Ruthenium-catalyzed propargylic substitution reactions of propargylic alcohols with oxygen-, nitrogen-, and phosphorus-centered nucleophiles

FULL PAPER

Ruthenium-Catalyzed Propargylic Substitution Reactions of Propargylic

Alcohols with Oxygen-, Nitrogen-, and Phosphorus-Centered Nucleophiles

Yoshiaki Nishibayashi,*^[a]Marilyn Daisy Milton,^[a]Youichi Inada,^[a]Masato Yoshikawa,^[a]

Issei Wakiji,^[b]Masanobu Hidai,*^[c]and Sakae Uemura*^[a]

Abstract: The scope and limitations of

the ruthenium-catalyzed propargylic

substitution reaction of propargylic al-

cohols with heteroatom-centered nucle-

ophiles are presented. Oxygen-, nitro-

gen-, and phosphorus-centered nucleo-

philes such as alcohols, amines, amides,

and phosphine oxide are available for

this catalytic reaction. Only the thio-

late-bridged diruthenium complexes

can work as catalysts for this reaction.

Results of some stoichiometric and cat-

alytic reactions indicate that the cata-

lytic propargylic substitution reaction

proceeds via an allenylidene complex

formed in situ, whereby the attack of

nucleophiles to the allenylidene C_g

atom is a key step. Investigation of the

relative rate constants for the reaction

of propargylic alcohols with several

para-substituted anilines reveals that

the attack of anilines on the allenyli-

dene C_gatom is not involved in the

rate-determining step and rather the

acidity of conjugated anilines of an al-

kynyl complex, which is formed after

the attack of aniline on the C_gatom, is

considered to be the most important

factor to determine the rate of this cat-

alytic reaction. The key point to pro-

mote this catalytic reaction by using

the thiolate-bridged diruthenium com-

plexes is considered to be the ease of

the ligand exchange step between a vi-

nylidene ligand on the diruthenium

complexes and another propargylic al-

cohol in the catalytic cycle. The reason

why only the thiolate-bridged diruthe-

nium complexes promote the ligand ex-

change step more easily with respect to

other monoruthenium complexes in

this catalytic reaction should be that

one Ru moiety, which is not involved

in the allenylidene formation, works as

an electron pool or a mobile ligand to

another Ru site. The catalytic proce-

dure presented here provides a versa-

tile, direct, and one-step method for

propargylic substitution of propargylic

alcohols in contrast to the so far well-

known stoichiometric and stepwise

Nicholas reaction.

Keywords: alcohols

nucleophilic subsitution

propargylic alcohols · ruthenium

·

amines

·

Introduction

Allylic substitution reactions of allylic alcohol derivatives

with nucleophiles catalyzed by transition-metal complexes

are one of the most successful and reliable methods in or-

ganic synthesis.^[1]The process is catalyzed by various transi-

tion-metal complexes derived from nickel, palladium, plati-

num, cobalt, rhodium, iridium, iron, ruthenium, molybde-

num, and tungsten.^[1]A variety of nucleophiles such as alco-

hols, amines, thiols, and active methine and methylene com-

pounds are available for this reaction, which proceeds via

(h-allyl)metal species to afford a wide variety of allylated

products with high chemo-, regio-, and stereoselectivities.^[1]

In sharp contrast, much less attention has been paid to

the propargylic substitution reactions of propargylic alcohol

derivatives with nucleophiles. The Nicholas reaction has so

far been known to be an effective tool for propargylic sub-

stitution reaction.^[2]In addition to heteroatom-centered nu-

cleophiles, such as alcohols, amines, and thiols, a wide varie-

[a] Dr. Y. Nishibayashi, Dr. M. D. Milton, Y. Inada, M. Yoshikawa,

Prof. Dr. S. Uemura

Department of Energy and Hydrocarbon Chemistry

Graduate School of Engineering, Kyoto University, Katsura

Nishikyo-ku, Kyoto, 615-8510 (Japan)

Fax : (+81)75-383-2517

E-mail: ynishiba@scl.kyoto-u.ac.jp

uemura@scl.kyoto-u.ac.jp

[b] I. Wakiji

Department of Chemistry and Biotechnology

Graduate School of Engineering, The University of Tokyo

Hongo, Bunkyo-ku, Tokyo 113-8656 (Japan)

[c] Prof. Dr. M. Hidai

Department of Materials Science and Technology

Faculty of Industrial Science and Technology

Tokyo University of Science, Noda, Chiba 278-8510 (Japan)

Chem. Eur. J. 2005, 11, 1433 – 1451

DOI: 10.1002/chem.200400833

ꢀ 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

1433

ty of carbon-centered nucleophiles, including simple ketones

such as acetone, are also available for the Nicholas reac-

tion.^[2,3]This reaction, however, has some drawbacks: a stoi-

chiometric amount of [Co₂(CO)₈] is required, and several

steps are necessary to obtain propargylic-substituted prod-

ucts from propargylic alcohols via cationic propargyl com-

plexes [Co₂(CO)₆(propargyl)]⁺.^[2,3]On the other hand, sever-

al catalytic propargylic substitution reactions have been re-

cently reported, in which some transition-metal complexes,

such as copper, titanium, iridium, ruthenium, rhenium, and

palladium complexes, worked as effective catalysts to give

the corresponding propargylic compounds from propargylic

alcohols or their derivatives.^[4]The kind of available nucleo-

philes, however, depends a lot on the nature of transition-

metal complexes. To the best of our knowledge, no general

method for catalytic propargylic substitution reactions has

so far been reported.

We have long been interested in the development of ho-

mogeneous catalysis of polynuclear transition-metal com-

plexes, since direct and indirect cooperation of several tran-

sition metals can be expected for the activation of substrates

to provide novel transformations that are not attainable at a

conventional monometallic center.^[11]Toward this end, our

studies have been focused on the synthesis and reactivity of

polynuclear noble-metal complexes with bridging sulfur li-

gands.^[12]In the course of our investigation, we have so far

synthesized a series of thiolate-bridged diruthenium com-

plexes, such as [(Cp*)Ru(m₂-SiPr)₂Ru(Cp*)] (Ru^II–Ru^II)

(Cp*=h⁵-C₅Me₅) and [(Cp*)Ru(m₂-SiPr)₃Ru(Cp*)] (Ru^II–

Ru^III), and disclosed that these complexes provide unique

reaction sites for various stoichiometric transformations of

terminal alkynes.^[13]During our further study on this subject

using

the thiolate-bridged diruthenium

complexes

[(Cp*)RuCl(m₂-SR)₂Ru(Cp*)Cl] (Ru^III–Ru^III) (R=Me (1a),

Et (1b), nPr (1c), iPr (1d)), and [(Cp*)RuCl(m₂-SiPr)₂Ru-

(Cp*)(OH₂)]OTf (Ru^III–Ru^III) (1e; OTf=OSO₂CF₃),^[14]we

eventually found that these complexes work as good cata-

lysts for propargylic substitution reaction of propargylic al-

cohols bearing a terminal alkyne with a variety of nucleo-

philes.^[15]Not only heteroatom-centered but also carbon-cen-

Since the first discovery of the allenylidene complex in

1976, transition-metal allenylidene (M=C=C=C<) com-

plexes have attracted a great deal of attention as a new type

of organometallic intermediate.^[5]In fact, cationic transition-

metal allenylidene complexes [M⁺=C=C=CR¹R²], readily

available by dehydration of propargylic alcohols coordinated

to an unsaturated metal center, can be regarded as stabilized

propargylic cations because of the extensive contribution of

+

1

2

[6]

ꢀ

the metal–alkynyl resonance form [M CꢁCC R R ].

Theoretical studies also indicate that the C_aand C_gatoms

of allenylidene ligands are electrophilic centers, while the

C_batom behaves as a nucleophilic site.^[7]In fact, stoichio-

metric reactions of allenylidene ruthenium complexes with

a variety of nucleophiles have been reported, in which

nucleophiles attack either the allenylidene C_aor C_gatom to

afford Fischer-type carbenes or alkynyl complexes, respec-

tively.^[7]

tered nucleophiles could be employed for this catalytic

propargylic substitution reaction, which proceeded via an al-

lenylidene ruthenium complex as a key intermediate. Here,

we describe the scope and limitations of catalytic propargyl-

ic substitution reaction of propargylic alcohols with hetero-

atom-centered nucleophiles such as alcohols, amines,

amides, and diphenylphosphine oxide in detail together with

unambiguous X-ray structural determination of an inter-

mediate allenylidene complex. In addition, some mechanis-

tic consideration on the reaction pathway, including the re-

sults of stoichiometric reactions of allenylidene intermedi-

ates with nucleophiles, are presented in this article. Results

of the catalytic reaction of propargylic alcohols with thiols^[16]

and carbon-centered nucleophiles including simple ketones,

such as acetone,^[17]and 1,3-dicarbonyl compounds, such as

1,3-cyclohexanedione,^[18]have been reported separately.

It is now known that nucleophilic addition at C_goccurs re-

gioselectively when electron-rich and/or bulky metallic frag-

ments are used, leading to a large variety of s-alkynyl com-

1

2

[7]

ꢀ

plexes [M CꢁCC(Nu)R R ]. Especially, Gimeno and co-

workers have developed an interesting synthetic procedure

for the propargylic substitution reaction of 2-propyn-1-ols

mediated by the metallic complex [Ru(h⁵-C₉H₇)(PPh₃)₂]⁺.^[8]

Here, allenylidene complexes are formed in the first step

and they are subsequently transformed into the correspond-

ing s-alkynyl derivatives, which undergo a selective protona-

tion to afford the vinylidene complexes. Finally, demetala-

tion from the vinylidene complexes with acetonitrile leads

to the functionalized terminal alkynes in high yields. This

synthetic methodology is considered to be an alternative to

the Nicholas reaction^[2](vide supra), although a stoichiomet-

ric amount of ruthenium complex is required and also sever-

al steps are necessary to obtain propargylic-substituted

products from propargylic alcohols. In addition, quite re-

cently, some unprecedented reactivities of allenylidene com-

plexes have been reported, but all of them are limited to

stoichiometric reactions.^[9]In fact, only a few examples of

catalytic reactions via allenylidene intermediates have been

reported until now.^[10]

Results and Discussion

Propargylic substitution reaction with oxygen-centered nu-

cleophiles: At first, the propargylic substitution reaction of

propargylic alcohols with various alcohols was investigated

to obtain the corresponding ethers. A variety of thiolate-

bridged diruthenium complexes and monoruthenium com-

plexes were examined as catalysts in the reaction of 1-

phenyl-2-propyn-1-ol (2a) with EtOH. Typical results are

shown in Table 1. Interestingly, only the thiolate-bridged di-

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Chem. Eur. J. 2005, 11, 1433 – 1451

Ruthenium Catalysis

FULL PAPER

Table 1. Propargylic substitution reaction of propargylic alcohol 2a with EtOH.^[a]

[RuCl₂(PPh₃)₂],

[RuCl₂(p-

[RuCl(h⁵-

cymene)]₂,

and

C₉H₇)(PPh₃)₂],

which

are

known to react with propargylic

alcohols to produce the corre-

sponding allenylidene com-

plexes (vide infra),^[7]did not

work at all as catalysts under

the conditions investigated here

(Table 1, entries 12–17). The

use of AgOTf in place of

NH₄BF₄did not promote the

catalytic reactions at all. When

MeOH and iPrOH were used

in place of EtOH, the corre-

sponding methyl and isopropyl

ethers (3b and 3c) were ob-

tained in 84 and 91% yields, re-

spectively (Table 1, entries 18

and 19).

Ruthenium catalyst (mol%)^[b]

Additive (mol%)^[b]

Conditions

T [8C]/t [min]

GLC yield [%]

1

2

3

4

5

6

7

8

9

10

11

12

13

14

15

16

17

18

19

[(Cp*)RuCl(SMe)]₂(1a) (5)

[(Cp*)RuCl(SMe)]₂(1a) (1)

[(Cp*)RuCl(SMe)]₂(1a) (5)

–

NH₄BF₄(10)

–

60/15

25/60

60/15

85

95 (88)^[c]

32

90

0

81

83

78

69

1

0

1

[d]

–

[(Cp*)RuCl(SEt)]₂(1b) (5)

[(Cp*)RuCl(SnPr)]₂(1c) (5)

[(Cp*)RuCl(SiPr)]₂(1d) (5)

[(Cp*)RuCl(SiPr)₂Ru(Cp*)Cl]OTf (1e) (5)

[(Cp*)Ru(SiPr)₃Ru(Cp*)] (1 f) (5)

[(Cp*)Ru(SiPr)₂Ru(Cp*)] (1g) (5)

[(Cp*)RuCl(PPh₃)₂] (5)

[CpRuCl(PPh₃)₂] (5)

[RuCl₂(dppe)₂] (5)

[RuCl₂(PPh₃)₃] (5)

[{RuCl₂(p-cymene)}₂] (5)

–

NH₄BF₄(10)

[(C₉H₇)RuCl(PPh₃)₂] (5)

[(Cp*)RuCl(SMe)]₂(1a) (5)

Results of various reactions

between propargylic and nucle-

ophilic alcohols catalyzed by 1a

and NH₄BF₄are shown in

Table 2. Propargylic substitu-

tion reaction of 1-monoalkyl-

(84)^[c,e]

(91)^[c,f]

[a] All the reactions of 2a (0.20 mmol) with EtOH (5 mL) were carried out in the presence of catalyst.

