Ruthenium complexes of electronically coupled cyclopentadienone ligands - Catalysts for transformations of propargyl alcohols

Article abstract of DOI:10.1002/ejoc.200700064

A series of donor- and acceptor-substituted ruthenium cyclopentadienone complexes were synthesized and their catalytic activities towards propargyl alcohols focused on amination reactions have been investigated. It is shown that the substituents of the cyclopentadienone ligand determine the mode of activation of propargyl alcohols by these complexes leading to different central intermediates in catalytic cycles. Catalytic transformations of propargyl alcohols to α- or β-amino ketones, enamino ketones, α,β-unsaturated imines, ketones, alkenes and conjugated enynes could be achieved. Wiley-VCH Verlag GmbH & Co. KGaA, 2007.

Full text of DOI:10.1002/ejoc.200700064

FULL PAPER
DOI: 10.1002/ejoc.200700064
Ruthenium Complexes of Electronically Coupled Cyclopentadienone Ligands –
Catalysts for Transformations of Propargyl Alcohols
Edgar Haak*[a]
Keywords: Homogeneous catalysis / Propargyl alcohols / Ruthenium / Vinylidene complexes / Synthetic methods
A series of donor- and acceptor-substituted ruthenium cyclo-
pentadienone complexes were synthesized and their cata-
lytic activities towards propargyl alcohols focused on amin-
ation reactions have been investigated. It is shown that the
substituents of the cyclopentadienone ligand determine the
mode of activation of propargyl alcohols by these complexes
leading to different central intermediates in catalytic cycles.
Catalytic transformations of propargyl alcohols to α- or β-
amino ketones, enamino ketones, α,β-unsaturated imines,
ketones, alkenes and conjugated enynes could be achieved.
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2007)
Introduction
Results and Discussion
In the course of the investigation of ruthenium-catalyzed
amination reactions of propargyl alcohols, complexes of
type 2 were recently found to be active in enamino ketone
formation (Scheme 2, Table 1).[10]
Ruthenium complexes of electronically coupled cyclo-
pentadienone ligands catalyze a brought range of homogen-
eous hydrogen transfer reactions such as disproportionation
of aldehydes to esters,[1] reduction of aldehydes and
ketones,[2] Oppenauer type oxidations of alcohols and
amines,[3,4] racemisation of alcohols and amines[5,6] and the
oxidation of alcohols without hydrogen acceptor.[7] The
Shov complex [{(η5-Ph4C4CO)2H}Ru2(CO)4(µ-H)] repre-
sents the most famous catalyst of this type.[8] Cyclopen-
tadienone ruthenium(0) species like complex 1 that are also
accessible from monomeric complexes of type 2 act as the
catalytically active species in the oxidation step
(Scheme 1).[9]
Scheme 2. Ruthenium-catalyzed enamino ketone formation.
Table 1. Enamino ketone formation from various substrates.
Amines
R
RЈ
E/Z
Yield of 3 [%]
Aniline
Aniline
Aniline
Pyrrolidine
-Proline methyl ester
Allylamine
Benzhydrylamine
Benzylamine
(R)-α-Methylbenzylamine
(R)-1-Cyclohexylethylamine
Tryptamine
-Tryptophan methyl ester
-Alanine methyl ester
Ph
Me
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
H
H
Me
H
H
H
H
H
H
H
H
H
H
Z
Z
Z
E
E
Z
Z
Z
Z
Z
Z
Z
Z
49[a] (3a)
47[a] (3b)
52[a] (3c)
48[b] (3d)
65[b] (3e)
53[b] (3f)
39[b] (3h)
25[b] (3i)
14[b] (3j)
20[b] (3k)
11[b] (3l)
17[b] (3m)
16[b] (3n)
Scheme 1. Formation of coordinative unsaturated species 1.
Due to the electronic coupling of the dienone ligand and
its basic coordination site this type of complexes could pro-
vide unique features towards catalytic transformations of
various substrates.
[a] Reactions were stopped after 5 h. [b] Reactions were stopped
after 8 h.
