Kaohsiung Medical University Institutional Repository:Item 310902000/6960

A principal goal of organometallic chemistry is the

cat-alytic synthesis of organic compounds by using the

chem-istry of organic ligands covalently bound to transition metals.

Most organometallic chemistry has focused on complexes

with covalent metal-carbon or metal-hydrogen bonds.

Transi-tion metals have been workhorse elements in many

commer-cialized catalytic processes that include hydrogenations,

hy-droformylations, acetic acid production, and other C–C and

C–H bond forming processes.

1—5)

_{Although carbon–oxygen,}

carbon–nitrogen, or carbon–sulfur bonds are found in the

majority of important organic molecules, catalytic

organo-metallic reaction chemistry that leads to the formation of

bon–heteroatom bonds is less common than that forming

car-bon–carbon and carbon–hydrogen bonds. Transition metal

h

3

_{-allyl complexes, as well as transition metal s -alkyl}

com-plexes, play important roles as active species and key

inter-mediates in many reactions catalyzed by transition metal

complexes.

6)

_{The palladium-catalyzed allylation is an}

estab-lished, efficient, and highly stereo- and chemoselective

method for C–C, C–N, and C–O bond formation, which has

been widely applied to organic chemistry.

7—10)

_{The processes}

have been shown to proceed by attack of nucleophiles on

intermediate

h

3

-allylpalladium(II) complexes generated

by oxidative addition of allylic compounds including

halides,

11—13)

_esters,

14—26)

_carbonates,

27—36)

_carbamates,

37—39)

phosphates,

40—42)

_{and related derivatives}

43—49)

_{to a Pd(0)}

complex. Because these substrates are synthesized from the

corresponding allylic alcohols, palladium-catalyzed

conver-sion of allylic alcohols directly into allylation products are

highly desirable, especially from the viewpoint of the atom

economy.

50,51)

For achieving the palladium-catalyzed C–O

bond cleavage of allylic alcohols, various other processes to

facilitate the bond cleavage have been reported.

52)

_These

processes include conversion of allylic alcohols into the

es-ters of inorganic acids (e.g., As

2

O

3

,

53)

B

2

O

3

,

54)

CO

2 8)

) or

em-ployment of a Lewis acid (e.g., BEt

3

,

55—57)

BF

3

,

58)

BPh

3

,

59,60)

SnCl

261—64)

). However, there have been only limited and

spo-radic reports dealing with the direct cleavage of the C–O

bond in allylic alcohols on interaction with a transition metal

complex.

65—72)

Successful applications using allylic alcohols

directly in catalytic processes are even more limited. This

ap-parently stems from the poor capability of a nonactivated

hy-droxyl to serve as a leaving group.

59,60)

We have recently

re-ported our attempts and some successful applications of a

process involving the C–O bond cleavage with direct use of

allylic alcohols catalyzed by palladium complexes.

73—76)

Herein, we report the application of this methodology to the

palladium-catalyzed allylation of acidic and less nucleophilic

anilines

77—80)

_{using allylic alcohols directly.}

The allylation process is straightforward. We studied the

reactions of acidic and less nucleophilic anilines

81)

with allyl

alcohol (2a). When a mixture of diphenylamine (1a, 1 mmol)

and allyl alcohol (2a, 1.2 mmol) was refluxed in the presence

of catalytic amounts of Pd(OAc)

₂

(0.01 mmol), PPh

₃

(0.04 mmol), Ti(OPr

i

)

4

(0.25 mmol), and molecular sieves

(MS 4 Å) (200 mg) in benzene (5 ml) under nitrogen for 3 h,

the product N-allyldiphenylamine (3a) was formed 68%

yield (entry 1 in Table 1). Phenothiazine (1b) behaved the

same (entry 4). 2-Nitroaniline (1c) gave only monoallylation

product under similar experimental conditions, but its meta

isomer 1d, free of steric constraints, gave diallylated

prod-ucts 4d (entries 7, 10). 4-Cyanoaniline (1f ) also gave

mono-and diallylated products in high yields (entry 15). Using

cin-namyl alcohol (2b) as allylating agent worked well with

acidic and less nucleophilic anilines (entries, 2, 5, 8, 11, 13,

15). The sterically more demanding 2-cyclohexenol (2c), was

an inefficient allylation reagent for 1a and for the more acidic

anilines, although at reflux temperature (entries 3, 6, 9, 12,

14, 16). Reaction of 2c with steric constraints amines 1a—c

gave the worst yields.

In summary, we have shown that palladium-catalyzed

ally-lation of anilines using allylic alcohols directly is a simple

and efficient route for C–N bond formation. The effect of

ad-dition of Ti(OPr

i

₎

4

to promote the palladium-catalyzed

allyl-OH bond cleavage remarkably enhanced both the reaction

rate and yield. The amination of allylic alcohol worked well

with acidic and less nucleophilic anilines, giving generally

high yields of the corresponding allylic anilines. Anilines

with steric constraints gave lower chemical yields. The

steri-cally more demanding 2-cyclohexenol (2c) was an inefficient

allylation reagent.