[b] Mol% to 2a. [c] Isolated yield. [d] In the absence of catalyst. [e] MeOH was used in place of EtOH. Yield

of 3b. [f] iPrOH was used in place of EtOH. Yield of 3c.

and

1,1-dialkyl-substituted

ruthenium complexes worked effectively. In fact, in the pres-

ence of a catalytic amount of 1a, the treatment of 2a in

EtOH at 608C for 15 min gave the corresponding propargyl-

ic ether (3a) in 85% GLC yield with a complete regioselec-

tivity (Table 1, entry 1). The formation of neither an allenic

by-product nor another regioisomer of 3a was observed by

propargylic alcohols (2b–2d) at 608C occurred rapidly to

afford the corresponding ethers (3d–3 f, respectively) in

high yields (Table 2, entries 1–3). In contrast, reactions of

1,1-diaryl-substituted propargylic alcohols (2e and 2 f) were

sluggish under identical conditions, a prolonged time being

required to produce the diaryl-substituted ethers (3g and

3h) in moderate yields (Table 2, entries 4 and 5). In addition

to the use of EtOH, MeOH, and iPrOH, other types of alco-

hols bearing a chiral moiety could also be employed for the

propargylic substitution reaction as nucleophiles, with 1,2-di-

chloroethane (ClCH₂CH₂Cl) used as the solvent in place of

the alcohols. When the reactions of 2a with five equivalents

of chiral alcohols were carried out in ClCH₂CH₂Cl at 608C

for 1 h, a mixture of two diastereomeric isomers was ob-

tained in moderate to high yields with the isomer ratio of

approximately 1:1 (Table 2, entries 6–10). The exact ratios of

two diastereomeric isomers are shown in the Experimental

Section.

1

GLC and H NMR spectroscopy. The addition of NH₄BF₄

improved the catalytic activity (95% GLC yield: Table 1,

entry 2), probably by affording a cationic thiolate-bridged

diruthenium complex with a vacant site. The use of 1 mol%

of 1a decreased the yield of 3a (Table 1, entry 3). The reac-

tion at room temperature was completed within 1 h to give

3a in 90% GLC yield (Table 1, entry 4). On the other hand,

in the absence of 1a, no reaction occurred at all (Table 1,

entry 5). The kind of bridging thiolato ligands in the diruthe-

nium complex did not have much influence on the catalytic

activity. The complex with the sterically demanding SiPr

group (1d) exhibited a slightly lower catalytic activity, while

the complexes with SEt and SnPr groups (1b and 1c, respec-

tively) showed almost the same catalytic activity as 1a

(Table 1, entries 6–8). A cationic thiolate-bridged dirutheni-

um complex (1e) also worked as a catalyst for the propar-

gylic etherification (Table 1, entry 9). In sharp contrast to

the reactivity of the thiolate-bridged diruthenium(Ru^III–

Ru^III) complexes (1d and 1e), both diruthenium(Ru^II–Ru^III)

and diruthenium(Ru^II–Ru^II) complexes^[13](1 f and 1g) were

ineffective (Table 1, entries 10 and 11). It is worth noting

that conventional monoruthenium complexes such as

[RuCl(Cp*)(PPh₃)₂], [RuCl(Cp)(PPh₃)₂] (Cp=h⁵-C₅H₅),

[RuCl₂(dppe)₂] (dppe=1,2-bis(diphenylphosphino)ethane),

As has been reported,^[19]cycloaddition of propargylic al-

cohols with phenols bearing electron-donating groups pro-

ceeded to give the corresponding 4H-1-benzopyrans in good

yields (Scheme 1). However, propargylation of phenol with

2a afforded the corresponding phenyl propargylic ether

Scheme 1. Cycloaddition of propargylic alcohols with phenols bearing

electron-donating groups.

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Y. Nishibayashi, M. Hidai, S. Uemura et al.

Table 2. Propargylic substitution reactions of propargylic alcohols (2) with alcohols catalyzed by 1a.^[a]

firmed that the cycloaddition

proceeded via an allenylidene

intermediate.^[19]

The Williamson reaction is

the well-known and most

widely used method for the

preparation of unsymmetric

ethers.^[20]The procedure in-

volves S_N2 reactions between

an alkyl halide or pseudohalide

with an alkoxide anion pre-

pared from an alcohol. Howev-

er, this method is not useful

when the ethers are sensitive to

the basic conditions, such as

halogenated ethers, due to col-

lateral elimination reaction. In

our system, functional groups in

alcohols such as halogen,

alkene, and alkyne were toler-

ant as summarized in Table 3.

Reactions of 2a with alcohols

bearing halogen, alkene, or

alkyne moiety afforded the cor-

responding propargylic ethers

in moderate to good yields, re-

spectively (Table 3, entries 1–4),

showing that this method is

useful for a direct approach to

highly functionalized propargyl-

ic ethers. Unfortunately, no

etherification occurred when

1,2-propanediol was used as a

nucleophile (Table 3, entry 5).

Intramolecular cyclization of

propargylic alcohols bearing a

hydroxyl group at a suitable po-

sition in the same molecule af-

forded the corresponding cyclic

ethers in moderate to high

Propargylic

alcohol (2)

Alcohol

Conditions

T [8C]/t [min]

Propargylic

ether (3)

Yield [%]^[b]

1

2

3

4

iPrOH

EtOH

60/15

75

54

57

62

25/30

60/1200

5

EtOH

60/1200

60/60

61

6^[c]

80^[d]

92^[d]

7^[c]

60/60

8^[c]

60/60

69^[d]

9^[c]

64^[d]

10^[c]

60/60

71^[d]

[a] Reactions of propargylic alcohol (2; 0.60 mmol) with alcohol (15 mL) were carried out in the presence of

1a and NH₄BF₄(entries 1–5). [b] Isolated yield. [c] Reactions of propargylic alcohol (2) (0.60 mmol) with alco-

hol (3.0 mmol) were carried out in the presence of 1a and NH₄BF₄in ClCH₂CH₂Cl (15 mL) (runs 6–10).

[d] The ratio of two diastereomeric isomers is given in the Experimetal Section.

(3n) in 65% isolated yield [Eq. (1)], indicating that phenols

without electron-donating groups can be propargylated to

give the corresponding aryl propargylic ethers. In fact, the

reaction of 2a with 3,4,5-trimethylphenol gave a mixture of

propargylic ether (3o) and 4H-1-benzopyran in a 2:1 ratio

[Eq. (2)]. When the reaction of 2a with 2-naphthol was car-

ried out at 608C for 1 h, 1-phenyl-1H-naphtho[2,1-b]pyran

was isolated in 80% yield [Eq. (3)].^[19]Previously, we con-

yields with a complete regioselectivity. Thus, cyclization pro-

ceeded rapidly with 1-(2-hydroxymethylphenyl)-2-propyn-1-

ol (2g) to afford the corresponding five-membered-ring

product (3t) in 92% isolated yield [Eq. (4,)], while 6-hep-

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Ruthenium Catalysis

FULL PAPER

Table 3. Propargylic substitution reactions of propargylic alcohol 2a with

alcohols.^[a]

Alcohol

Propargylic

Yield [%]^[b]

ether (3)

1

2

3

81

77

50

4

5

87

–

[c]

–

1,1-dialkyl-substituted propargylic alcohols (2c–2d) in

ClCH₂CH₂Cl in the presence of 1a (5 mol%) and NH₄BF₄

(10 mol%) at 608C for 15 min gave the corresponding con-

jugated enynes (4b and 4c) in high yields (Table 4, entries 2

and 3). Similarly, the dehydration of ethisterone and mestra-

nol proceeded smoothly to give the corresponding enynes

(4d and 4e) in 86% and 76% isolated yields, respectively

(Table 4, entries 4 and 5). Spectroscopic data of these

enynes (4d and 4e) were in accordance with those previous-

[a] Reactions of propargylic alcohol 2a (0.60 mmol) with alcohol

(3.0 mmol) were carried out in the presence of 1a and NH₄BF₄in

ClCH₂CH₂Cl (15 mL) at 608C for 1 h. [b] Isolated yield. [c] A mixture of

several unidentified products was formed.

tyne-1,5-diol and 7-octyne-1,6-diol (2h and 2i) gave the cor-

responding six- and seven-membered-ring products (3u and

3v) in only 40% and 33% yields, respectively [Eq. (5)].

Cyclization proceeded well with

a symmetrical diol 2j to give a

Table 4. Dehydration of propargylic alcohol (2) catalyzed by 1a.^[a]

mixture of two diastereomeric

isomers (3w) in 67% yield with

the isomer ratio of ca. 2:1 (dl

isomers

:

meso

isomer)

[Eq. (6)]

Propargylic

Conditions

Enyne (4)

Yield [%]^[b]

Interestingly, treatment of 2-

phenyl-3-butyn-2-ol in EtOH at

608C in the presence of a cata-

lytic amount of 1a and NH₄BF₄

led to the formation of 2-

phenyl-1-buten-3-yne (4a) in

alcohol (2)

T [8C]/t [min]

1

2

3

60/60

60/15

95 (91)^[c]

86^[d]

almost

quantitative

yield

(Table 4, entry 1), not the ex-

pected ethyl 1-phenyl-2-propyn-

yl ether. Typical results are

shown in Table 4. In the ab-

sence of 1a, the formation of

the conjugated enyne was not

observed at all. This result

prompted us to treat suitably

1,1-disubstituted propyn-1-ols

in nonpolar solvents, because

dehydration can afford the cor-

responding conjugated enynes,

91^[d]

4

5

60/60

86

76

which are important synthetic [a] Reactions of propargylic alcohol (2; 0.60 mmol) were carried out in the presence of 1a and NH₄BF₄in

ClCH₂CH₂Cl (15 mL). [b] Isolated yield. [c] At RT for 1 h. [d] GLC yield.

intermediates. Thus, heating of

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Y. Nishibayashi, M. Hidai, S. Uemura et al.

ly reported, which were produced by the stoichiometric de-

hydration of 4d and 4e assisted by a monoruthenium com-

plex.^[21]Thus, in the absence of nucleophiles, the thiolate-

bridged diruthenium complexes promoted the catalytic de-

hydration of propargylic alcohols into the corresponding

conjugated enynes in high yields. Separately, it was con-

firmed that no dehydration proceeded in the absence of 1a.

NH₄BF₄. The propargylic substitution reaction of 1-aryl- and

1-alkyl-substituted propargylic alcohols (2k–2p) with 5a at

608C for 1 h proceeded smoothly to afford the correspond-

ing N-propargylic anilines (6b–6g) in moderate to high

yields (Table 5, entries 2–7). In contrast, 1,1-diaryl-substitut-

ed propargylic alcohols such as 2e and 2 f did not react at

all even after a prolonged reaction time (76 h).

Propargylic amination of 2a with a variety of anilines was

also investigated in the presence of 1a and NH₄BF₄. Typical

results are shown in Table 6. Amination of 2a with 2-(tri-

Propargylic substitution reaction with nitrogen-centered nu-

cleophiles: Next, similar substitution with anilines was inves-

tigated in the presence of a catalytic amount of 1a. Typical

results are shown in Table 5. For example, treatment of 2a

with five equivalents of aniline (5a) in ClCH₂CH₂Cl in the

presence of 1a (5 mol%) and NH₄BF₄(10 mol%) at 608C

for 1 h afforded N-phenyl-1-phenyl-2-propynylamine (6a) in

77% isolated (89% GLC) yield (Table 5, entry 1). Similar

Table 6. Propargylic amination of propargylic alcohol 2a with amines

(5).^[a]

Amine (5)

Conditions

Propargylic

Yield [%]^[b]

T [8C]/t [h]

amine (6)

Table 5. Propargylic amination of propargylic alcohols (2) with aniline

(5a).^[a]

1

2

60/1

68

Propargylic

alcohol (2)

Propargylic

amine (6)

Yield [%]^[b]

77 (89)^[c]

82

1

2

3

4

5

60/1

60/3

60/1

88

64

83

68

95

82

59

86

71

3

4

5

6

7

6

7

60/1

60/5

16

41

PhNHMe 5g

[a] Reactions of propargylic alcohol 2a (0.60 mmol) with amines (5,

3.0 mmol) were carried out in the presence of 1a and NH₄BF₄in

ClCH₂CH₂Cl (18 mL). [b] Isolated yield.

[a] Reactions of propargylic alcohol (2; 0.60 mmol) with aniline (5a;

3.0 mmol) were carried out in the presence of 1a and NH₄BF₄in

ClCH₂CH₂Cl (18 mL) at 608C for 1 h. [b] Isolated yield. [c] GLC yield.

fluoromethyl)aniline (5b), methyl 2-aminobenzoate (5c),

and 4-nitroaniline (5d) proceeded rapidly to afford the cor-

responding propargylic amines (6h, 6i, and 6j) in 68, 82,

and 88% isolated yields, respectively (Table 6, entries 1–3).

The results indicate that functional groups such as ester and

nitro groups are tolerant during the catalytic amination. On

the other hand, in the case of 4-methylaniline (5e), a longer

to the etherification, the amination proceeded only when

the thiolate-bridged diruthenium(Ru^III–Ru^III) complexes

such as 1b and 1c were used as catalysts. In these cases, cat-

alytic amination occurred to give 6a in 64% and 75%

yields, respectively. Reactions of various propargylic alco-

hols with 5a were carried out in the presence of 1a and

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Chem. Eur. J. 2005, 11, 1433 – 1451

Ruthenium Catalysis

FULL PAPER

reaction time (3 h) was required to produce N-propargylic

4-methylaniline (6k) in 64% yield (Table 6, entry 4), while

no reaction occurred with 4-methoxyaniline (5h) even for

3 h. Thus, the introduction of an electron-releasing moiety

such as p-methyl or p-methoxy group in the aromatic group

of anilines decreased the reaction rate. Propargylation of ar-

omatic ring proceeded instead of propargylic amination

when 2a was treated with N,N-diphenylamine (5i) under the

same reaction conditions [Eq. (7)].

tams, and sulfonamides gave useful amidated products di-

rectly from propargylic alcohols. Reactions of propargylic al-

cohols with an acyclic amide such as acetamide (7a) were

investigated at first. Treatment of 2a with five equivalents of

7a at 608C for 1 h in the presence of 1a (5 mol%) and

NH₄BF₄(10 mol%) gave the corresponding propargylic

amide (8a) in 73% isolated yield with a complete regiose-

lectivity (Table 7, entry 1). The amidation proceeded

Table 7. Propargylic amidation of propargylic alcohols (2) with acet-

amide 7a.^[a]

Propargylic

alcohol (2)

Propargylic

amine (8)

Yield [%]^[b]

73 (79)^[c]

It is considered that two phenyl groups around the nitro-

gen atom of N,N-diphenylamine and low basicity of 5i may

inhibit the amination. The propargylation of a benzene ring

of 5i proceeded smoothly. Previously, we reported the prop-

argylic substitution reaction of 2a with phenol to produce

phenyl 1-phenyl-2-propynyl ether in high yield [Eq. (1)].^[15]

For comparison of the reactivity between hydroxy and

amino groups in the aromatic ring, the reaction of 2a with

2-aminophenol (5j) was carried out, but 2a was almost com-

pletely recovered together with the formation of a small

amount of unidentified products. No further information

was obtained as to the unreactivity of 5j. Unfortunately, the

use of primary alkylamines such as benzylamine (5k), ethyl-

amine (5l), and tert-butylamine (5m) for this propargylic

amination was in vain, showing that amines with high basici-

ty are not applicable to the propargylic amination (vide

infra) under these catalytic conditions.