[a] University of Braunschweig, Department of Organic Chemistry,
Hagenring 30, 38106 Braunschweig, Germany
Fax: +49-531-3915388
The reactivity of internal propargyl alcohols and the fact
that tertiary propargyl alcohols are not converted exclude
E-mail: e.haak@tu-bs.de
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E. Haak
FULL PAPER
the initial formation of vinylidene or allenylidene species by
activation of the alkyne terminus. Interestingly, the investi-
gation of the stoichiometrical reaction of 1-phenyl-2-pro-
pyn-1-ol with 2a in the presence of DBU by NMR spec-
troscopy supports the assumption of the formation of
alkenyl complex 4 (Scheme 3, Table 2).
Scheme 3. Formation of a stabilized alkenyl complex.
Table 2. NMR shift data (δ values, ppm) of alkenyl complex 4.
Figure 1. New ruthenium complexes of electronically coupled li-
gands.
13C-NMR (50 MHz)
1H-NMR (200 MHz)
Ca
Cb
Cc
Cd
Ce
Cf
183.0
125.7
197.6
166.0
85.8
103.6
204.5
Hb
Hc
JHbHc
O–H
8.34
9.84
16.0 Hz
12.50
The ruthenium carbonyl complexes were directly ob-
tained from the dienone ligands and Ru3(CO)12. The dien-
ones 5L,[11a] 6aL and 6bL[11b] have already been published
by other groups and the dienones 6cL, 6dL, 7cL and 7dL
were synthesized according to these procedures under iden-
tical conditions. Since dienone 6cL exhibits C-nucleophilic-
CO
The catalytic enamino ketone formation is probably initi- ity the dienones 7aL, 8aL, 8bL and 8cL could be obtained
ated by base-catalyzed formation of a ruthenium alkenyl by acylation or amidation of 6cL (Scheme 5).
complex. Subsequent Michael addition of the amine and
The new complexes show interesting catalytic activities
β-H elimination give rise to the observed product and a towards propargyl alcohols. By reacting 1-phenyl-2-propyn-
ruthenium(II) hydride which regenerates the active catalyst 1-ol with aniline in the presence of 3 mol-% of one of the
with elimination of hydrogen (Scheme 4).
new complexes the α- and β-amino ketone as well as benzyl-
By variation of the substituents of the dienone fragment idene aniline are formed besides the enamino ketone in dif-
a broad range of new donor- and acceptor-substituted cy- ferent ratios. By using complexes of type 6 as catalysts the
clopentadienone complexes has been generated (Figure 1).
saturated product 9 dominates compared to the unsaturated
Scheme 4. Postulated catalytic cycle of the enamino ketone formation.
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Catalysts for Transformations of Propargyl Alcohols
FULL PAPER
Table 3. Product distributions (%) for catalysts 5–8.[a]
Catalyst
Product 3a Product 9 Product 10 Product 11
5
14
7
18
9
11
13
17
14
4
Ͻ 3
15
24
59
19
9
11
4
Ͻ 3
4
29
21
30
20
28
19
30
29
31
35
26
21
Ͻ 3
Ͻ 3
10
7
6a
6b
6c
6d
7a[b]
7b
7c
7d
8a
8b
8c
8
12
10
11
15
40
31
10
5
Ͻ 3
16
Ͻ 3
9
[a] Reactions were stopped after 5 h. [b] 9% 3-(phenylallyliden)-
aniline (12) as additional product.
The reaction catalyzed by complexes of type 6–8 needs
to proceed by a different mechanism than that catalyzed by
complexes of type 2. The internal propargyl alcohol 1-
phenyl-2-butyn-1-ol shows no reactivity and the tertiary
propargyl alcohol 1,1-diphenyl-2-propyn-1-ol is trans-
formed to a mixture of bezophenone and 1,1-diphenyle-
thane in the presence of a catalytic amount of one of the
complexes 6–8 in presence as well as in absence of the
amine. The highest activity regarding this fragmentation is
observed with complex 8a. If a catalytic amount of a strong
basic amine like pyrrolidine or DBU is added instead of
aniline the enyne 13 is formed as major product (Scheme 7).
