7 Hz, 4H), 2.45
(t, J ) 4.5 Hz, 4H), 4.96 (dd, J ) 17.7, 1.5 Hz, 1H), 5.06 (dd, J )
10.9, 1.5 Hz, 1H), 5.80 (dd, J ) 17.7, 10.9 Hz, 1H); 13C NMR (100
MHz, CDCl3) δ 14.1, 16.4, 22.6, 23.5, 25.2, 27.0 (2C), 32.6, 39.2,
47.1 (2C), 60.9, 112.7, 145.5. Anal. Calcd for C14H27N: C, 80.31; H,
13.00; N, 6.69. Found: C, 80.42; H, 13.14; N, 6.56.
Acknowledgment. Financial support by a Grant-in-Aid for
Science Research (12650857) from the Ministry of Education,
Culture, Sports, Science and Technology, a Research Grant from
the Yokohama Academic Foundation, and a Research Grant
from the Takamura Foundation is gratefully acknowledged. We
thank Hodogaya Chemical Co., Ltd. for the gift of methyl
chloroformate.
1-[1-Methyl-1-(n-pentyl)-2-propenyl]pyrrolidine (17ab). 1H NMR
(400 MHz, CDCl3) δ 0.88 (t, J ) 7.0 Hz, 3H), 1.11 (s, 3H), 1.26-
1.33 (m, 6H), 1.46-1.54 (m, 2H), 1.71-1.73 (m, 4H), 2.62 (br, 4H),
5.01 (dd, J ) 17.7, 1.5 Hz, 1H), 5.12 (dd, J ) 11.0, 1.5 Hz, 1H), 5.85
(dd, J ) 17.7, 11.0 Hz, 1H); 13C NMR (100 MHz, CDCl3) δ 14.1,
18.2, 22.6, 23.76 (2C), 23.81, 32.6, 40.1, 45.7 (2C), 59.1, 113.7, 142.5.
Anal. Calcd for C13H25N: C, 79.93; H, 12.90; N, 7.17. Found: C, 79.76;
H, 13.12; N, 7.05.
Supporting Information Available: Spectral data of known
compounds (3a, (E)-4a, 3b, 3c, (E)-4c, (E)-4e, (E)-4f, (E)-4g)
(pdf). This material is available free of charge via the Internet
at http://pubs.acs.org.
N-[1-Methyl-1-(n-pentyl)-2-propenyl]-n-butylamine (17ae). 1H
NMR (400 MHz, CDCl3) δ 0.88 (t, J ) 7.1 Hz, 3H), 0.90 (t, J ) 7.2
Hz, 3H), 1.11 (s, 3H), 1.17-1.46 (m, 13H), 2.39-2.49 (m, 2H), 4.99
(dd, J ) 17.6, 1.2 Hz, 1H), 5.05 (dd, J ) 10.8, 1.2 Hz, 1H), 5.69 (dd,
J ) 17.6, 10.8 Hz, 1H); 13C NMR (100 MHz, CDCl3) δ 14.0 (2C),
JA0112036