Interestingly, carbazole (5 f) worked effectively as an ami-

nating reagent to produce N-propargylic 9-H-carbazole (6l)

in 83% yield under the same reaction conditions (Table 6,

entry 5). In contrast, the reaction with secondary alkyl-

amines, such as N-methylaniline (5g), was sluggish under

identical conditions and a prolonged time was required to

improve the yield of the propargylic amine (6m) (Table 6,

entries 6 and 7). Previously, Esteruelas and co-workers re-

ported the stoichiometric reaction of a cationic allenylidene

complex [Ru(Cp)(C=C=CPh₂)(CO)(PiPr₃)]BF₄with pyra-

zole to afford [Ru(Cp){C=CHC(Ph)₂N(CH)₃N}(CO)-

(PiPr₃)]BF₄as a result of the addition of pyrazole to the

allenylidene moiety.^[22]However, the reaction using both

imidazole (5n) and pyrazole (5o) did not give any of the ex-

pected products under our catalytic conditions.

1

2

62

50

58

70

3

4

5

6

7

42

41^[d]

[a] Reactions of propargylic alcohols (2; 0.60 mmol) with acetamide 7a

(3.0 mmol) were carried out in the presence of 1a and NH₄BF₄in

ClCH₂CH₂Cl (18 mL) at 608C for 1 h. [b] Isolated yield. [c] At RT for

2 h. [d] 10 mol% of 1a was used.

smoothly even at room temperature for 2 h, with 8a being

obtained in 79% isolated yield. Typical results are shown in

Table 7. A variety of propargylic alcohols were available for

this catalytic amidation. Introduction of a p-fluoro, p-chloro,

p-methyl, or p-methoxy substituent to the aromatic ring of

The scope of the propargylic amination extends beyond

simple amine substrates. For example, selected amides, lac-

Chem. Eur. J. 2005, 11, 1433 – 1451

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1439

Y. Nishibayashi, M. Hidai, S. Uemura et al.

2a and the use of naphthyl moiety slightly decreased the

yield of the amidation product (Table 7, entries 2–6). 1-Al-

kenyl-substituted propargylic alcohol (2r) was converted

into the corresponding alkenyl propargylic amide (8g), but

in low yield (Table 7, entry 7). Unfortunately, no amidation

occurred when 1-cyclohexyl-2-propyn-1-ol (2p) was used in

the reaction with 7a.

high reactivity of acetamide (7a), the reaction of 2a with N-

methyl acetamide (7i) was sluggish; 64% yield of 8o being

obtained by using 10 mol% of 1a as catalyst (Table 8,

entry 8). In addition, propargylation of sulfonamides such as

methanesulfonamide (7j) and p-toluenesulfonamide (7k)

occurred easily to give the corresponding propargylic

amides (8p and 8q) (Table 9, entries 1 and 2), which may be

Reactions of 2a with other acyclic amides were investigat-

ed in the presence of 1a. Typical results are shown in

Table 8. Propargylation of saturated (7b and 7c) and unsa-

Table 9. Propargylic amidation of propargylic alcohol 2a with amides

(7).^[a]

Amide (7)

Conditions Propargylic

Yield [%]^[b]

T [8C]/t [h] amide (8)

Table 8. Propargylic amidation of propargylic alcohol 2a with amides

(7).^[a]

1

2

60/1

63

Amide (7)

Propargylic

amide (8)

Yield [%]^[b]

52

1

2

3

4

5

6

7

72

3

4

60/1

78

74

56

71

61

67

64

5

60/3

18

[a] Reactions of propargylic alcohol 2a (0.60 mmol) with amide (7;

3.0 mmol) were carried out in the presence of 1a (5 mol%) and NH₄BF₄

(10 mol%) in ClCH₂CH₂Cl (18 mL). [b] Isolated yield.

transformed into the corresponding propargylic amines by

reductive method.^[23]Typical results are shown in Table 9.

Reactions of 2a with four- and five-membered-ring lactams

(7l and 7m) proceeded in the presence of 1a and the corre-

sponding propargylic lactams (8r and 8s) were obtained in

78% and 74% yields, respectively (Table 9, entries 3 and 4).

However, the six-membered-ring lactam 7n reacted with 2a

to afford the corresponding propargylic lactam 8t in only

poor yield (Table 9, entry 5). The molecular structures of 8j

and 8q were unambiguously clarified by X-ray analysis.

8

64^[c]

Propargylic substitution reaction with phosphorus-centered

nucleophiles: Diphenylphosphine oxide (9) could be used as

a phosphorus-centered nucleophile. Treatment of 2a with

five equivalents of diphenylphosphine oxide in ClCH₂CH₂Cl

in the presence of 1a (5 mol%) and NH₄BF₄(10 mol%) at

258C for 1 h gave the corresponding propargylic diphenyl-

phosphine oxide (10a) in 84% yield with a complete regio-

selectivity. Typical results are shown in Table 10. When the

same reaction was carried out at 608C, 10a was produced in

only 56% yield together with some undesirable unidentified

[a] Reactions of propargylic alcohol (2a) (0.60 mmol) with amide (7;

3.0 mmol) were carried out in the presence of 1a and NH₄BF₄in

ClCH₂CH₂Cl (18 mL) at 608C for 1 h. [b] Isolated yield. [c] 10 mol% of

1a was used.

turated (7d) amides and benzamides (7e–7h) proceeded

smoothly to give the corresponding propargylic amides in

high yields (Table 8, entries 1–7). In sharp contrast to the

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Chem. Eur. J. 2005, 11, 1433 – 1451

Ruthenium Catalysis

FULL PAPER

Table 10. Reactions of propargylic alcohols (2) with diphenylphosphine oxide (9).^[a]

of diphenylphosphinous acid

may attack the C_gatom of the

allenylidene intermediates (vide

infra).

Various propargylic alcohols

could be employed for the

propargylation of phosphine

oxide. In most cases, higher

yields of products were ob-

tained when the catalytic reac-

tions were carried out at 258C

Propargylic

alcohol (2)

Conditions

T [8C]/t [h]

Propargylic

phosphine (10)

Yield [%]^[b]

84 (56)^[c]

1

2

25/1

81

74

84

78

87

88

(Table 10,

propargylation occurred in the

reaction of 1-cyclohexyl-2-

entries 2–9).

No

propyn-1-ol (2p) with diphenyl-

phosphine oxide even at 608C,

while the reaction of 1,1-diaryl

propargylic alcohols (2e and

2 f) proceeded to give the cor-

responding propargylic phos-

phine oxide (10j and 10k) in

90% and 96% isolated yields

[Eq. (9)]. On the other hand,

3

4

5

6

7

25/1

25/18

25/1

diphenylphosphine

(PPh₂H)

could not be used as a phospho-

rus-centered nucleophile for

this catalytic reaction and thus,

the reaction of 2a with diphe-

nylphosphine in the presence of

1 resulted in the formation of

an unstable and unidentified

product (by ³¹P NMR spectros-

copy). The high basicity of di-

phenylphosphine, which might

coordinate to ruthenium, may

be one of the reasons for this

unsuccessful substitution. The

molecular structures of 10a and

10b were unambiguously clari-

fied by X-ray analysis.

8

9

25/2

90

67

[a] Reactions of propargylic alcohol (2; 0.60 mmol) with diphenylphosphine oxide (9; 3.0 mmol) were carried

out in the presence of 1a and ClCH₂CH₂Cl (18 mL). [b] Isolated yield. [c] At 608C for 1 h.

products (Table 10, entry 1). Detailed investigation of the

reaction at 608C revealed that double phosphinylation of 2a

proceeded to afford the corresponding 2,3-bis(diphenylphos-

phinyl)-3-phenyl-1-propene as a minor product. Similar to

the amination and amidation, the propargylation of phos-

phine oxide proceeded only when the thiolate-bridged diru-

thenium(Ru^III–Ru^III) complex (1a) was used as catalyst. It is

known that an equilibrium is present between 9 and its tau-

tomer (9’, diphenylphosphinous acid) by migration of a hy-

drogen atom from a phosphorus atom to an oxygen atom

[Eq. (8)].^[24]In this catalytic reaction, the phosphorus atom

Isolation of intermediate allenylidene complexes and their

reactivity: As described in our preliminary communication,

an allenylidene complex (11a) could be isolated as an inter-

mediate by the reaction of 1a with one equivalent of propar-

gylic alcohol 2 f in the presence of NH₄BF₄in EtOH at

room temperature for 1 h (Scheme 2).^[15]The molecular

structure of 11a was determined previously by X-ray crystal-

lography,^[15]an ORTEP drawing of which is shown in

Chem. Eur. J. 2005, 11, 1433 – 1451

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1441

Y. Nishibayashi, M. Hidai, S. Uemura et al.

These data suggest the important contribution of the reso-

nance structure as shown in Scheme 3. The intramolecular

distance between the two ruthenium atoms (2.768(3) ꢁ) cor-

responds to a Ru Ru single bond (2.71–3.02 ꢁ).^[25]The com-

ꢀ

plex 11a offers a rare example of a multinuclear allenyl-

Scheme 2. Isolation of an allenylidene complex and its reactivity.

Figure 1 with selected bond lengths and angles in

Table 11.^[15]The ORTEP view displays an unsymmetrically

substituted dinuclear structure, in which the h¹-allenylidene

and Cl ligands are coordinated to the respective ruthenium

Scheme 3. The important contribution of the resonance structure of the

allenylidene complexes.

idene compound with only a terminal allenylidene ligand on

the bimetallic center.^[7]As described earlier, the stoichio-

metric reaction of 11a in EtOH at 608C for 20 h afforded

3h in 89% GLC yield.^[15]Here, stoichiometric reactions be-

tween the allenylidene complex [(Cp*)RuCl(m₂-SMe)₂-

Ru(Cp*)(C=C=CHPh)]BF₄(11b)^[17a]and anilines were in-

vestigated. Treatment of 11b with ten equivalents of aniline

(5a) in ClCH₂CH₂Cl at 608C for 3 h gave propargylic amine

6a in 22% isolated yield based on 11b (Scheme 4). In addi-

Scheme 4. Stoichiometric reaction of the allenylidene complex 11b with

Figure 1. ORTEP drawing for the cationic part of 11a. Hydrogen atoms

aniline.

are omitted for clarity.

tion, the propargylic amination of 2a with 5a in the pres-

ence of 5 mol% of 11b proceeded to afford 6a in 71%

yield. These results indicate that the propargylic substitution

reaction generally proceeds via allenylidene complexes like

11b.

Table 11. Selected bond lengths [ꢁ] and angles [8] for 11a.^[15]

ꢀ

Ru1 Ru2

2.768(3)

2.316(7)

2.303(6)

1.91(2)

2.396(7)

2.307(7)

Ru2 S2

2.312(6)

1.20(3)

1.47(3)

1.80(3)

1.86(2)

ꢀ

Ru1 S1

C23 C24

ꢀ

Ru1 S2

C24 C25

ꢀ

Ru1 C23

S1 C21

ꢀ

Theoretical studies clearly indicate that the C_aand C_g

atoms of the allenylidene moiety are electrophilic centers,

while the C_batom works as a nucleophilic site.^[7]It is known

that both primary and secondary amines attack on the C_a

atom in allenylidene complexes such as [CpRu(C=C=

CPh₂)(CO)(PiPr₃)]BF₄to afford the corresponding azonia-

butadienyl complexes [CpRu{C(CH=CPh₂)=NR’’₂}(CO)-

(PiPr₃)]BF₄(R’’=aryl, alkyl, alkenyl, or H).^[26]In contrast,

the nucleophilic attack of amine on the allenylidene C_g

atom is limited to the reaction of cationic allenylidene com-

plex [CpRu(C=C=CPh₂)(PPh₃)₂]PF₆with dimethylamine to

form [CpRu{CꢁCCPh₂(NHMe₂)}(PPh₃)₂]PF₆.^[27]In our

system, the steric bulkiness of the two Cp* ligands present

at diruthenium core seems to inhibit the nucleophilic attack

of the amine on the C_aatom in the allenylidene ligand.

Ru2 Cl1

S2 C22

ꢀ

Ru2 S1

Ru2-Ru1-C23

S1-Ru1-S2

Ru1-Ru2-Cl1

S1-Ru2-S2

97.9(7)

106.3(3)

94.3(2)

Ru1-S1-Ru2

Ru1-S2-Ru2

Ru1-C23-C24

C23-C24-C25

73.6(2)

73.7(2)

171.0(2)

174.0(2)

106.2(2)

centers in a mutual cis configuration, and it is in a full ac-

cordance with the NMR and IR spectroscopic observations.

The allenylidene moiety C23-C24-C25 is almost linear

ꢀ

(174(2)8). The C23 C24 bond (1.20(3) ꢁ) is significantly

shorter than the normal carbon–carbon double bond, where-

ꢀ

as the C24 C25 bond (1.47(3) ꢁ) is significantly longer.

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Chem. Eur. J. 2005, 11, 1433 – 1451

Ruthenium Catalysis

FULL PAPER

Thus, the amine attacks regioselectively on the C_gatom in

allenylidene complexes like 11b.