In the absence of an amine the catalytic fragmentations are
also observed with the secondary propargyl alcohol 1-
phenyl-2-propyn-1-ol forming benzaldehyde and styrene.
Scheme 5. Synthesis of the ligands 6L–8L.
product 3a, whereas the asymmetric complex 6c shows the
highest activity. When the acceptor-substituted complex 5
or the donor/acceptor-substituted complexes 7a–c or 8c are
used as catalysts the unsattured product 3a is formed pref-
erentially. If the reaction is catalyzed by complex 7a, 3-
(phenylallyliden)aniline (12) is formed as an additional by-
product (9%). The hydrogen-bridged complexes 8a+b lead
to the formation of the imine 11 as major product. The
Markownikow hydroamination product 10 is formed in all
cases in 19–35% yield (Scheme 6, Table 3).
Scheme 7. Reactivity of a tertiary propargyl alcohol.
It is very likely that the initial formation of a ruthenium
γ-hydroxyvinylidene complex (V) occurs in all cases. Its fur-
ther transformation depends on the reaction partner and
the catalyst used. 1,3-Hydride shift leads to enamino
ketones or β-amino ketones by the formation of an alkenyl
species in analogy to complex 4, whereas the product ratio
is depending on the ratio of reductive elimination vs. β-hy-
dride elimination (pathway A, Scheme 8). Fragmentation to
the alkyne complex by elimination of an aldehyde or ketone
leads to regeneration of the active catalyst by elimination
of acetylene (pathway B, Scheme 8). Generation of the al-
kene can be rationalized by the formation of an allenylidene
complex which is attacked in α-position by the initially
Scheme 6. Catalytic activities of complexes 5–8.
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E. Haak
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Scheme 8. Postulated mechanisms of the observed product formation.
Scheme 9. Catalytic formation of α,β-unsaturated imines.
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Catalysts for Transformations of Propargyl Alcohols
FULL PAPER
eliminated water. The resulting acyl complex generates the
decarbonylated product under reformation of the tricar-
bonyl complex (pathway C, Scheme 8). The alternative at-
tack of the amine on an allenylidene species or on vinyl-
idene complex V combined with a following elimination of
water leads to an azadiene complex. The latter regenerates
the active catalyst by reductive elimination of the α,β-unsat-
urated imine (pathway D, Scheme 8). In case of the enyne
formation a second equivalent of the propargyl alcohol acts
as nucleophile. The resulting not donor-stabilized complex
undergoes reductive elimination (pathway E, Scheme 8).
It is well known that propargyl alcohols form allenylid-
ene species with ruthenium(II) complexes under acidic con-
ditions by elimination of water.[12] In fact, the tertiary pro-
pargyl acetate 14 generates with aniline the α,β-unsaturated
imine 15 in the presence of a catalytic amount of 6c. The
yield can be increased by adding 6 mol-% of NH4PF6. A
Experimental Section
All reactions were carried out in a dry atmosphere under argon by
using standard Schlenck techniques. The chemicals used were dried
and purified according to common procedures. Products were iden-
tified by spectroscopic analysis (1H NMR, 13C NMR, IR, MS,
HRMS).
General Catalytic Procedure: 1 mmol of the propargyl alcohol and
1 mmol of the amine or amine equivalent were dissolved in 0.5 mL
of toluene and 0.03 mmol of the catalyst were added. The mixture
was stirred at 100 °C for 5–8 hours under argon. Using allylamine
the reaction was performed in a closed tube. Evaporation of the
solvent and chromatography on silica furnished the detected prod-
ucts.