Experimental

General Considerations All reactions were carried out under a nitro-gen atmosphere. Solvents were dried and distilled by known methods. Col-umn chromatography was performed on silica gel. All melting points were uncorrected. IR absorption spectra were recorded on a Perkin-Elmer System 2000 FT-IR spectrophotometer. Proton and carbon-13 NMR were measured with a Unity-400 spectrometer. Carbon multiplicities were obtained from DEPT experiments. Chemical shifts (d) and coupling constants (Hz) were measured with respect to TMS or chloroform-d1. MS and high-resolution

mass spectra (HR-MS) were taken on a Hewlett-Packard 5989A or JEOL

1266 Chem. Pharm. Bull. 53(10) 1266—1269 (2005) Vol. 53, No. 10

∗ To whom correspondence should be addressed. e-mail: [email protected] © 2005 Pharmaceutical Society of Japan

Palladium-Catalyzed Allylation of Acidic and Less Nucleophilic Anilines

Using Allylic Alcohols Directly

Yi-Chun H

SU

, Kim-Hong G

AN

, and Shyh-Chyun Y

ANG

*

Graduate Institute of Pharmaceutical Sciences, Kaohsiung Medical University; Kaohsiung 807, Taiwan, R.O.C.

Received May 23, 2005; accepted July 6, 2005

The direct activation of C–O bonds in allylic alcohols by palladium complexes has been accelerated by car-rying out the reactions in the presence of titanium(IV) isoproxide and 4 Å molecular sieves. The acidic and less nucleophilic anilines such as diphenylamine, phenothiazine, 4-cyanoaniline, and nitroanilines are efficiently ally-lated under palladium catalysis using allylic alcohols as allylating reagents.

JMS D-100 instrument, with a direct inlet system.

General Procedure for the Palladium-Catalyzed Allylation of Ani-lines. Reaction with Diphenylamine (1a) A mixture of diphenylamine (1a) (169 mg, 1 mmol), allyl alcohol (2a) (70 mg, 1.2 mmol), Pd(OAc)2

(2.3 mg, 0.01 mmol), PPh3 (10.5 mg, 0.04 mmol), Ti(OPri)4 (0.075 ml,

0.25 mmol), and MS 4 Å (200 mg) in benzene (5 ml) was refluxed under ni-trogen for 3 h. After cooling, the reaction mixture was filtered through Celite and the solvent was distilled under reduced pressure. Column chromatogra-phy (n-hexane/EtOAc 5 : 1) of the residue afforded 3a in 68% yields.

N-Allyldiphenylamine (3a)82) 1_{H-NMR (CDCl} 3) d 4.33 (2H, ddt, J
1.6, 1.6, 4.0 Hz), 5.14 (1H, ddt, J
1.2, 1.6, 8.4 Hz), 5.25 (1H, ddt, J
1.2, 1.6, 13.6 Hz), 5.91 (1H, ddt, J
4.0, 8.4, 13.6 Hz), 6.91 (2H, t, J
6.0 Hz), 7.01 (4H, d, J
6.8 Hz), 7.23 (4H, dd, J
6.0, 6.8 Hz); 13_C-NMR (CDCl3) d 54.7 (t), 116.3 (t), 120.7 (d), 121.2 (d), 129.2 (d), 134.3 (d), 147.8 (s); EI-MS m/z: 209 (M), 194, 182, 167, 117, 104, 91, 77; HR-MS m/z: 209.1201 (Calcd for C15H15N: 209.1204). N-Cinnamyldiphenylamine (5a)82) 1_{H-NMR (CDCl} 3) d 4.47 (2H, dd, J
1.6, 5.2 Hz), 6.29 (1H, dt, J
5.2, 16.0 Hz), 6.55 (1H, dt, J
1.6, 16.0 Hz), 6.90—6.94 (2H, m), 7.03—7.06 (4H, m), 7.14—7.18 (1H, m), 7.21—7.30 (8H, m); 13_{C-NMR (CDCl} 3) d 54.3 (t), 120.8 (d), 121.3 (d), 126.1 (d), 126.3 (d), 127.4 (d), 128.5 (d), 129.3 (d), 131.3 (d), 136.9 (s), 147.8 (s); EI-MS m/z: 285 (M), 194, 193, 167, 117, 115, 91, 77; HR-MS m/z: 285.1517 (Calcd for C21H19N: 285.1517). N-Allylphenothiazine (3b) 1_{H-NMR (CDCl} 3) d 4.34 (2H, ddd, J
2.0, 2.4, 4.4 Hz), 5.18 (1H, ddt, J
2.0, 2.4, 17.6 Hz), 5.22 (1H, ddt, J
2.0, 2.0, 10.4 Hz), 5.88 (1H, ddt, J
4.4, 10.4, 17.6 Hz), 6.74 (2H, dd, J
1.2, 8.4 Hz), 6.79 (2H, ddd, J
1.2, 7.6, 8.4 Hz), 6.97—7.01 (4H, m); 13_{C-NMR (CDCl} 3) d 50.9 (t), 115.1 (d), 117.3 (t), 122.2 (d), 122.8 (s), 126.6 (d), 127.0 (d), 132.9 (d), 144.2 (s); EI-MS m/z: 239 (M), 199, 198, 171, 167, 154, 127, 69; HR-MS m/z: 239.0768 (Calcd for C15H13NS: 239.0769). N-Cinnamylphenothiazine (5b)82) 1_{H-NMR (CDCl} 3) d 4.57 (2H, dd, J
1.6, 4.4 Hz), 6.31 (1H, dt, J
4.4, 16.4 Hz), 6.53 (1H, dt, J
1.6, 16.4 Hz), 6.82—6.86 (4H, m), 7.00—7.06 (4H, m), 7.17—7.32 (5H, m); 13_C-NMR (CDCl3) d 50.9 (t), 115.3 (d), 122.4 (d), 123.0 (s), 124.8 (d), 126.3 (d), 126.8 (d), 127.3 (d), 127.6 (d), 128.6 (d), 132.0 (d), 136.4 (s), 144.4 (s); EI-MS m/z: 315 (M), 198, 171, 166, 154, 140, 127, 115, 91, 77; HR-MS m/z: 315.1080 (Calcd for C21H17NS: 315.1082). October 2005 1267