The stoichiometric reaction of an allenylidene complex

(11a) with diphenylphosphine oxide (9) gave propargylic

phosphine oxide 10k in 80% yield (Scheme 5), indicating

Figure 2. Plot of log(k_X/k_H) vs s values for the ruthenium-catalyzed prop-

argylic substitution reactions of propargylic alcohol (2a) with substituted

anilines.

Scheme 5. Stoichiometric reaction of the allenylidene complex 11a with

diphenylphosphine oxide.

that the phosphorus–carbon bond formation also proceeds

through the nucleophilic attack of the phosphorus atom to

the C_gatom of the allenylidene ligand. Several examples of

nucleophilic addition of secondary and tertiary phosphines

to the C_gatom of the ruthenium and rhenium allenylidene

complexes have already been reported to afford the corre-

sponding g-phosphonioalkynyl and their rearranged a-phos-

phonioallenyl complexes.^[28]

Catalytic reaction pathway for propargylic substitution—

amination as a representative example: The relative reactivi-

ty of substituted anilines (XC₆H₄NH₂, X=p-Me, H, p-Cl)

for the reactions with 2a in the presence of 1a was deter-

mined (Scheme 6 and Table 12). The relative rates were de-

termined by the conversion of 2a when conversions were

low (<10%). The rate data correlate well with the Ham-

mett linear free-energy relationship with use of s values

(Figure 2). Better correlation (1=2.3) was obtained with a s

value rather than s⁺, suggesting the absence of electrophilic

species in the rate-determining step. This result indicates

that the attack of anilines on the C_gatom in the allenylidene

ligand is not involved in the rate-determining step. The acid-

ity of conjugated anilines on an

Scheme 6. The relative reactivity of substituted anilines.

Table 12. Relative rate constants for the ruthenium-catalyzed propargylic

substitution reactions of propargylic alcohol (2a) with substituted ani-

lines.

X in XC₆H₄NH₂

s

(s⁺)

k_X/k_H

log(k_X/k_H)

p-Me

H

ꢀ0.17

0

(ꢀ0.31)

(0)

0.278

0

-0.556

0

0.388

p-Cl

0.23

(0.11)

2.444

alkynyl complex (C’), which is

formed after the attack of ani-

lines on the C_gatom of the

allenylidene complex (B), is

considered to be the most im-

portant factor to determine the

rate of the catalytic reactions of

2a with anilines (Scheme 7).

Thus, the higher acidity of the

proton of conjugated anilines in

the alkynyl complex promotes

the hydrogen atom shift onto

the C_batom on the ligand to

Scheme 7. The acidity of conjugated anilines on an alkynyl complex is considered to be the most important

factor.

give the vinylidene complex (D’). This proton 1,3-migration

step should be involved in the rate-determining step. In fact,

the proton migration did not occur in the reactions with al-

kylamines of low acidity, such as benzylamine and ethyl-

amine, and also with anilines bearing electron-releasing

moiety at aromatic ring, such as p-methoxyaniline. On the

other hand, good correlation (1=ꢀ0.39) was also obtained

with a s value when the relative reactivity of substituted

propargylic alcohol (XC₆H₄CH(OH)CꢁCH, X=p-Me, H, p-

Cl) with 5a was determined in the presence of 1a

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Y. Nishibayashi, M. Hidai, S. Uemura et al.

(Scheme 8). The 1 value, however, was quite smaller than

that obtained for the reaction of 2a with anilines.

By considering all the experimental evidence, a reaction

pathway of this catalytic propargylic substitution reaction is

proposed in Scheme 9 for amination with aniline as a repre-

the thiolate-bridged diruthenium complexes can promote

the catalytic propargylic substitution reaction. The key point

to promote our catalytic reaction by using the thiolate-

bridged diruthenium complexes is considered to be the ease

of the ligand exchange steps in the catalytic cycle (D!E in

Scheme 9). In fact, Gimeno and co-workers reported the re-

action of the allenylidene complexes with nucleophiles to

give the corresponding vinylidene complexes, and confirmed

that the ligand exchange of the vinylidene moiety with an-

other ligand did not proceed smoothly to give the corre-

sponding terminal alkyne, which is derived from the vinyl-

idene ligand.^[8]In order to obtain some information of the

ease of ligand exchange for our catalytic reaction by using

the thiolate-bridged diruthenium complexes, the following

stoichiometric reactions between the allenylidene complex

[(Cp*)RuCl(m₂-SMe)₂Ru(Cp*)(C=C=CHPh)]BF₄(11b)^[17a]

and anilines were investigated in the presence of a variety

of an additive (Table 13). Although no improved yield was

Scheme 8. The relative reactivity of substituted propargylic alcohols.

Table 13. Reactions of allenylidene complex 11b with aniline (5a) in the

presence of additive.^[a]

Additive

Equiv^[b]

Yield of 6a [%]^[c]

1

2

3

–

22^[d]

21

56

NH₄BF₄

NH₄Cl

5

4

1

39

5

1

53^[e]

Scheme 9. A reaction pathway of the catalytic propargylic substitution re-

action.

[a] Reactions of allenylidene complex 11b (0.02 mmol) with aniline (5a;

0.2 mmol) were carried out in the presence of an additive in ClCH₂CH₂Cl

(2 mL). [b] Equivalents of additive relative to 11b. [c] GLC yield. [d] Iso-

lated yield. [e] 6b was also obtained in 49% GLC yield.

sentative example. Initially, a vinylidene complex (A) is

formed in the reaction of 1a with propargylic alcohol in the

presence of NH₄BF₄. Dehydration of A leads to an allenyl-

idene complex (B), and subsequent nucleophilic attack of

aniline on the C_gatom in the allenylidene ligand results in

the formation of an alkynyl complex (C), in which the

higher acidity of the proton of conjugated anilines in C pro-

motes a hydrogen atom shift into the C_batom on the ligand

to give another vinylidene complex (D). Thus, the addition

of NH bond of the amine to the C_g=C_bdouble bond of the

allenylidene group takes place to yield the vinylidene com-

plex D. The complex D is then transformed into the h²-coor-

dinated propargylic amine tautomer (E), which liberates the

product propargylic amine (F) by the reaction with a prop-

argylic alcohol and regenerates the complex A.^[8,29]

observed in the presence of NH₄BF₄(Table 13, entry 2), the

addition of either NH₄Cl or another terminal alkyne much

improved the yield of 6a (Table 13, entries 3 and 4). The re-

action of 11b with 5a in the presence of propargylic alcohol

2k gave 6a in 53% yield together with 6b in 49% yield

(Table 13, entry 5). These results indicate that the liberation

of product 6a (or F’) from the intermediate E’ may be accel-

erated by a ligand exchange^[8,29]with NH₄Cl, producing a

stable starting complex 1a (Scheme 10). In the case of the

addition of another terminal alkyne, a similar ligand ex-

change^[8,26]from E’ with the alkyne occurs smoothly to give

the product F’ and the corresponding vinylidene complex A’

(Scheme 11). Thus, it has now been found that the ligand ex-

change of the vinylidene moiety in the thiolate-bridged diru-

thenium complexes proceeds quite smoothly, clarifying the

key point for our catalytic reaction.

Although reactions in the presence of many types of

ruthenium complexes have been carried out until now, only

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Chem. Eur. J. 2005, 11, 1433 – 1451

Ruthenium Catalysis

FULL PAPER

ease of the charge transfer from

one Ru atom to the other in

the

complexes

(synergistic

effect) may be one of the im-

portant factors to promote the

ligand exchange (step a), which

is a key step for the catalytic re-

action.^[30]As a result, we con-

sider that newly obtained ex-

perimental results support our

previous proposal for the cata-

lytic reaction pathway. Thus,

our new findings described in

this paper provide the basis of

the catalytic reaction pathway,

which we have already pro-

Scheme 10. The liberation of product from the intermediate may be accelerated by a ligand exchange with

NH₄Cl.

Scheme 11. The liberation of product from the intermediate may be accelerated by a ligand exchange with an- posed in our previous paper. Fi-

other terminal alkyne.

nally, we summarized a full re-

action pathway of this catalytic

propargylic substitution reac-

The above results of the stoichiometric and catalytic reac-

tions indicate that allenylidene complexes such as 11a are

one of the key intermediates for the propargylic substitution

reactions. However, we have previously reported one exam-

ple of the propargylic substitution reaction of propargylic al-

cohols bearing not only terminal acetylene but also internal

acetylene units.^[16]At present, we should also consider the

possibility of Nicholas type activation by coordination of

acetylene unit of propargylic alcohols on the diruthenium

sites.^[2]

tion in Scheme 13 by using NuH as a nucleophile. Further

work is currently in progress aiming at the elucidation of

the more detailed reaction mechanism assisted by quantum

calculations.

Conclusion

A general procedure for the catalytic propargylic substitu-

tion reactions of propargylic alcohols with heteroatom-cen-

tered nucleophiles is reported. Oxygen-, nitrogen-, and

phosphorus-centered nucleophiles such as alcohols, amines,

amides, and phosphine oxide are available for this catalytic

reaction. The most characteristic feature of this reaction is

the direct use of propargylic alcohols as effective substrates,

the only expected byproduct in stoichiometry being water

(H₂O). It is noteworthy that only the thiolate-bridged diru-

thenium complexes promote this catalytic reaction. Results

of some stoichiometric and catalytic reactions indicate that

the catalytic propargylic substitution reaction proceeds via

allenylidene complexes, for which the attack of nucleophiles

to the C_gatom of the allenyl-

As described in our previous paper,^[30]we believe that the

reason why only the diruthenium complexes promote the

ligand exchange step more easily in our catalytic reaction

should be that one Ru moiety, which is not involved in the

allenylidene formation, works as an electron pool or a

mobile ligand to another Ru site (Scheme 9), by taking into

account of the theoretical report of synergistic effects of two

equal Rh metals in the dirhodium-catalyzed reaction be-

tween diazo compound and alkane.^[31]To prove the possibili-

ty of the synergistic effects of two ruthenium atoms as de-

scribed in Scheme 12, a series of chalcogenolate (S, Se, Te)-

idene ligand is a key step. Fur-

thermore, the key point to pro-

mote the catalytic reaction by

using the thiolate-bridged diru-

thenium complexes is consid-

ered to be the ease of the

ligand exchange step between a

vinylidene ligand on the diru-

Scheme 12. The possibility of the synergistic effects of two ruthenium atom s.

thenium complexes and another

bridged diruthenium complexes (neutral and cationic) have

been prepared and their catalytic activities toward the prop-

argylic substitution reactions as well as electronic properties

have been investigated to prove the proposed reaction path-

way.^[30]Results of both catalytic and stoichiometric reactions

and electronic behaviors of the complexes indicate that the

propargylic alcohol in the catalytic cycle. Our new findings

described in this paper provide the basis of the catalytic re-

action pathway, which we have already proposed in our pre-

vious paper. The procedure in this paper provides a versatile

and direct method for propargylic substitution of propargyl-

ic alcohols.

Chem. Eur. J. 2005, 11, 1433 – 1451

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ꢀ 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

1445

Y. Nishibayashi, M. Hidai, S. Uemura et al.

TLC (SiO₂) with EtOAc-n-hexane (1/9) to give 3a as a pale yellow oil

(0.53 mmol, 88% yield).

Data for 3a: ¹H NMR: d=1.26 (t, J=7.0 Hz, 3H), 2.63 (d, J=2.0 Hz,

1H), 3.55 (qd, J=7.0, 8.8 Hz, 1H), 3.75 (qd, J=7.0, 8.8 Hz, 1H), 5.16 (d,

J=2.0 Hz, 1H), 7.33–7.40 (m, 3H), 7.52 ppm (d, J=7.3 Hz, 2H);

¹³C NMR: d=15.1, 63.9, 71.1, 75.3, 81.8, 127.3, 128.4, 128.5, 138.3 ppm;

IR (neat): n˜ =2114 (CꢁC), 3293 cm^ꢀ1(ꢁCH); elemental analysis calcd

(%) for C₁₁H₁₂O: C 82.46, H 7.55; found: C 82.56, H, 7.47.

Data for 3b: Yield 84%; a pale yellow oil; ¹H NMR: d=2.66 (d, J=

2.5 Hz, 1H), 3.45 (s, 3H), 5.09 (s, 1H), 7.34–7.40 (m, 3H), 7.51 ppm (d,

J=7.8 Hz, 2H); ¹³C NMR: d=55.9, 72.7, 75.8, 81.2, 127.3, 128.5, 128.5,

137.9 ppm; IR (neat): n˜ =2114 (CꢁC), 3293 cm^ꢀ1(ꢁCH); elemental anal-

ysis calcd (%) for C₁₀H₁₀O: C 82.16, H 6.89; found: C 82.33, H 6.77.

Data for 3c: Yield 91%; a pale yellow oil; ¹H NMR: d=1.22 (d, J=

5.6 Hz, 3H), 1.25 (d, J=5.6 Hz, 3H), 2.58 (d, J=2.0 Hz, 1H), 3.98 (sept,

J=5.6 Hz, 1H), 5.20 (s, 1H), 7.32–7.39 (m, 3H), 7.51 ppm (d, J=8.0 Hz,

2H); ¹³C NMR: d=21.6, 22.7, 68.5, 69.7, 74.6, 82.6, 127.2, 128.3, 128.5,

139.0 ppm; IR (neat): n˜ =2114 (CꢁC), 3293 cm^ꢀ1(ꢁCH); elemental anal-

ysis calcd (%) for C₁₂H₁₄O: C 82.72, H 8.10; found: C 82.61, H 8.07.

Data for 3d: Yield 75%; a pale yellow oil; ¹H NMR: d=0.89 (t, J=

6.8 Hz, 3H), 1.13 (d, J=6.0 Hz, 3H), 1.21 (d, J=6.0 Hz, 3H), 1.30 (m,

4H), 1.45 (m, 2H), 1.69 (m, 2H), 2.37 (s, 1H), 3.90 (sept, J=6.0 Hz, 1H),

4.08 ppm (t, J=6.4 Hz, 1H); ¹³C NMR: d=14.0, 21.2, 22.6, 23.2, 25.0,

31.5, 36.1, 66.6, 69.7, 72.5, 84.1 ppm; IR (neat): n˜ =2110 (CꢁC),

3312 cm^ꢀ1(ꢁCH); elemental analysis calcd (%) for C₁₁H₂₀O: C 78.51, H

11.98; found: C 78.11, H 11.58.