Z-3a (C15H13NO): 110 mg (49%) yellow crystals. 1H NMR
(400 MHz, CDCl3): δ = 5.94 (d, J = 7.8 Hz, 1 H), 6.99 (t, J =
7.4 Hz, 1 H), 7.01 (d, J = 7.7 Hz, 2 H), 7.25 (dd, J = 8.6, 7.4 Hz,
2 H), 7.33–7.45 (m, 4 H), 7.86 (d, J = 6.7 Hz, 2 H), 12.07 (br. d, J
similar result is observed if the secondary propargyl alcohol = 11.4 Hz, 1 H, NH) ppm. 13C NMR (100 MHz, DEPT, CDCl3):
δ = 93.7 (CH), 116.3 (CH), 123.7 (CH), 127.3 (CH), 128.4 (CH),
129.7 (CH), 131.5 (CH), 139.2 (C), 140.2 (C), 144.9 (CH), 191.0
1-phenyl-2-propyn-1-ol is treated with phenyl or naphthyl
isocyanate as amine equivalent. Using 3 mol-% 6c the α,β-
unsaturated imines 12 and 16 are obtained in moderate
yields (Scheme 9). A plausible mechanism starts again from
the initial formation of a vinylidene species that is attacked
in α-position. Using an isocyanate that forms a carbamate
with the propargyl alcohol this nucleophilic attack occurs
intra molecularly. After elimination of the leaving group in
β-position the α,β-unsaturated system is reductively elimin-
ated (Scheme 9).
(C) ppm. IR: ν = 3053, 2957, 2923, 2854, 1626, 1593, 1579, 1549,
˜
1511, 1493, 1471, 1449, 1356, 1288, 1236, 1215, 1177, 1154, 1074,
1038, 1017, 976, 888, 786, 741, 708, 686 cm–1. MS (EI): m/z (%) =
223 (52) [M+], 222 (100), 146 (28), 118 (11), 105 (11), 77 (28).
Z-3b (C10H11NO): 76 mg (47%) colourless oil. 1H NMR
(400 MHz, CDCl3): δ = 2.16 (s, 3 H), 5.20 (d, J = 6.6 Hz, 1 H),
7.02 (d, J = 7.6 Hz, 2 H), 7.16 (t, J = 7.4 Hz, 1 H), 7.23 (dd, J =
12.0, 4.3 Hz, 1 H), 7.31 (t, J = 7.5 Hz, 2 H), 11.60 (br. s, 1 H, NH)
ppm. 13C NMR (100 MHz, DEPT, CDCl3): δ = 29.5 (CH3), 97.4
(CH), 116.1 (CH), 123.4 (CH), 129.6 (CH), 140.4 (C), 143.0 (CH),
198.9 (C) ppm. IR: ν = 3252, 3038, 2962, 2925, 2869, 1640, 1596,
˜
1567, 1477, 1451, 1356, 1271, 1219, 1199, 1178, 1157, 1075, 1024,
Conclusions
968, 912, 745, 690, 558. MS (EI): m/z (%) = 161 (60) [M+], 146
The ligand system used provides a broad range of pos- (100), 118 (32), 91 (22), 77 (32). HRMS: calcd. 161.08406, found:
161.08404.
sible variations. Basicity of the carbonyl group and the de-
gree of electronic coupling can be regulated by the donor-
and acceptor-substituents. Donor substituents in 3 and 4
position strongly influences the electron density of the
Z-3c (C16H15NO): 123 mg (52%) yellow crystals. 1H NMR
(400 MHz, CDCl3): δ = 2.13 (s, 3 H), 5.89 (s, 1 H), 7.14 (dd, J =
7.4, 8.4 Hz, 1 H), 7.17 (d, J = 7.5 Hz, 2 H), (dd, J = 8.6, 7.4 Hz, 2
metal centre and its mode of action while acceptor substitu- H), 7.42–7.45 (m, 3 H), 7.92 (dd, J = 7.8, 2.0 Hz, 2 H), 13.11 (br.
s, 1 H, NH) ppm. 13C NMR (100 MHz, DEPT, CDCl3): δ = 20.1
(CH3), 93.9 (CH), 124.4 (CH), 125.4 (CH), 126.7 (CH), 127.9 (CH),
128.8 (CH), 130.5 (CH), 138.3 (C), 139.6 (C), 161.8 (C), 188.3 (C)
ents in 2 and 5 position allow the formation of stabilizing
hydrogen bridges after oxidative addition of protic nucleo-
philes. The donor groups in the side chains of complexes 6d
ppm. IR: ν = 3093, 3057, 3035, 1586, 1544, 1519, 1494, 1431, 1377,
˜
and 7b could lead to interactions with the metal centre or
with metal bonded substrates in intermediates of a catalytic
cycle. Finally the chiral complexes 6c, 7a–c and 8a–c repre-
sent interesting motives regarding applications in asymmet-
ric catalysis.