Table 1. Palladium-Catalyzed Allylation of Acidic Anilines 1 with Allylic Alcohols 2a)

Entry 1 2 Products Yield (%)b)

1 68 2 1a 83 3 1a trace 4 2a 76 5 1b 2b 70 6 1b 2c 5 7 2a 84 8 1c 2b 78 9 1c 2c 5 10 2a 6729 11 1d 2b 6930 12 1d 2c 34 2a 3a 2b 5a 1a 2c 7a 1b 3b 5b 7b 1c 3c 5c 7c 1d 3d 4d 5d 7d 6d Table 1. (Continued)

Entry 1 2 Products Yield (%)b)

13 2b 7719

14 1e 2c 34

15 2b 7326

16 1f 2c 27

a) Reaction conditions: 1 (1 mmol), 2 (1.2 mmol), Pd(OAc)2 (0.01 mmol), PPh3

(0.04 mmol), Ti(OPri

)4(0.25 mmol), and MS 4 Å (200 mg) in benzene (5 ml) were

re-fluxed for 3 h. b) Isolated yield.

1e 5e 1f 5f 6f 6e 7f 7e

N-(Cyclohex-2-enyl)phenothiazine (7b) 1_{H-NMR (CDCl} 3) d 1.78— 1.86 (1H, m), 1.95—2.04 (2H, m), 2.14—2.24 (2H, m), 2.29—2.37 (1H, m), 4.71—4.77 (1H, m), 5.94—5.98 (1H, m), 6.18—6.22 (1H, m), 6.89 (2H, dt, J
0.8, 6.0 Hz), 7.07—7.11 (4H, m), 7.15 (2H, dd, J
0.8, 6.4 Hz); 13_C-NMR (CDCl3) d 22.7 (t), 24.9 (t), 26.9 (t), 58.3 (d), 117.1 (d), 122.4 (d), 125.8 (s), 126.9 (d), 127.3 (d), 129.8 (d), 131.4 (d), 145.6 (s); EI-MS m/z: 279 (M), 207, 167, 149, 121, 104; HR-MS m/z: 279.1081 (Calcd for C18H17NS: 279.1082). N-Allyl-2-nitroaniline (3c)83,84) _{mp 51—53 °C; IR (KBr) cm}1_{: 3387;} 1_{H-NMR (CDCl} 3) d 3.93 (2H, ddd, J
0.8, 1.2, 4.4 Hz), 5.21 (1H, ddt, J
0.8, 0.8, 8.4 Hz), 5.28 (1H, ddt, J
0.8, 1.2, 14.0 Hz), 5.92 (1H, ddt, J
4.4, 8.4, 14.0 Hz), 6.60 (1H, ddd, J
0.8, 5.6, 6.4 Hz), 6.78 (1H, d, J
6.8 Hz), 7.38 (1H, ddd, J
0.8, 5.6, 6.8 Hz), 8.10 (1H, ddd, J
0.8, 0.8, 6.4 Hz), 8.15 (1H, bs); 13_{C-NMR (CDCl} 3) d 45.2 (t), 114.1 (d), 115.4 (d), 116.8 (t), 126.6 (d), 131.9 (s), 133.3 (d), 136.1 (d), 145.3 (s); EI-MS m/z: 178 (M), 151, 131, 130, 119, 105, 91, 78, 77; HR-MS m/z: 178.0742 (Calcd for C9H10N2O2: 178.0742). N-Cinnamyl-2-nitroaniline (5c)82) _{mp 70—71 °C; IR (KBr) cm}1_: 3386; 1_{H-NMR (CDCl} 3) d 4.14 (2H, dd, J
1.6, 5.6 Hz), 6.29 (1H, dt, J
5.6, 16.0 Hz), 6.62 (1H, dt, J
1.6, 16.0 Hz), 6.67 (1H, dd, J
1.6, 7.2 Hz), 6.89 (1H, dd, J
1.2, 8.8 Hz), 7.22—7.27 (1H, m), 7.30—7.38 (4H, m), 7.42 (1H, ddd, J
1.6, 6.8, 8.8 Hz), 8.19 (1H, dd, J
1.6, 8.8 Hz), 8.25 (1H, bs); 13_{C-NMR (CDCl} 3) d 44.9 (t), 114.1 (d), 115.6 (d), 124.7 (d), 126.4 (d), 126.8 (d), 127.8 (d), 128.6 (d), 132.1 (s), 132.2 (d), 136.2 (d), 136.3 (s), 145.2 (s); EI-MS m/z: 254 (M), 219, 207, 130, 117, 115, 91, 77; HR-MS m/z: 254.1053 (Calcd for C15H14N2O2: 254.1055). 3-(2-Nitrophenylamino)cyclohexene (7c) IR (KBr) cm1: 3375; 1 H-NMR (CDCl3) d 1.63—1.82 (3H, m), 1.96—2.18 (3H, m), 4.17—4.23 (1H, m), 5.75 (1H, ddt, J