Data for 3e: Yield 54%; a pale yellow oil; ¹H NMR: d=1.20 (t, J=

6.8 Hz, 3H), 1.73 (m, 4H), 1.92–1.98 (m, 4H), 2.45 (s, 1H), 3.58 ppm (q,

J=6.8 Hz, 2H); ¹³C NMR: d=15.7, 23.2, 39.4, 60.0, 72.2, 79.7, 85.8 ppm;

IR (neat): n˜ =2108 (CꢁC), 3306 cm^ꢀ1(ꢁCH); elemental analysis calcd

(%) for C₉H₁₄O: C 78.21, H 10.21; found: C 78.45, H 10.33.

Data for 3 f: Yield 57%; a pale yellow oil; ¹H NMR: d=1.21 (t, J=

6.8 Hz, 3H), 1.26 (m, 4H), 1.52–1.66 (m, 4H), 1.89 (m, 2H), 2.44 (s, 1H),

3.62 ppm (q, J=6.8 H, 2Hz); ¹³C NMR: d=15.8, 22.7, 25.4, 29.7, 37.1,

58.4, 73.2, 85.6 ppm; IR (neat): n˜ =2103 (CꢁC), 3308 cm^ꢀ1(ꢁCH); ele-

mental analysis calcd (%) for C₁₀H₁₆O: C 78.90, H 10.59; found: C 78.51,

H 10.48.

Data for 3g: Yield 62%; a pale yellow oil; ¹H NMR: d=1.27 (t, J=

7.2 Hz, 3H), 2.86 (d, J=2.0 Hz, 1H), 3.54 (q, J=7.2 Hz, 2H), 7.22–7.33

(m, 6H), 7.56 ppm (d, J=8.0 Hz, 4H); ¹³C NMR: d=15.3, 60.4, 77.2,

79.9, 83.5, 126.5, 127.6, 128.1, 143.4 ppm; IR (neat): n˜ =2110 (CꢁC),

3285 cm^ꢀ1(ꢁCH); elemental analysis calcd (%) for C₁₇H₁₆O: C 86.41; H

6.82; found: C 85.97, H 6.67.

Data for 3h: Yield 61%; a pale yellow oil; ¹H NMR: d=1.26 (t, J=

7.2 Hz, 3H), 2.31 (s, 6H), 2.83 (s, 1H), 3.52 (q, J=7.2 Hz, 2H), 7.10 (d,

J=7.6 Hz, 4H), 7.42 ppm (d, J=7.6 Hz, 4H); ¹³C NMR: d=15.3, 21.0,

60.2, 76.8, 79.6, 83.9, 126.4, 128.8, 137.2, 140.7 ppm; IR (neat): n˜ =2110

(CꢁC), 3287 cm^ꢀ1(ꢁCH); elemental analysis calcd (%) for C₁₉H₂₀O: C

86.32, H , 7.63; found: C 85.95, H 7.51.

Scheme 13. A full reaction pathway of the catalytic propargylic substitu-

tion reaction.

Experimental Section

1

General methods: H NMR (400, 300, and 270 MHz) and ¹³C NMR (100,

75, and 67.8 MHz) spectra were recorded using CDCl₃as solvent. Quanti-

tative GLC analyses were performed on a Shimadzu GC-14A instrument

equipped with a flame ionization detector using a 25 mꢂ0.25 mm CBP10

fused silica capillary column. GC-MS analyses were carried out on a Shi-

madzu GC-MS QP-5000 spectrometer. Elemental analyses were per-

formed at Microanalytical Center of Kyoto University. Mass spectra were

measured on a JEOL JMS600H mass spectrometer. All reactions were

carried out under a dry nitrogen atmosphere. Solvents were dried by the

usual methods and distilled before use.

Materials: Thiolate-bridged diruthenium complexes^[15,30](1) and the

allenylidene complexes^[15,17](11) were prepared according to our previous

procedures. Propargylic alcohol (2a) was a commercial product. Other

propargylic alcohols were prepared by the reactions of the corresponding

aldehydes with ethynylmagnesium bromide. Propargylic products (3o,^[19]

3u,^[32]4d,^[21]and 4e^[21]) were previously prepared by us or other groups.

When phenol and chiral alcohols were used as nucleophiles, the reactions

were carried out in ClCH₂CH₂Cl as solvent. A typical experimental pro-

cedure for the reaction of 2a and phenol is as follows. Compound 1a

(0.03 mmol) and NH₄BF₄(0.06 mmol) were placed in a 20 mL flask

under N₂. Anhydrous ClCH₂CH₂Cl (15 mL) was added, and then the

mixture was magnetically stirred at room temperature. After the addition

of 2a (0.60 mmol) and phenol (3.00 mmol), the reaction flask was kept at

608C for 60 min. The reaction mixture was treated with brine (50 mL)

and then extracted with diethyl ether (20 mLꢂ3). The ether layer was

dried over anhydrous MgSO₄. For isolation, the extract was concentrated

under reduced pressure by an aspirator, and then the residue was purified

by HPLC (the eluent: CHCl₃) to give 3n as a pale yellow oil (0.39 mmol,

65% yield).

Ruthenium-catalyzed propargylic substitution reactions of propargylic al-

cohols with nucleophiles: A typical experimental procedure for the reac-

tion of 1-phenyl-2-propyn-1-ol (2a) with EtOH catalyzed by 1a is de-

scribed below. Complex 1a (0.03 mmol) and NH₄BF₄(0.06 mmol) were

placed in a 20 mL flask under N₂. Anhydrous EtOH (15 mL) was added,

and then the mixture was magnetically stirred at room temperature.

After the addition of 2a (0.60 mmol), the reaction flask was kept at 608C

for 15 min. The reaction mixture was treated with brine (50 mL) and

then extracted with diethyl ether (20 mLꢂ3). The ether layer was dried

over anhydrous MgSO₄. For isolation, the extract was concentrated under

reduced pressure by an aspirator, and then the residue was purified by

Data for 3n: ¹H NMR: d=2.68 (d, J=2.0 Hz, 1H), 5.83 (s, 1H), 7.01 (t,

J=7.2 Hz, 1H), 7.09 (d, J=7.2 Hz, 2H), 7.31 (t, J=8.4 Hz, 2H), 7.37–

7.43 (m, 3H), 7.61 ppm (d, J=7.2 Hz, 2H); ¹³C NMR: d=69.7, 76.6, 80.9,

116.1, 121.8, 127.2, 128.7, 128.8, 129.4, 137.4, 157.3 ppm; IR (neat): n˜ =

1446

ꢀ 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

www.chemeurj.org

Chem. Eur. J. 2005, 11, 1433 – 1451

Ruthenium Catalysis

FULL PAPER

2120 (CꢁC), 3289 cm^ꢀ1(ꢁCH); elemental analysis calcd (%) for

2.4 Hz, 1H), 7.32–7.54 ppm (m, 5H); ¹³C NMR: d=3.68, 56.1, 69.5, 74.5,

75.9, 81.0, 83.2, 127.6, 128.5, 128.6, 137.7 ppm; elemental analysis calcd

(%) for C₁₃H₁₂O: C 84.75, H 6.57; found: C 84.48, H 6.72.

Data for 3t: Yield 92%; a pale yellow oil; ¹H NMR: d=2.61 (d, J=

2.4 Hz, 1H), 5.09 (d, J=12 Hz, 1H), 5.23 (d, J=12 Hz, 1H), 5.89 (d, J=

2.4 Hz, 1H), 7.26–7.37 ppm (m, 4H); ¹³C NMR: d=73.0, 73.1, 74.2, 82.0,

121.1, 121.7, 127.8, 128.3, 138.6, 138.8 ppm; elemental analysis calcd (%)

for C₁₀H₈O: C 83.31, H 5.59; found: C 82.96, H 5.43.

Data for 3w: Yield 67%; a pale yellow oil; ¹H NMR: d=2.65 (s, 1H),

2.68 (s, 1H), 5.93 (s, 1H), 6.10 (s, 1H), 7.48 (d, J=3.3 Hz, 1H), 7.59 (d,

J=3.3 Hz, 1H), 7.79–7.85 ppm (m, 4H); ¹³C NMR: d=71.8, 72.0, 75.0,

75.1, 81.0, 81.3, 120.7, 120.8, 126.5, 126.6, 128.1, 133.6, 137.0, 137.1 ppm;

HRMS: m/z calcd for C₁₆H₁₀O [M⁺]: 218.0732; found: 218.0726.

C₁₅H₁₂O: C 86.51, H 5.81; found: C 86.49, H 5.78.

Data for 3i: Yield 80%; a pale yellow oil; two diastereomers with a ratio

of 50:50; ¹H NMR: d=0.88 (t, J=7.2 Hz, 3H), 0.92 (d, J=7.2 Hz, 3H),

1.15 (m, 1H), 1.49 (m, 1H), 1.71 (m, 1H), 2.61 (s, 1H), 3.26 and 3.36 (dd

each, J=8.0 Hz, 1H), 3.46 and 3.54 (dd each, J=8.0 Hz, 1H), 5.14 (s,

1H), 7.23–7.39 (m, 3H), 7.53 ppm (d, J=7.2 Hz, 2H); ¹³C NMR: d=11.2

and 11.2, 16.6 and 16.6, 26.2 and 26.2, 34.8 and 34.9, 71.2 and 71.3, 73.5

and 73.6, 75.2 and 75.2, 81.9 and 82.0, 127.1, 128.2, 128.4, 138.5 ppm; IR

(neat): n˜ =2114 (CꢁC), 3306 cm^ꢀ1(ꢁCH); elemental analysis calcd (%)

for C₁₄H₁₈O: C 83.12, H 8.97; found: C 83.17, H 8.89.

Data for 3j: Yield 92%; a pale yellow oil; two diastereomers with a ratio

1

of 51:49; H NMR: d=1.31 (brs, 3H), 2.61 (s, 1H), 3.08 (brs, 1H), 3.51–

3.79 (m, 2H), 5.14 and 5.19 (s each, 1H), 7.23–7.44 ppm (m, 10H);

¹³C NMR: d=18.4 and 18.5, 39.8, 71.2, 73.7 and 73.9, 75.5 and 75.6, 81.5

and 81.6, 126.3, 127.1 and 127.1, 127.3, 128.3 and 128.4, 138.1 and 138.1,

144.1 and 144.2 ppm; IR (neat): n˜ =2114 (CꢁC), 3289 cm^ꢀ1(ꢁCH); ele-

mental analysis calcd (%) for C₁₈H₁₈O: C 86.36, H 7.25; found: C 86.15,

H 7.28.

Ruthenium-catalyzed propargylic amination of propargylic alcohols with

amines: A typical experimental procedure for the reaction of 1-phenyl-2-

propyn-1-ol (2a) with aniline (5a) catalyzed by 1a is described below.

Compound 1a (0.03 mmol) and NH₄BF₄(0.06 mmol) were placed in a

20 mL flask under N₂. Anhydrous ClCH₂CH₂Cl (18 mL) was added, and

then the mixture was magnetically stirred at room temperature. After the

addition of 2a (0.60 mmol) and 5a (3.00 mmol), the reaction flask was

kept at 608C for 1 h. For the isolation of 6a, the solvent was removed

under reduced pressure and the residue was purified by HPLC (the

eluent: CHCl₃) to give pure 6a as a yellow oil (95.7 mg, 0.46 mmol,

77%).

Data for 3k: Yield 69%; a pale yellow oil; two diastereomers with a

ratio of 55:45; ¹H NMR: d=1.44 and 1.52 (d each, J=6.8 Hz, 3H), 2.54

and 2.61 (d each, J=2.0 Hz, 1H), 4.44 and 5.00 (q each, J=6.8 Hz, 1H),

4.88 and 4.96 (s each, 1H), 7.30–7.47 ppm (m, 10H); ¹³C NMR: d=23.7

and 24.2, 68.2 and 68.5, 74.4 and 74.9, 75.3 and 75.8, 81.8 and 82.8, 126.4

and 126.7, 127.3 and 127.4, 127.7 and 127.8, 128.3, 128.4 and 128.5, 128.6

and 128.6, 138.4 and 138.7, 142.6 and 142.7 ppm; IR (neat): n˜ =2114 (Cꢁ

C), 3289 cm^ꢀ1(ꢁCH); elemental analysis calcd (%) for C₁₇H₁₆O: C 86.41,

H, 6.82; found: C 86.30, H 6.95.

1

N-Phenyl-1-phenyl-2-propynylamine (6a): H NMR: d=2.43 (d, J=2 Hz,

1H), 4.01 (br, 1H), 5.26 (s, 1H), 6.69 (d, J=8 Hz, 2H), 6.77 (d, J=7 Hz,

1H), 7.16–7.21 (m, 2H), 7.30–7.38 (m, 3H), 7.58 ppm (d, J=7 Hz, 2H);

¹³C NMR: d=49.7, 73.1, 82.9, 113.9, 118.7, 127.1, 128.1, 128.7, 129.1,

138.9, 146.2 ppm; IR (KBr): n˜ =2114 (CꢁC), 3279 (ꢁCH), 3372 cm^ꢀ1

(NH); elemental analysis calcd (%) for C₁₅H₁₃N: C 86.92, H 6.32, N,

6.76; found: C 86.70, H 6.68, N 7.10.

Data for 3l: Yield 64%; a white solid, m.p. 81.5–82.08C; two diastereo-

mers with a ratio of 70:30; ¹H NMR: d=1.48 and 1.60 (d each, J=

6.6 Hz, 3H), 1.52 and 1.57 (d each, J=6.6 Hz, 1H), 2.52 and 2.62 (d each,

J=2.1 Hz, 1H), 4.91 and 5.01 (d each, J=2.1 Hz, 1H) 7.26–7.87 ppm (m,

12H); ¹³C NMR: d=23.7 and 24.1, 68.4 and 68.7, 74.5 and 75.1, 75.4 and

76.0, 81.8 and 82.8, 124.1 and 124.3, 125.8 and 126.0, 126.0 and 126.1,

127.2 and 127.3, 127.6 and 127.6, 127.8 and 127.8, 128.2 and 128.6, 128.4

and 128.4, 128.0 and 128.3, 128.4 and 128.4, 133.1 and 133.1 ppm; elemen-

tal analysis calcd (%) for C₂₁H₁₈O: C 88.08, H 6.34; found: C 87.89, H

6.21.

N-Phenyl-1-(4-fluorophenyl)-2-propynylamine (6b): Yield 68%; a yellow

solid, m.p. 47.1–47.98C; ¹H NMR: d=2.45 (d, J=2 Hz, 1H), 4.01 (br,

1H), 5.24 (s, 1H), 6.69 (d, J=8 Hz, 2H), 6.78 (t, J=7 Hz, 1H), 7.04 (t,

J=8 Hz, 2H), 7.19 (t, J=7 Hz, 2H), 7.52–7.56 ppm (dd, J=8, 5 Hz, 2H);

¹³C NMR: d=49.0, 73.4, 82.7, 114.0, 115.5 (d, J=22 Hz), 118.8, 128.9 (d,

J=8 Hz), 129.2, 134.7 (d, J=3 Hz), 146.0, 162.4 ppm (d, J=246 Hz); IR

(KBr): n˜ =2097 (CꢁC), 3187 (ꢁCH), 3345 cm^ꢀ1(NH); elemental analysis

calcd (%) for C₁₅H₁₂FN: C 79.98, H 5.37, N, 6.22; found: C 80.11, H 5.66,

N 6.03.

Data for 3m: Yield 71%; a pale yellow oil; two diastereomers with a

1

ratio of 70:30; H NMR: d=0.49 and 0.49 (d each, J=6.9 Hz, 1H), 0.83–

0.95 (m, 9H), 0.97–1.68 (m, 6H), 2.16–2.38 (m, 2H), 2.54 and 2.57 (d

each, J=1.8 Hz, 1H), 3.23 and 3.62 (dt each, J=4.2, 10 Hz, 1H), 5.14

and 5.28 (d each, J=1.8 Hz, 1H) 7.28–7.51 ppm (m, 5H); ¹³C NMR: d=

15.6 and 16.2, 21.1 and 21.1, 22.3 and 22.4, 22.9 and 23.2, 24.9 and 25.2,

31.5 and 31.6, 34.4 and 34.5, 39.7 and 41.1, 48.1 and 48.5, 67.8 and 69.8,

74.3 and 74.7, 76.6 and 78.1, 82.7 and 83.6, 127.2 and 127.5, 128.2 and

128.4, 139.1 and 139.3 ppm; elemental analysis calcd (%) for C₁₉H₂₆O: C

84.39, H 9.69; found: C 84.15, H 9.80.

N-Phenyl-1-(4-chlorophenyl)-2-propynylamine (6c): Yield 95%; a yellow

solid; ¹H NMR: d=2.47 (d, J=2 Hz, 1H), 4.03 (br, 1H), 5.25 (d, J=

2 Hz, 1H), 6.69 (d, J=8 Hz, 2H), 6.79 (t, J=7 Hz, 1H), 7.19 (t, J=7 Hz,

2H), 7.34 (d, J=8 Hz, 2H), 7.52 ppm (d, J=8 Hz, 2H); ¹³C NMR: d=

49.3, 73.5, 82.5, 114.0, 118.9, 128.4, 128.8, 129.1, 133.9, 137.4, 145.9 ppm;

elemental analysis calcd (%) for C₁₅H₁₂ClN: C 74.53, H 5.00, N, 5.79;

found: C 74.22, H 4.81, N 5.57.

N-Phenyl-1-(4-methylphenyl)-2-propynylamine (6d): Yield 82%;

a

1

yellow solid, m.p. 68.8–70.08C; ¹H NMR: d=2.33 (s, 3H), 2.42 (d, J=

2 Hz, 1H), 3.98 (br, 1H), 5.22 (d, J=2 Hz, 1H), 6.69 (d, J=8 Hz, 2H),

6.76 (t, J=7 Hz, 1H), 7.16–7.20 (m, 4H), 7.46 ppm (d, J=8 Hz, 2H);

¹³C NMR: d=21.1, 49.4, 72.9, 83.1, 113.9, 118.6, 127.0, 129.1, 129.4, 136.0,

137.9, 146.2 ppm; IR (neat): n˜ =2110 (CꢁC), 3268 (ꢁCH), 3386 cm^ꢀ1

(NH); elemental analysis calcd (%) for C₁₆H₁₅N: C 86.84, H 6.83, N 6.33;

found: C 86.71, H 6.79, N 6.11.

Data for 3p: Yield 81%; a pale yellow oil; H NMR: d=2.68 (d, 1H, J=

2.4 Hz), 2.62–2.69 (m, 2H), 3.74–3.82 (m, 1H), 3.86–3.93 (m, 1H), 5.28

(d, J=2.4 Hz, 1H), 7.24–7.55 ppm (m, 5H); ¹³C NMR: d=42.6, 67.9,

71.5, 76.3, 80.8, 127.3, 128.5, 128.6, 137.4 ppm; elemental analysis calcd

(%) for C₁₁H₁₁ClO: C 67.87, H, 5.70; found: C 67.97, H 5.84.

Data for 3q: Yield 77%; a pale yellow oil; ¹H NMR: d=2.66 (d, J=

2.1 Hz, 1H), 4.22 (d, J=1.0 Hz, 1H), 4.23 (d, J=1.0 Hz, 1H), 5.25 (d, J=

2.1 Hz, 1H), 5.40 (d, J=1.0 Hz, 1H), 5.53 (d, J=1.0 Hz, 1H), 7.31–

7.55 ppm (m, 5H); ¹³C NMR: d=70.3, 70.4, 76.3, 80.7, 114.4, 127.4, 128.5,

128.7, 137.4, 137.5 ppm; HRMS: m/z calcd for C₁₂H₁₂ClO [M⁺+H]:

207.0577; found: 207.0584.

Data for 3r: Yield 50%; a pale yellow oil; ¹H NMR: d=2.66 (d, J=

2.0 Hz, 1H), 4.31 (m, 2H), 5.23 (d, J=2.0 Hz, 1H), 6.31 (dt, J=6.0,

16 Hz, 1H), 6.65 (d, J=16 Hz, 1H), 7.21–7.55 ppm (m, 10H); ¹³C NMR:

d=68.8, 70.3, 75.6, 81.5, 125.2, 126.4, 127.2, 127.6, 128.3, 128.4, 133.1,

136.4, 138.0 ppm; elemental analysis calcd (%) for C₁₈H₁₆O: C 87.06, H,

6.49; found: C 86.76, H 6.59.

N-Phenyl-1-(4-methoxyphenyl)-2-propynylamine (6e): Yield 59%; a pale

yellow oil; ¹H NMR: d=2.45 (d, J=2 Hz, 1H), 3.78 (s, 3H), 3.90 (br,

1H), 5.22 (d, J=2 Hz, 1H), 6.71 (d, J=8 Hz, 2H), 6.77 (t, J=8 Hz, 1H),

6.90 (d, J=9 Hz, 2H), 7.20 (t, J=8 Hz, 2H), 7.50 ppm (d, J=8 Hz, 2H);

¹³C NMR: d=49.1, 55.2, 72.9, 83.1, 113.9, 114.0, 118.6, 128.4, 129.1, 131.0,

146.2, 159.4 ppm; IR (neat): n˜ =2114 (CꢁC), 3287 (ꢁCH), 3395 cm^ꢀ1

(NH); HRMS: m/z calcd for C₁₆H₁₅NO [M⁺]: 237.11536; found:

237.11618.

N-Phenyl-1-(1-naphthyl)-2-propynylamine (6 f): Yield 86%; a pale yellow

oil; ¹H NMR: d=2.49 (d, J=2 Hz, 1H), 4.08 (br, 1H), 5.88 (s, 1H), 6.72

(d, J=8 Hz, 2H), 6.78 (t, J=7 Hz, 1H), 7.19 (t, J=8 Hz, 2H), 7.42–7.48

(m, 3H), 7.79–7.85 (m, 2H), 7.94 (d, J=7 Hz, 1H), 8.05 ppm (m, 1H);

Data for 3s: Yield 87%; a pale yellow oil; ¹H NMR: d=1.87 (t, J=

2.4 Hz, 3H), 2.64 (d, J=2.4 Hz, 1H), 4.19–4.37 (m, 2H), 5.40 (d, J=

Chem. Eur. J. 2005, 11, 1433 – 1451

www.chemeurj.org

ꢀ 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

1447

Y. Nishibayashi, M. Hidai, S. Uemura et al.

¹³C NMR: d=47.3, 73.6, 82.6, 113.6, 118.5, 123.3, 125.3, 125.3, 125.9,

126.6, 128.8, 129.2, 129.2, 130.5, 133.6, 133.9, 146.2 ppm; IR (neat): n˜ =

2114 (CꢁC), 3289 (ꢁCH), 3397 cm^ꢀ1(NH); HRMS: m/z calcd for

C₁₉H₁₅N [M⁺] 257.12045; found: 257.12069.

3449 cm^ꢀ1(NH); elemental analysis calcd (%) for C₁₁H₁₁NO: C 76.28, H

6.40, N 8.09; found: C 76.66, H 6.36, N 7.70.

Data for 8b: Yield 62%; a white solid, m.p. 118.5–118.88C; ¹H NMR:

d=2.01 (s, 3H), 2.50 (d, J=2.0 Hz, 1H), 5.97 (dd, J=5.8, 2.0 Hz, 1H),

6.08 (d, J=5.8 Hz, 1H), 7.01 (t, J=5.8 Hz, 2H), 7.46 ppm (m, 2H);

¹³C NMR: d=23.2, 43.9, 73.2, 81.4, 115.5 (d, J=23 Hz), 128.8 (d, J=

8 Hz), 134.1, 164.9 ppm (d, J=256 Hz); elemental analysis calcd (%) for

C₁₁H₁₀FNO: C 69.10, H 5.27, N 7.33; found: C 69.23, H 5.27, N 7.36.

N-Phenyl-1-cyclohexyl-2-propynylamine (6g): Yield 71%; a yellow solid,

m.p. 75.5–76.58C; ¹H NMR: d=1.18–1.31 (m, 5H), 1.67–1.90 (m, 6H),

2.21 (d, J=2 Hz, 1H), 3.75 (brs, 1H), 3.94 (dd, J=5 and 2 Hz, 1H), 6.68

(d, J=8 Hz, 2H), 6.75 (t, J=8 Hz, 1H), 7.19 ppm (t, J=8 Hz, 2H);

¹³C NMR: d=25.8, 26.0, 26.2, 28.4, 29.7, 41.9, 51.0, 71.6, 83.4, 113.8,

118.2, 129.1, 146.7 ppm; IR (KBr): n˜ =2101 (CꢁC), 3260 (ꢁCH),

3384 cm^ꢀ1(NH); elemental analysis calcd (%) for C₁₅H₁₉N: C 84.46, H

8.98, N, 6.57; found: C 84.21, H 8.79, N 6.83.

Data for 8c: Yield 50%;

a pale yellow solid, m.p. 118.8–119.88C;

¹H NMR: d=2.03 (s, 3H), 2.51 (s, 1H), 6.00 (brs, 2H), 7.31 (d, J=

8.6 Hz, 2H), 7.43 ppm (d, J=8.6 Hz, 2H); ¹³C NMR: d=23.2, 43.9, 73.4,

81.2, 128.3, 128.7, 134.0, 136.7, 168.8 ppm; elemental analysis calcd (%)

for C₁₁H₁₁ClNO: C 63.62, H 4.85, N 6.75; found: C 63.45, H 4.91, N 6.55.

N-(2-Trifluoromethylphenyl)-1-phenyl-2-propynylamine (6h): Yield 68%;

a pale yellow oil; ¹H NMR: d=2.49 (d, J=2 Hz, 1H), 4.77 (s, 1H), 5.34

(s, 1H), 6.79 (t, J=8 Hz, 1H), 6.90 (d, J=8 Hz, 1H), 7.31–7.41 (m, 4H),

7.47 (d, J=8 Hz, 1H), 7.58 ppm (d, J=8 Hz, 2H); ¹³C NMR: d=49.3,

73.7, 82.1, 113.4, 114.5 (q, J=29 Hz), 117.4, 124.9 (q, J=271 Hz), 126.6

(q, J=5 Hz), 127.0, 128.4, 129.0, 133.0, 138.2, 143.7 ppm; IR (neat): n˜ =

2118 (CꢁC), 3297 (ꢁCH), 3465 cm^ꢀ1(NH); HRMS: m/z calcd for

C₁₆H₁₂F₃N [M⁺]: 275.09216; found: 275.09223.

Data for 8d: Yield 58%; a white solid, m.p. 98.8–99.98C; ¹H NMR: d=

1.96 (s, 3H), 2.32 (s, 3H), 2.45 (d, J=2.4 Hz, 1H), 5.90 (dd, J=8.6,

2.4 Hz, 1H), 6.54 (brd, J=8.6 Hz, 1H), 7.12 (d, J=7.8 Hz, 2H), 7.35 ppm

(d, 2H, J=7.8 Hz); ¹³C NMR: d=21.1, 23.0, 44.2, 72.6, 81.9, 126.7, 129.1,

135.2, 137.7, 168.8 ppm; elemental analysis calcd (%) for C₁₂H₁₃NO: C

76.98, H 7.00, N 7.48; found: C 76.70, H, 6.97, N, 7.36.