2.0, 3.2, 10.0 Hz), 5.96 (1H, ddt, J
1.6, 3.6, 10.0 Hz), 6.63 (1H, ddd, J
1.6, 6.8, 8.4 Hz), 6.91 (1H, d, J
8.4 Hz), 7.42 (1H, ddd, J
1.6, 6.8, 8.4 Hz), 8.09 (1H, bs), 8.18 (1H, dd, J
1.6, 8.4 Hz); 13_C-NMR (CDCl3) d 19.5 (t), 24.9 (t), 28.7 (t), 47.4 (d), 114.1 (d), 115.1 (d), 126.6 (d), 127.1 (d), 131.6 (d), 136.1 (d), 136.1 (s), 144.6 (s); EI-MS m/z: 218 (M), 200, 190, 183, 171, 157, 144, 131, 106, 79, 77; HR-MS m/z: 217.0974 (Calcd for C12H13N2O2: 217.0977). N-Allyl-3-nitroaniline (3d) mp 64—65 °C; IR (KBr) cm1: 3406; 1 H-NMR (CDCl3) d 3.82 (2H, ddd, J
1.2, 1.6, 4.0 Hz), 4.32 (1H, bs), 5.20 (1H, ddt, J
1.2, 1.2, 8.0 Hz), 5.29 (1H, ddt, J
1.2, 1.6, 14.0 Hz), 5.91 (1H, ddt, J
4.0, 8.0, 14.0 Hz), 6.88 (1H, dd, J
1.6, 6.4 Hz), 7.25 (1H, dd, J
6.4, 6.4 Hz), 7.38 (1H, dd, J
1.6, 2.0 Hz), 7.49 (1H, d, J
2.0, 6.4 Hz); 13_C-NMR (CDCl3) d 46.1 (t), 106.4 (d), 111.8 (d), 116.8 (t), 118.9 (d), 129.7 (d), 134.1 (d), 148.9 (s), 149.3 (s); EI-MS m/z: 178 (M), 151, 131, 130, 117, 105, 104, 77; HR-MS m/z: 178.0743 (Calcd for C9H10N2O2: 178.0742). N,N-Diallyl-3-nitroaniline (4d) 1_{H-NMR (CDCl} 3) d 3.99 (4H, ddd, J
1.2, 1.6, 3.6 Hz), 5.18 (2H, ddt, J
1.2, 1.6, 13.6 Hz), 5.21 (2H, ddt, J
1.2, 1.2, 8.4 Hz), 5.85 (2H, ddt, J
3.6, 8.4, 13.6 Hz), 6.93 (1H, ddd, J
0.8, 2.0, 6.8 Hz), 7.28 (1H, ddd, J
1.2, 6.8, 8.0 Hz), 7.47—7.49 (2H, m); 13_{C-NMR (CDCl} 3) d 52.9 (t), 106.4 (d), 110.8 (d), 116.6 (t), 117.8 (d), 129.6 (d), 132.6 (d), 149.2 (s), 149.4 (s); EI-MS m/z: 218 (M), 191, 171, 157, 145, 130, 117, 91, 77; HR-MS m/z: 218.1052 (Calcd for C13H17N2O2: 218.1055). N-Cinnamyl-3-nitroaniline (5d) mp 115—116 °C; IR (KBr) cm1: 3393; 1_{H-NMR (CDCl} 3) d 3.92 (2H, dd, J
1.2, 5.6 Hz), 4.26 (1H, bs), 6.24 (1H, dt, J
5.6, 16.0 Hz), 6.60 (1H, dt, J
1.2, 16.0 Hz), 6.87 (1H, dd, J
2.0, 8.4 Hz), 7.20—7.40 (7H, m), 7.49 (1H, dd, J
2.0, 8.0 Hz); 13_C-NMR (CDCl3) d 45.8 (t), 106.6 (d), 112.0 (d), 118.8 (d), 125.5 (d), 126.4 (d), 127.8 (d), 128.6 (d), 129.7 (d), 132.2 (d), 136.5 (d), 148.7 (s), 149.4 (s); EI-MS m/z: 254 (M), 237, 207, 159, 117, 115, 91; HR-MS m/z: 254.1053 (Calcd for C15H14N2O2: 254.1055). N,N-Dicinnamyl-3-nitroaniline (6d) 1_{H-NMR (CDCl} 3) d 4.18 (4H, dd, J
1.6, 5.2 Hz), 6.23 (2H, dt, J
5.2, 16.0 Hz), 6.53 (2H, dt, J