Data for 8e: Yield 70%;

a pale yellow solid, m.p. 129.8–130.28C;

¹H NMR: d=1.97 (s, 3H), 2.47 (d, J=2.2 Hz, 1H), 3.78 (s, 3H), 5.91 (dd,

J=6.2, 2.2 Hz, 1H), 6.47 (d, J=6.2 Hz, 1H), 6.84 (d, J=8.6 Hz, 2H),

7.39 ppm (d, J=8.6 Hz, 2H); ¹³C NMR: d=23.1, 43.9, 55.2, 72.6, 81.9,

113.8, 128.1, 130.3, 159.2, 168.8 ppm; elemental analysis calcd (%) for

C₁₂H₁₃NO₂: C 70.92, H 6.45, N 6.89; found: C 70.71, H 6.44, N 6.90.

Methyl 2-(1-phenyl-2-propynylamino)benzoate (6i): Yield 82%; a yellow

solid, m.p. 72.0–72.58C; H NMR: d=2.47 (d, J=2 Hz, 1H), 3.80 (s, 3H),

1

3.90 (brs, 1H), 5.36 (dd, J=6, 2 Hz, 1H), 6.66 (t, J=8 Hz, 1H), 6.82 (d,

J=9 Hz, 1H), 7.29–7.39 (m, 3H), 7.58 (d, J=8 Hz, 2H), 7.93 (dd, J=8,

2 Hz, 1H), 8.26 ppm (d, J=6 Hz, 1H); ¹³C NMR: d=48.6, 51.7, 73.1,

82.6, 111.1, 112.5, 116.0, 127.0, 128.2, 129.0, 131.6, 134.5, 138.6, 149.1,

168.9 ppm; IR (KBr): n˜ =2123 (CꢁC), 3266 (ꢁCH), 3360 cm^ꢀ1(NH);

HRMS: m/z calcd for C₁₇H₁₆NO₂[M⁺+H]: 266.11810; found: 266.11791.

1

Data for 8 f: Yield 42%; a white solid, m.p. 144.0–145.08C; H NMR: d=

1.99 (s, 3H), 2.53 (d, J=2.4 Hz, 1H), 6.13 (dd, J=8.6, 2.4 Hz, 1H), 6.49

(d, J=8.6 Hz, 1H), 7.44–7.53 (m, 3H), 7.77–7.82 (m, 3H), 7.96 ppm (m,

1H); ¹³C NMR: d=23.1, 44.6, 73.2, 81.6, 124.7, 125.8, 126.2, 127.5, 127.9,

128.5, 132.8, 132.9, 135.3, 168.9 ppm; elemental analysis calcd (%) for

C₁₅H₁₃NO: C 80.69, H 5.87, N 6.27; found: C 80.42, H 5.71, N 6.09.

Data for 8g: Yield 41%; a yellow solid, m.p. 142.0–143.48C; ¹H NMR:

d=1.90 (s, 3H), 2.33 (d, J=2.4 Hz, 1H), 5.23–5.30 (ddd, J=9.2, 7.3,

2.4 Hz, 1H), 5.96 (d, J=9.2 Hz, 1H), 6.23 (d, J=7.3 Hz, 1H), 7.19–

7.40 ppm (m, 10H); ¹³C NMR: d=23.1, 40.9, 71.5, 82.5, 124.3, 127.5,

127.7, 128.0, 128.2, 129.4, 138.1, 141.1, 144.6, 168.4 ppm; elemental analy-

sis calcd (%) for C₁₉H₁₇NO: C 82.88, H 6.22, N 5.09; found: C 82.63, H

6.40, N 4.99.

Data for 8h: Yield 72%; a yellow solid, m.p. 117.2–118.88C; ¹H NMR:

d=1.13 (d, J=7.2 Hz, 3H), 1.16 (d, J=7.2 Hz, 3H), 2.35 (sept, J=

7.2 Hz, 1H), 2.47 (d, J=2.2 Hz, 1H), 6.00 (dd, J=2.2, 8.4 Hz, 1H), 6.16

(d, J=8.4 Hz, 1H), 7.29–7.37 (m, 3H), 7.46 ppm (m, 2H); ¹³C NMR: d=

19.3, 19.5, 35.4, 44.2, 72.9, 81.8, 126.7, 127.9, 128.5, 138.3, 175.5 ppm; ele-

mental analysis calcd (%) for C₁₃H₁₅NO: C 77.58, H 7.51, N 6.96; found:

C 77.29, H 7.38, N 6.88.

N-(4-Nitrophenyl)-1-phenyl-2-propynylamine (6j): Yield 88%; a yellow

solid, m.p. 122.3–123.88C; ¹H NMR: d=2.55 (d, J=2 Hz, 1H), 4.99 (brs,

1H), 5.37 (s, 1H), 6.67 (d, J=9 Hz, 2H), 7.34–7.43 (m, 3H), 7.57 (d, J=

8 H, 2Hz), 8.07 ppm (d, J=9 Hz, 2H); IR (neat): n˜ =2116 (CꢁC), 3376

(ꢁCH), 3407 cm^ꢀ1(NH); elemental analysis calcd (%) for C₁₅H₁₂N₂O₂: C

71.42, H 4.79, N 11.10; found: C 70.99, H 4.86, N 10.91.

N-(4-Methylphenyl)-1-phenyl-2-propynylamine (6k): Yield 64%;

a

1

yellow oil; H NMR: d=2.24 (s, 3H), 2.44 (s, 1H), 3.81 (br, 1H), 5.24 (s,

1H), 6.64 (d, J=8 Hz, 2H), 7.01 (d, J=8 Hz, 2H), 7.29–7.38 (m, 3H),

7.59 ppm (d, J=8 Hz, 2H); ¹³C NMR: d=20.4, 50.1, 73.1, 83.0, 114.2,

127.2, 128.0, 128.1, 128.7, 129.6, 139.0, 143.8 ppm; IR (neat): n˜ =2112 (Cꢁ

C), 3289 (ꢁCH), 3403 cm^ꢀ1(NH); elemental analysis calcd (%) for

C₁₆H₁₅N: C 86.84, H 6.83, N 6.33; found: C 86.64, H, 6.58, N 6.03.

9-(1-Phenyl-2-propynyl)-9H-carbazole (6l): Yield 83%; a pale purple

1

solid, m.p. 97.6–98.78C; H NMR: d=2.54 (s, 1H), 6.74 (s, 1H), 7.18–7.21

(m, 5H), 7.30–7.38 (m, 6H), 8.06 ppm (d, J=8 Hz, 2H); ¹³C NMR: d=

48.7, 75.3, 79.0, 110.0, 119.6, 120.3, 123.5, 125.7, 126.4, 128.1, 128.6, 136.2,

139.4 ppm; IR (KBr): n˜ =2124 (CꢁC), 3289 cm^ꢀ1(ꢁCH); elemental anal-

ysis calcd (%) for C₂₁H₁₅N: C 89.65, H 5.37, N 4.98; found: C 89.35, H

5.40, N 5.00.

Data for 8i: Yield 56%;

a pale yellow solid, m.p. 145.5–147.18C;

¹H NMR: d=1.20 (m, 3H), 1.39 (m, 2H), 1.67–1.91 (m, 6H), 2.05–2.16

(m, 1H), 2.47 (s, 1H), 6.04 (br, 1H), 7.29 (m, 3H), 7.47 ppm (m, 2H);

¹³C NMR: d=25.7, 29.4, 29.6, 44.1, 45.2, 72.8, 81.9, 126.7, 128.0, 128.5,

138.4, 174.5 ppm; elemental analysis calcd (%) for C₁₆H₁₉NO: C 79.63, H

7.94, N 5.80; found: C 79.34, H, 7.87, N 5.72.

N-Methyl-N-phenyl-1-phenyl-2-propynylamine (6m): Yield 41%; a pale

1

yellow oil; H NMR: d=2.52 (d, J=2 Hz, 1H), 2.70 (s, 3H), 5.81 (s, 1H),

6.86 (t, J=8 Hz, 1H), 6.99 (d, J=8 Hz, 2H), 7.24–7.39 (m, 5H), 7.58 ppm

(d, 2H, J=8 Hz); ¹³C NMR: d=33.6, 56.3, 74.8, 79.9, 115.2, 118.9, 127.5,

127.8, 128.4, 129.2, 137.8, 150.0 ppm; IR (neat): n˜ =2110 (CꢁC),

3291 cm^ꢀ1(ꢁCH); HRMS: m/z calcd for C₁₆H₁₅N [M⁺]: 221.12045;

found: 221.12048.

1

Data for 8j: Yield 71%; a white solid, m.p. 103.4–104.18C; H NMR: d=

2.48 (d, J=2.4 Hz, 1H), 5.62 (dd, J=2.4, 10.2 Hz, 1H), 6.06 (dd, J=9.7,

17 Hz, 1H), 6.13 (d, J=9.7 Hz, 1H), 6.27 (d, J=17 Hz, 1H), 6.56 (d, J=

10.2 Hz, 1H), 7.28–7.37 (m, 3H), 7.47–7.51 ppm (m, 2H); ¹³C NMR: d=

44.5, 73.1, 81.5, 126.9, 127.4, 128.1, 128.6, 130.0, 137.9, 164.2 ppm; elemen-

tal analysis calcd (%) for C₁₂H₁₁NO: C 77.81, H 5.99, N 7.56; found: C

77.86, H 6.01, N 7.38.

Data for 8k: Yield 71%; a white solid; ¹H NMR: d=2.53 (d, J=2 Hz,

1H), 6.86 (dd, J=2, 8 Hz, 1H), 6.83 (d, J=8 Hz, 1H), 7.25–7.79 (m, 8H),

7.58 ppm (d, J=8 Hz, 2H); ¹³C NMR: d=44.5, 73.1, 81.5, 126.9, 127.4,

128.1, 128.6, 130.0, 137.9, 164.2 ppm; IR (neat): n˜ =2123 (CꢁC), 3279 (ꢁ

CH), 3326 cm^ꢀ1(NH); HRMS: m/z calcd for C₁₆H₁₄NO [M⁺+H]:

236.10754; found: 236.10770.

N-(4-Chlorophenyl)-1-phenyl-2-propynylamine: Yield 93%;

a yellow

solid; ¹H NMR: d=2.48 (d, J=2 Hz, 1H), 4.06 (br, 1H), 5.24 (d, J=

2 Hz, 1H), 6.64 (d, J=8 Hz, 2H), 7.12 (d, J=8 Hz, 2H), 7.37 (m, 3H),

7.57 ppm (d, J=8 Hz, 2H); ¹³C NMR: d=50.0, 73.4, 82.5, 115.1, 123.4,

127.1, 128.3, 128.8, 128.9, 138.4, 144.7 ppm; elemental analysis calcd (%)

for C₁₅H₁₂ClN: C 74.53, H 5.00, N 5.79; found: C 74.31, H 4.96, N 5.39.

N-(1-Phenyl-2-propynyl)acetamide (8a): Yield 79%; a white solid, m.p.

1

84.0–85.68C; H NMR: d=1.96 (s, 3H), 2.47 (d, J=2.2 Hz, 1H), 5.98 (dd,

1

J=8.7, 2.2 Hz, 1H), 6.75 (d, J=8.7 Hz, 1H), 7.27–7.36 (m, 3H), 7.58 ppm

(d, J=8.0 Hz, 2H); ¹³C NMR: d=22.9, 44.3, 72.8, 81.7, 126.9, 128.0,

128.6, 138.2, 169.1 ppm; IR (neat): n˜ =2114 (CꢁC), 3293 (ꢁCH),

Data for 8l: Yield 61%; a white solid, m.p. 138.8–139.98C; H NMR: d=

2.52 (d, J=2.2 Hz, 1H), 6.17 (dd, J=2.2, 8.1 Hz, 1H), 6.82 (d, J=8.1 Hz,

1H), 7.31 (m, 5H), 7.54 (d, J=6.2 Hz, 2H), 7.68 ppm (d, J=8.1 Hz, 2H);

1448

ꢀ 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

www.chemeurj.org

Chem. Eur. J. 2005, 11, 1433 – 1451

Ruthenium Catalysis

FULL PAPER

¹³C NMR: d=45.1, 73.4, 81.4, 127.0, 128.2, 128.5, 128.7, 131.8, 137.8,

137.9, 165.1 ppm; elemental analysis calcd (%) for C₁₆H₁₂ClNO: C 71.25,

H 4.48, N 5.19; found: C 71.22, H 4.67, N 4.96.

Data for 8m: Yield 67%; a white solid, m.p. 138.9–139.98C; ¹H NMR:

d=2.35 (s, 3H), 2.49 (d, J=2.4 Hz, 1H), 6.19 (dd, J=2.4, 8.6 Hz, 1H),

6.87 (d, J=8.4 Hz, 1H), 7.14 (d, J=7.8 Hz, 2H), 7.23–7.35 (m, 3H), 7.53

(d, J=6.2 Hz, 2H), 7.65 ppm (d, J=7.8 Hz, 2H); ¹³C NMR: d=21.4,

44.8, 73.1, 81.7, 126.9, 127.0, 128.0, 128.5, 129.0, 130.6, 138.1, 142.0,

166.0 ppm; elemental analysis calcd (%) for C₁₇H₁₅NO: C 81.90, H 6.06,

N 5.62; found: C 81.88, H 6.15, N 5.41.

1H), 6.99–7.12 (m, 4H), 7.41–7.56 (m, 6H), 7.73–7.85 ppm (m, 4H); ele-

mental analysis calcd (%) for C₂₂H₁₉P: C 79.98, H 5.80; found: C 79.85,

H 5.69.

Data for 10e: Yield 78%; a white solid, m.p. 160.0–160.88C; ¹H NMR:

d=2.22 (s, 3H), 2.40 (dd, J=2.7, 5.6 Hz, 1H), 4.60 (dd, J=2.7, 18.5 Hz,

1H), 6.98–7.10 (m, 4H), 7.37–7.56 (m, 6H), 7.72–7.85 ppm (m, 4H); ele-

mental analysis calcd (%) for C₂₂H₁₉OP: C 79.98; H 5.80; found: C 79.95,

H 5.77.

Data for 10 f: Yield 87%; a brownish white solid, m.p. 182.4–184.18C;

¹H NMR: d=2.14 (s, 3H), 2.31 (dd, J=2.7, 5.6 Hz, 1H), 4.88 (dd, J=2.7,

17.1 Hz, 1H), 7.04–7.16 (m, 3H), 7.26–7.29 (m, 1H), 7.34–7.51 (m, 3H),

7.56–7.70 (m, 3H), 7.81–7.88 ppm (m, 4H); elemental analysis calcd (%)

for C₂₂H₁₉OP: C 79.98, H 5.80; found: C 80.25, H 5.79.

1

Data for 8n: Yield 64%; a pale yellow oil; H NMR: d=2.61 and 2.69 (s

each, 1H), 2.78 and 2.89 (s each, 3H), 5.87 (brs, 1H), 7.03–7.61 ppm (m,

10H); GCMS: m/z (%): 249 (20) [M⁺], 248 (28) [M⁺ꢀ1], 220 (15), 144

(14), 118 (47), 115 (55) [PhCHCCH⁺], 105 (100) [PhCO⁺], 89 (9), 77

(84) [Ph⁺]; IR (neat): n˜ =1636 (C=O), 2116 (CꢁC), 3289 cm^ꢀ1(ꢁCH); el-

emental analysis calcd (%) for C₁₇H₁₅NO: C 81.90, H 6.06, N, 5.62;

found: C 82.27, H 6.13, N 5.64.

Data for 10g: Yield 88%; a pale yellow solid, m.p. 170.6–171.68C;

¹H NMR: d=2.39 (dd, J=2.6, 5.4 Hz, 1H), 3.74 (s, 3H), 4.60 (dd, J=2.6,

18.5 Hz, 1H), 6.73–6.80 (m, 2H), 7.12 (d, J=7.0 Hz, 2H), 7.41–7.57 (m,

6H), 7.73–7.84 ppm (m, 4H); elemental analysis calcd (%) for

C₂₂H₁₉O₂P: C 76.29, H 5.53; found: C 76.12, H 5.56.

1

Data for 8o: Yield 64%; a yellow oil; H NMR: d=2.15 (s, 3H), 2.53 (d,

Data for 10h: Yield 90%; a white solid, m.p. 153.8–154.68C. ¹H NMR:

d=2.46 (dd, J=2.7, 5.4 Hz, 1H), 4.77–4.85 (dd, J=2.7, 18.9 Hz, 1H),

7.41–7.46 (m, 8H), 7.67–7.82 ppm (m, 9H); HRMS: m/z calcd for

C₂₅H₁₉OP [M⁺]: 366.1174; found: 366.1169.

J=2.7 Hz, 1H), 2.82 (s, 3H), 6.91 (d, J=2.7 Hz, 1H), 7.27–7.39 (m, 3H),

7.42–7.48 ppm (m, 2H); ¹³C NMR: d=21.8, 31.1, 48.1, 74.3, 79.6, 127.2,

128.3, 128.6, 136.2, 170.1 ppm; HRMS: m/z calcd for C₁₂H₁₃NO [M⁺]:

187.0997; found: 187.0999.

Data for 8p: Yield 63%; a white solid, m.p. 78.2–78.88C; ¹H NMR: d=

2.65 (d, J=2.2 Hz, 1H), 2.98 (s, 3H), 5.27 (d, J=2.2 H, 1Hz), 5.27 (dd,

J=2.2, 8.4 Hz, 1H), 7.31–7.39 (m, 3H), 7.51 ppm (m, 2H); ¹³C NMR: d=

41.5, 48.8, 75.2, 80.9, 127.1, 128.5, 128.7, 136.5 ppm; elemental analysis

calcd (%) for C₁₀H₁₁NO₂S: C 57.39, H 5.30, N 6.69; found: C 57.44, H

5.35, N 6.58.

Data for 8q: Yield 52%; a white solid, m.p. 131.0–132.08C; ¹H NMR:

d=2.29 (s, 1H), 2.40 (s, 3H), 5.30 (brs, 2H), 7.23–7.27 (m, 5H), 7.42 (d,

J=8.1 Hz, 2H), 7.74 ppm (d, J=8.1 Hz, 2H); ¹³C NMR: d=21.5, 48.8,

74.7, 80.3, 127.1, 127.3, 128.4, 128.6, 129.4, 136.9, 137.1, 143.5 ppm; ele-

mental analysis calcd (%) for C₁₆H₁₅NO₂S: C 67.34, H 5.30; found: C

67.07, H 5.25.

Data for 8r: Yield 78%; a yellow oil; ¹H NMR: d=2.58 (d, J=2.4 Hz,

1H), 2.88–3.37 (m, 4H), 5.86 (d, J=2.4 Hz, 1H), 7.27–7.48 ppm (m, 5H);

¹³C NMR: d=36.1, 36.2, 46.7, 74.4, 78.3, 127.0, 128.1, 128.5, 135.4,

166.3 ppm; HRMS: m/z calcd for C₁₂H₁₂NO [M⁺+H]: 186.0919; found:

186.0921.

Data for 8s: Yield 74%; a yellow oil; ¹H NMR: d=1.86–2.03 (m, 2H),

2.40–2.46 (m, 2H), 2.55 (d, J=2.2 Hz, 1H), 3.05 (m, 1H), 3.55 (m, 1H),

6.31 (d, J=2.2 Hz, 1H), 7.28–7.38 (m, 3H), 7.46 ppm (d, J=6.2 Hz, 2H);

¹³C NMR: d=20.4, 21.7, 30.9, 41.4, 68.7, 76.1, 126.8, 127.4, 127.7, 127.8,

172.2 ppm; HRMS: m/z calcd for C₁₃H₁₃NO [M⁺]: 199.0997; found:

199.0998.

Data for 8t: Yield 18%; a yellow oil; ¹H NMR: d=1.67–1.79 (m, 4H),

2.47 (m, 3H), 2.84 (m, 1H), 3.43 (m, 1H), 7.02 (s, 1H), 7.29–7.37 (m,

3H), 7.47 ppm (d, J=6.5 Hz, 2H); ¹³C NMR: d=21.2, 23.1, 32.5, 42.5,

47.8, 74.3, 79.6, 127.4, 127.8, 128.4, 136.2, 169.2 ppm; HRMS: m/z calcd

for C₁₄H₁₅NO [M⁺]: 213.1154; found: 213.1151.

Data for 10a: Yield 84%; a white solid, m.p. 145.6–146.88C; ¹H NMR:

d=2.42 (dd, J=3.0, 6.0 Hz, 1H), 4.65 (dd, J=3.0, 18 Hz, 1H), 7.18–

7.84 ppm (m, 15H); ³¹P NMR: d=29.9 ppm; IR (neat): n˜ =1191 (P=O),

2116 (CꢁC), 3295 cm^ꢀ1(ꢁCH); HRMS: m/z calcd for C₂₁H₁₈OP [M⁺

+H]: 317.1094; found: 317.1087.

Data for 10b: Yield 81%; a white solid, m.p. 154.8–156.48C; ¹H NMR:

d=2.42 (dd, J=2.6, 6.0 Hz, 1H), 4.59 (dd, J=2.6, 18.6 Hz, 1H), 6.86 (t,

J=8.6 Hz, 2H), 7.18–7.25 (m, 2H), 7.43–7.25 (m, 6H), 7.73–7.83 ppm (m,

4H); elemental analysis calcd (%) for C₂₁H₁₆FOP: C 75.44, H 4.82;

found: C 75.04, H 4.85.

Data for 10c: Yield 74%; a white solid, m.p. 150.2–151.88C; ¹H NMR:

d=2.42 (dd, J=2.6, 5.4 Hz, 1H), 4.6 (dd, J=2.6, 19.2 Hz, 1H), 7.16 (s,

4H), 7.41–7.55 (m, 6H), 7.74–7.82 ppm (m, 4H); elemental analysis calcd

(%) for C₂₁H₁₆ClOP: C 71.90, H 4.60; found: C 72.05, H 4.64.

1

Data for 10i: Yield 67%; a yellow viscous oil; H NMR: d=2.28 (dd, J=

5.4, 2.7 Hz, 1H), 4.17–4.27 (dd, J=2.7, 18 Hz, 1H), 6.13 (dd, J=6.9,

18 Hz, 1H), 6.96–7.85 ppm (m, 20H); HRMS: m/z calcd for C₂₉H₂₃OP

[M⁺]: 418.1487; found: 418.1489.

Data for 10j: Yield 90%; a white solid, m.p. 198.2–199.88C; ¹H NMR:

d=2.91 (dd, J=1.0, 5.4 Hz, 1H), 7.14–7.27 (m, 10H), 7.36–7.41 (m, 2H),

7.65–7.78 ppm (m, 8H); elemental analysis calcd (%) for C₂₇H₂₁OP: C

82.64, H 5.39; found: C 82.34, H 5.46.

1

Data for 10k: Yield 96%; a white solid, m.p. >2508C; H NMR: d=2.27

(s, 6H), 2.85 (dd, J=1.0, 5.4 Hz, 1H), 7.00 (d, J=8.4 Hz, 4H), 7.24–7.31

(m, 4H), 7.40–7.45 (m, 2H), 7.59 (d, J=8.4 Hz, 4H), 7.67–7.73 ppm (m,

4H); HRMS: m/z calcd for C₂₉H₂₆OP [M⁺+H]: 421.1721; found:

421.1705.

Preparation

of

[(Cp*)RuCl(m₂-SMe)₂Ru(Cp*)(C=C=C(p-tol)₂)]BF₄·

CH₂Cl₂(11a·CH₂Cl₂):^[15]Compound 1a (144 mg, 0.20 mmol) and NH₄BF₄

(22 mg, 0.20 mmol) were placed in a 20 mL flask under N₂. Anhydrous

EtOH (10 mL) was added, and then the mixture was magnetically stirred

at room temperature. After the addition of 2 f (47 mg, 0.20 mmol), the re-

action flask was kept at room temperature for 1 h. A purple solid precipi-

tated was filtered off, washed with n-hexane, and recrystallized from

CH₂Cl₂/n-hexane

to

give

black

crystals

of

11a·CH₂Cl₂

(167 mg,0.168 mmol, 84%); ¹H NMR: d=1.66 (s, 15H), 1.84 (s, 15H),

2.33 (s, 6H), 2.66 (s, 6H), 7.19 (d, J=7.6 Hz, 4H), 7.51 ppm (d, J=

7.6 Hz, 4H); ¹³C NMR: d=10.4, 10.7, 19.6, 22.0, 98.8, 104.5, 129.9, 132.1,

140.4, 144.5, 162.2, 182.6, 296.6 ppm. IR (KBr): n˜ =1946 cm^ꢀ1(C=C=C);

elemental analysis calcd (%) for C₃₉H₅₀BClF₄Ru₂S₂·CH₂Cl₂: C 48.42, H

5.28; found: C 48.29, H 5.31.

Preparation of [(Cp*)RuCl(m₂-SMe)₂Ru(Cp*)(=C=C=CHPh)]BF₄(11b):

A typical experimental procedure for the preparation of [(Cp*)RuCl(m₂-

SMe)₂Ru(Cp*)(C=C=CHPh)]BF₄(11b) is described below. Comopund

1a (510 mg, 0.80 mmol), NH₄BF₄(109 mg, 1.04 mmol), and MgSO₄(1 g)

were placed in a 200 mL flask under N₂. Anhydrous THF (100 mL) was

added, and then the mixture was magnetically stirred at room tempera-

ture. After the addition of 2a (219 mg, 1.66 mmol), the reaction flask was

kept at room temperature for 30 min. Then, the solvent was removed

under reduced pressure, and the residue was recrystallized from CH₂Cl₂/

diethyl ether to give black crystals of 11b (378 mg, 0.467 mmol, 58%).

¹H NMR: d=1.66 (s, 15H), 1.85 (s, 15H), 2.73 (s, 6H), 7.39 (t, J=7.5 Hz,

2H), 7.66 (t, J=7.5 Hz, 1H), 7.72 (d, J=7.5 Hz, 2H) 8.89 ppm (s, 1H);

¹³C NMR: d=10.4, 10.6, 20.1, 99.4, 105.6, 130.2, 132.4, 134.0, 142.6, 151.2,

198.0, 319.7 ppm; IR (KBr): n˜ =1945 cm^ꢀ1(C=C=C); elemental analysis

calcd (%) for C₃₁H₄₂BClF₄Ru₂S₂: C 46.36, H 5.27; found: C 46.00, H 5.15.

X-ray crystallographic data: CCDC 247325 (8j), CCDC 247326 (8q),

CCDC 247327 (10a) and CCDC 247328 (10b) contain the supplementary

crystallographic data for this paper. These data can be obtained free of

Data for 10d: Yield 84%; a white solid, m.p. 148.9–150.68C; ¹H NMR:

d=2.28 (s, 3H), 2.39 (dd, J=2.7, 5.6 Hz, 1H), 4.60 (dd, J=2.7, 18.8 Hz,

Chem. Eur. J. 2005, 11, 1433 – 1451

www.chemeurj.org

ꢀ 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

1449

Y. Nishibayashi, M. Hidai, S. Uemura et al.

Figure 3. ORTEP drawings of 8j (top left), 8q (top right), 10a (bottom left), and 10b (bottom right) with 50% probability ellipsoids.

charge from The Cambridge Crystallographic Data Centre via

www.ccdc.cam.ac.uk/data_request/cif. ORTEP drawings of 8j, 8q, 10a,

and 10b are shown in Figure 3.

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Acknowledgment

This work was supported by a Grant-in-Aid for Scientific Research for

Young Scientists (A) (No. 15685006) from the Ministry of Education,

Culture, Sports, Science and Technology, Japan. Y.I. is a recipient of a

JSPS Predoctoral Fellowship for Young Scientists.

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Received: August 8, 2004

Published online: January 13, 2005

Chem. Eur. J. 2005, 11, 1433 – 1451

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ꢀ 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

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Article Doi

Ruthenium-catalyzed propargylic substitution reactions of propargylic alcohols with oxygen-, nitrogen-, and phosphorus-centered nucleophiles

DOI: 10.1002/chem.200400833

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