1.6, 16.0 Hz), 7.03 (1H, dd, J
2.4, 8.4 Hz), 7.21—7.24 (2H, m), 7.51 (1H, dd, J
2.0, 8.0 Hz), 7.61 (1H, t, J
2.4 Hz), 7.27—7.36 (9H, m); 13_{C-NMR (CDCl} 3) d 52.4 (t), 106.5 (d), 111.0 (d), 118.0 (d), 124.2 (d), 126.4 (d), 127.7 (d), 128.6 (d), 129.8 (d), 132.0 (d), 136.4 (s), 149.2 (s), 149.2 (s); EI-MS m/z: 370 (M), 355, 335, 327, 281, 253, 225, 207, 191, 165, 135, 115, 91, 77; HR-MS m/z: 370.1679 (Calcd for C24H22N2O2: 370.1681). 3-(3-Nitrophenylamino)cyclohexene (7d) mp 64—65 °C; IR (KBr) cm1: 3406; 1_{H-NMR (CDCl} 3) d 1.59—1.76 (3H, m), 1.89—1.96 (1H, m), 2.02—2.10 (2H, m) 3.98—4.08 (1H, m), 4.10 (1H, bs), 5.71 (1H, ddt, J
2.0, 3.2, 10.0 Hz), 5.89 (1H, ddt, J
2.0, 3.6, 10.0 Hz), 6.86 (1H, dd, J
2.4, 8.0 Hz), 7.24 (1H, t, J
8.0 Hz), 7.38 (1H, t, J
2.4 Hz), 7.47 (1H, dd, J
2.4, 8.0 Hz); 13_{C-NMR (CDCl} 3) d 19.5 (t), 25.1 (t), 28.6 (t), 47.9 (d), 106.6 (d), 111.5 (d), 119.1 (d), 127.4 (d), 129.8 (d), 131.1 (d), 148.0 (s), 149.5 (s); EI-MS m/z: 218 (M), 201, 190, 173, 157, 143, 117, 115, 79, 77; HR-MS m/z: 217.0974 (Calcd for C12H13N2O2: 217.0977). N,N-Diallyl-4-nitroaniline (4e) 1H-NMR (CDCl3) d 4.02 (4H, ddd, J
1.6, 1.6, 4.8 Hz), 5.16 (2H, ddt, J
1.6, 2.0, 17.2 Hz), 5.23 (2H, ddt, J
1.6, 2.0, 10.4 Hz), 5.84 (2H, ddt, J
4.8, 10.4, 17.2 Hz), 6.62 (2H, d, J
9.2 Hz), 8.07 (2H, d, J
9.2 Hz); 13_{C-NMR (CDCl} 3) d 52.9 (t), 110.7 (d), 116.8 (t), 126.0 (d), 131.7 (d), 137.1 (s), 153.2 (s); EI-MS m/z: 218 (M), 202, 191, 171, 157, 145, 130, 117, 91, 77; HR-MS m/z: 218.1054 (Calcd for C13H17N2O2: 218.1055). N-Cinnamyl-4-nitroaniline (5e)82) _{mp 142—143 °C; IR (KBr) cm}1_: 3349; 1_{H-NMR (CDCl} 3) d 4.03 (2H, dd, J
1.2, 5.6 Hz), 4.83 (1H, bs), 6.26 (1H, dt, J
1.6, 16.0 Hz), 6.57—6.63 (3H, m), 7.24—7.37 (5H, m), 8.09 (2H, d, J
8.8 Hz); 13_{C-NMR (CDCl} 3) d 45.4 (t), 111.3 (d), 124.6 (d), 126.4 (d), 127.9 (d), 128.6 (d), 132.6 (d), 136.2 (s), 138.1 (s), 153.1 (s); EI-MS m/z: 254 (M), 237, 221, 207, 177, 130, 117, 115, 91, 77; HR-MS m/z: 254.1054 (Calcd for C15H14N2O2: 254.1055). N,N-Dicinnamyl-4-nitroaniline (6e)82) _{mp 157—158 °C;} 1_H-NMR (CDCl3) d 4.25 (4H, dd, J
1.2, 5.2 Hz), 6.23 (2H, dt, J
5.2, 16.0 Hz), 6.52 (2H, dt, J
1.2, 16.0 Hz), 6.76 (2H, d, J
9.6 Hz), 7.24—7.37 (10H, m), 8.13 (2H, d, J
9.6 Hz); 13_{C-NMR (CDCl} 3) d 52.5 (t), 110.9 (d), 123.3 (d), 126.3 (d), 126.4 (d), 128.0 (d), 128.7 (d), 132.3 (d), 136.2 (s), 137.8 (s), 153.3 (s); EI-MS m/z: 370 (M), 279, 265, 189, 167, 149, 117, 115, 91, 77; HR-MS m/z: 370.1683 (Calcd for C24H22N2O2: 370.1681). 3-(4-Nitrophenylamino)cyclohexene (7e)82) _{mp 99—101 °C; IR (KBr)} cm1: 3422; 1_{H-NMR (CDCl} 3) d 1.63—1.77 (3H, m), 1.91—2.06 (1H, m), 2.06—2.09 (2H, m), 4.08 (1H, bs), 4.66—4.71 (1H, m), 5.70 (1H, ddt, J
1.6, 3.2, 10.0 Hz), 5.93 (1H, ddt, J
1.6, 3.6, 10.0 Hz), 6.54 (2H, d, J
9.2 Hz), 8.06 (2H, d, J
9.2 Hz); 13_{C-NMR (CDCl} 3) d 19.4 (t), 24.9 (t), 28.5 (t), 47.7 (d), 111.3 (d), 126.6 (d), 126.6 (d), 131.7 (d), 137.6 (s), 152.5 (s); EI-MS m/z: 218 (M), 202, 190, 171, 143, 130, 123, 117, 108, 81, 79, 77; HR-MS m/z: 218.1055 (Calcd for C12H14N2 O2: 218.1055). N-Cinnamyl-4-cyanoaniline (5f ) IR (KBr) cm1: 3428, 2215; 1 H-NMR (CDCl3) d 3.93 (2H, dd, J
1.6, 5.6 Hz), 4.60 (1H, bs), 6.22 (1H, dt, J
5.6, 12.0 Hz), 6.57 (1H, dt, J
1.6, 16.0 Hz), 6.58 (2H, d, J
8.8 Hz), 7.21—7.25 (1H, m), 7.30 (2H, dd, J
6.8, 8.0 Hz), 7.34 (2H, d, J
6.8 Hz), 7.38 (2H, d, J
8.8 Hz); 13_{C-NMR (CDCl} 3) d 45.1 (t), 98.3 (s), 112.4 (d), 120.6 (s), 125.3 (d), 126.3 (d), 127.7 (d), 128.6 (d), 132.0 (d), 133.6 (d), 136.4 (s), 151.2 (s); EI-MS m/z: 234 (M), 217, 117, 115, 91, 77; HR-MS m/z: 234.1157 (Calcd for C16H14N2: 234.1157). N,N-Dicinnamyl-4-cyanoaniline (6f ) mp 93—95 °C; IR (KBr) cm1: 2212; 1_{H-NMR (CDCl} 3) d 4.19 (4H, dd, J
1.2, 5.2 Hz), 6.22 (2H, dt, J
5.2, 16.0 Hz), 6.50 (2H, dt, J
1.2, 16.0 Hz), 6.77 (2H, d, J
8.8 Hz), 7.22—7.26 (2H, m), 7.31 (4H, dd, J
6.8, 8.0 Hz), 7.35 (4H, d, J
6.8 Hz), 7.47 (2H, d, J
8.8 Hz); 13_{C-NMR (CDCl} 3) d 52.1 (t), 98.1 (s), 112.0 (d), 120.5 (s), 123.8 (d), 126.4 (d), 127.8 (d), 128.6 (d), 131.9 (d), 133.6 (d), 136.3 (s), 151.3 (s); EI-MS m/z: 350 (M), 259, 245, 231, 198, 169, 144, 129, 117, 115, 102, 91, 77; HR-MS m/z: 350.1785 (Calcd for C25H22N2: 350.1782). 3-(4-Cyanophenylamino)cyclohexene (7f) IR (KBr) cm1: 3423, 2213; 1_{H-NMR (CDCl} 3) d 1.59—1.76 (3H, m), 1.87—1.93 (1H, m), 1.98—2.09 (2H, m), 4.01 (1H, bs), 4.28—4.38 (1H, m), 5.69 (1H, ddt, J
2.0, 3.2, 10.0 Hz), 5.90 (1H, ddt, J
1.6, 3.6, 10.0 Hz), 6.56 (2H, d, J
8.8 Hz), 7.39 (2H, d, J
8.8 Hz); 13_{C-NMR (CDCl} 3) d 19.4 (t), 25.0 (t), 28.5 (t), 47.4 (d), 98.2 (s), 112.4 (d), 120.6 (s), 127.0 (d), 131.3 (d), 133.7 (d), 150.4 (s); EI-MS m/z: 198 (M), 197, 170, 169, 153, 129, 119, 118, 91, 79, 77; HR-MS m/z: 198.1155 (Calcd for C13H14N2: 198.1157).

Acknowledgments We gratefully acknowledge the National Science Council of the Republic of China for financial support.

References and Notes

1) Gagné M. R., Nolan S. P., Marks T. J., Organometallics, 9, 1716— 1718 (1990).

2) Walsh P. J., Baranger A. M., Bergman R. G., J. Am. Chem. Soc., 114, 1708—1719 (1992).

3) McGrane P. L., Jensen M., Livinghouse T., J. Am. Chem. Soc., 114, 5459—5460 (1992).

4) Baranger A. M., Walsh P. J., Bergman R. G., J. Am. Chem. Soc., 115, 2753—2763 (1993).

5) Brunet J., Commenges G., Neibecker D., Philippot K., J. Organomet. Chem., 469, 221—228 (1994).

6) Collman J. P., Hegedus L. S., Norton J. R., Finke R. G., “Principles and Applications of Organotransition Metal Chemistry,” University Science Books, Mill Valley, CA, 1987.

7) Connell R. D., Rein T., Åkermark B., Helquist P., J. Org. Chem., 53, 3845—3849 (1988).

8) Sakamoto M., Shimizu I., Yamamoto A., Bull. Chem. Soc. Jpn., 69, 1065—1078 (1996).

9) Tsuji J., “Transition Metal Reagents and Catalysts,” Wiley, New York, 2000.

10) Tsutsumi K., Yabukami T., Fujimoto K., Kawase T., Morimoto T., Kakiuchi K., Organometallics, 22, 2996—2999 (2003).

11) Goldeski S. A., “Comprehensive Organic Synthesis,” Vol. 4, Chap. 3.3, ed. by Trost B. M., Fleming I., Pergamon Press, New York, 1991. 12) Harrington P. J., “Comprehensive Organometallic Chemistry II,” Vol.

12, Chap. 8.2, ed. by Abel E. W., Stone F. G. A., Wilkinson G., Perga-mon Press, New York, 1995.

13) Tsuji J., “Palladium Reagents and Catalysts,” Wiley, New York, 1995. 14) Trost B. M., Acc. Chem. Res., 13, 385—393 (1980).

15) Backvall J. E., Acc. Chem. Res., 16, 335—342 (1983). 16) Tsuji M., Minami I., Acc. Chem. Res., 20, 140—145 (1987). 17) Trost B. M., Angew. Chem. Int. Ed. Engl., 28, 1173—1192 (1989). 18) Oppolzer W., Angew. Chem., Int. Ed. Engl., 28, 38—52 (1989). 19) Tsuji J., Synthesis, 1990, 739—749 (1990).

20) Trost B. M., Pure Appl. Chem., 64, 315—322 (1992). 21) Backvall J. E., Pure Appl. Chem., 64, 429—437 (1992).

22) Frost C. G., Howarth J., Williams J. M. J., Tetrahedron: Asymmetry, 3, 1089—1122 (1992).

23) Giambastiani G., Poli G., J. Org. Chem., 63, 9608—9609 (1998). 24) Uozumi Y., Danjo H., Hayashi T., J. Org. Chem., 64, 3384—3388

(1999).

25) Rajesh S., Banerji B., Iqbal J., J. Org. Chem., 67, 7852—7857 (2002). 26) Wallner O. A., Szabo K. J., J. Org. Chem., 68, 2934—2943 (2003). 27) Tsuji J., Shimizu I., Minami I., Ohashi Y., Tetrahedron Lett., 23,

4809—4812 (1982).

28) Trost B. M., Hung M. H., J. Am. Chem. Soc., 105, 7757—7759 (1983). 29) Takahashi T., Jinbo Y., Kitamura K., Tsuji J., Tetrahedron Lett., 25,

5921—5924 (1984).

30) Tsuji J., Shimizu I., Minami I., Ohashi Y., Sugiura T., Takahashi K., J. Org. Chem., 50, 1523—1529 (1985).

31) Stary I., Kocovsky P., J. Am. Chem. Soc., 111, 4981—4982 (1989). 32) Stary I., Zajicek J., Kocovsky P., Tetrahedron, 48, 7229—7250 (1992). 33) Goux C., Massacret M., Lhoste P., Sinou D., Organometallics, 14,

4585—4593 (1995).

34) Deardorff D. R., Savin K. A., Justman C. J., Karanjawala Z. E., Shep-peck J. E., II, Hager D. C., Aydin N., J. Org. Chem., 61, 3616—3622 (1996).

35) Kadota J., Katsuragi H., Fukumoto Y., Murai S., Organometallics, 19, 979—983 (2000).

36) Kamijo S., Jin T., Yamamoto Y., J. Am. Chem. Soc., 123, 9453—9454 (2001).

37) Minami I., Ohashi Y., Shimizu I., Tsuji J., Tetrahedron Lett., 26, 2449—2452 (1985).

38) Minami I., Yuhara M., Tsuji J., Tetrahedron Lett., 28, 2737—2740 (1987).

39) Hayashi T., Yamamoto A., Ito Y., Tetrahedron Lett., 28, 4837—4840 (1987).

40) Ziegler F. E., Kneisley A., Wester R. T., Tetrahedron Lett., 27, 1221— 1224 (1986).

41) Ziegler F. E., Wester R. T., Tetrahedron Lett., 27, 1225—1228 (1986). 42) Ziegler F. E., Cain W. T., Kneisley A., Stirchak E. P., Wester R. T., J.

Am. Chem. Soc., 110, 5442—5452 (1988).

43) Imidoesters: Schenck T. G., Bosnich B., J. Am. Chem. Soc., 107, 2058—2066 (1985).

44) Xanthates: Auburn P. R., Wheland J., Bosnich B., J. Chem. Soc., Chem. Commun., 1986, 146—147 (1986).

45) Nitrogroups: Ono N., Hamamoto I., Kamimura A., Kaji A., J. Org. Chem., 51, 3734—3736 (1986).

46) Nitrogroups: Tamura R., Kai Y., Kakihana M., Hayashi K., Tsuji M., Nakamura T., Oda D., J. Org. Chem., 51, 4375—4385 (1986). 47) Nitrogroups: Tamura R., Kato M., Saegusa K., Kakihana M., Oda D.,

J. Org. Chem., 52, 4121—4124 (1987).

48) Nitrogroups: Tamura R., Kamimura A., Ono N., Synthesis, 1991, 423—434 (1991).

49) Sulfones: Trost B. M., Schmuff N. R., Miller M. J., J. Am. Chem. Soc.,

102, 5979—5981 (1980).

50) Trost B. M., Science, 254, 1471—1477 (1991).

51) Trost B. M., Angew. Chem. Int. Ed. Engl., 34, 259—281 (1995). 52) Yamamoto A., Adv. Organomet. Chem., 34, 111—147 (1992). 53) Lu X., Lu L., Sun J., J. Mol. Catal., 41, 245—251 (1987).

54) Lu X., Jiang X., Tao X., J. Organomet. Chem., 344, 109—118 (1988). 55) Tamaru Y., Horino Y., Araki M., Tanaka S., Kimura M., Tetrahedron

Lett., 41, 5705—5709 (2000).

56) Kimura M., Horino Y., Mukai R., Tanaka S., Tamaru Y., J. Am. Chem. Soc., 123, 10401—10402 (2001).

57) Horino Y., Naito M., Kimura M., Tanaka S., Tamaru Y., Tetrahedron Lett., 42, 3113—3116 (2001).

58) Tsay S., Lin L. C., Furth P. A., Shum C. C., King D. B., Yu S. F., Chen B., Hwu J. R., Synthesis, 1993, 329—334 (1993).

59) Stary I., Stara I. G., Kocovsky P., Tetrahedron Lett., 34, 179—182 (1993).

60) Stary I., Stara I. G., Kocovsky P., Tetrahedron, 50, 529—537 (1994). 61) Masuyama Y., Takahara J. P., Kurusu Y., J. Am. Chem Soc., 110,

4473—4474 (1988).

62) Masuyama Y., Tsunoda T., Kurusu Y., Chem. Lett., 1989, 1647—1650 (1989).

63) Takahara J. P., Masuyama Y., Kurusu Y., J. Am. Chem. Soc., 114, 2577—2586 (1992).

64) Masuyama Y., Kagawa M., Kurusu Y., Chem. Lett., 1995, 1121—1122 (1995).

65) Lumin S., Falck J. R., Capdevila J., Karara A., Tetrahedron Lett., 33, 2091—2094 (1992).

66) Hirai Y., Shibuya K., Fukuda Y., Yokoyama H., Yamaguchi S., Chem. Lett., 1997, 221—222 (1997).

67) Ozawa F., Okamoto H., Kawagishi S., Yamamoto S., Minami T., Yoshifuji M., J. Am. Chem. Soc., 124, 10968—10969 (2002). 68) Manabe M., Kobayashi S., Org. Lett., 5, 3241—3244 (2003). 69) Kayaki Y., Koda T., Ikariya T., J. Org. Chem., 69, 2595—2597 (2004). 70) Kinoshita H., Shinokubo H., Oshima K., Org. Lett., 6, 4085—4088

(2004).

71) Patil N. C., Yamamoto Y., Tetrahedron Lett., 45, 3101—3103 (2004). 72) Komine N., Sako A., Hirahara S., Hirano M., Komiya S., Chem. Lett.,

34, 246—247 (2005).

73) Yang S. C., Hung C. W., Synthesis, 1999, 1747—1752 (1999). 74) Yang S. C., Tsai Y. C., Organometallics, 20, 763—770 (2001). 75) Shue Y. J., Yang S. C., Lai H. C., Tetrahedron Lett., 44, 1481—1485

(2003).

76) Yang S. C., Lai H. C., Tsai Y. C., Tetrahedron Lett., 45, 2693—2697 (2004).

77) Bordwell F. G., Acc. Chem. Res., 21, 456—463 (1988).

78) Bordwell F. G., Algrim D. J., J. Am. Chem. Soc., 110, 2964—2968 (1988).

79) Bordwell F. G., Zhang X. M., Cheng J. P., J. Org. Chem., 58, 6410— 6416 (1993).

80) Dean J. A., “Handbook of Organic Chemistry,” McGraw-Hill, U.S.A., 1987.

81) pKavalues in DMSO of amines of Table 1 according to the ref. 77—

79: diphenylamine, 1a, 24.95, phenothioazine, 1b, 22.7, 4-nitroaniline,

1e, 20.9, 4-cyanoaniline, 1f, 25.26 as compared with aniline (30.6).

pKavalues in H2O of amines according to the ref. 80: diphenylamine,

1a, 0.9, 2-nitroaniline, 1c, 0.28, 3-nitroaniline, 1d, 2.46,

4-nitroani-line, 1e, 1.01 as compared with aniline (4.60).

82) Moreno-Manas M., Morral L., Pleixats R., J. Org. Chem., 63, 6160— 6166 (1998).

83) Murphy J. A., Rasheed F., Gastaldi S., Ravishanker T., Lewis N., J. Chem. Soc. Perkin Trans. 1, 10, 1549—1558 (1997).

84) Chauhan S. M. S., Singh R., Geetanjali, Synth. Commun., 33, 2899— 2906 (2003).