It could be shown that carbonyl(3,4-diaminocyclopen-
tadienone)ruthenium complexes activate the alkyne ter-
minus of propargyl alcohols leading very likely to the for-
mation of (γ-hydroxyvinylidene)ruthenium complexes
whereas 3,4-diphenyl-substituted analogues complexes acti-
vate the π-system of the triple bond forming alkenyl com-
1316, 1281, 1228, 1193, 1167, 1067, 1023, 853, 807, 748, 692, 557.
MS (EI): m/z (%) = 237 (41) [M+], 236 (100), 160 (28), 132 (43),
105 (44), 77 (57). HRMS: calcd. 237.11536, found: 237.11585.
E-3d (C13H15NO): 96 mg (48%) yellow oil. 1H NMR (300 MHz,
CDCl3): δ = 1.81–2.00 (m, 4 H), 3.33–3.46 (m, 4 H), 5.65 (d, J =
12.6 Hz, 1 H), 7.24–7.35 (m, 3 H), 7.81 (dd, J = 8.1, 1.9 Hz, 2 H),
7.92 (d, J = 12.4 Hz, 1 H) ppm. 13C NMR (75 MHz, DEPT,
CDCl3): δ = 25.1 (CH2), 47.0 + 52.3 (CH2), 93.0 (CH), 127.4 (CH),
128.0 (CH), 130.1 (CH), 140.5 (C), 150.0 (CH), 188.5 (C) ppm. IR:
ν = 3060, 2954, 2926, 2874, 1632, 1581, 1542, 1450, 1364, 1341,
˜
1300, 1267, 1245, 1220, 1178, 1142, 1052, 1026, 837, 761, 746, 693,
plexes. These different modes of activation allow several 618, 596, 558, 536 cm–1. MS (EI): m/z (%) = 201 (100) [M+], 172
(58), 131 (24), 124 (32), 105 (60), 96 (58), 77 (70), 70 (82). HRMS:
calcd. 201.11536, found: 201.11492.
catalytic transformations of propargyl alcohols. Further in-
vestigation of catalytic activities, development of broad-
ranged catalytic processes and separation of the enantio-
mers of the chiral complexes are subjects of the actual re-
search.
E-3e (C15H17NO3): 169 mg (65%) yellow oil (rotamers 4:1). 1H
NMR (300 MHz, CDCl3): δ = 1.90–2.34 (m, 4 H), 3.50–3.55 (m, 2
H), 3.75 (s, 3 H), 4.16 + 4.29 (t, J = 8.1 Hz, 1 H), 5.67 + 5.77 (d,
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E. Haak
FULL PAPER
J = 12.4 Hz, 1 H), 7.37–7.46 (m, 3 H), 7.87–8.01 (m, 3 H) ppm.
H, NH) ppm. 13C NMR (100 MHz, DEPT, CDCl3): δ = 23.7
13C NMR (75 MHz, DEPT, CDCl3): δ = 23.2 + 25.1 (CH2), 27.5 (CH3), 57.8 (CH), 90.7 (CH), 126.1 (CH), 127.1 (CH), 127.6 (CH),
+ 29.7 (CH2), 45.1 + 46.0 (CH2), 52.5 (CH3), 60.4 + 60.9 (CH),
92.9 + 94.8 (CH), 127.4 + 127.5 (CH), 127.9 + 128.0 (CH), 130.6
+ 131.0 (CH), 140.0 + 140.5 (C), 149.3 + 149.8 (CH), 166.3 +
128.2 (CH), 128.9 (CH), 130.9 (CH), 139.6 (C), 143.2 (C), 152.7
(CH), 190.0 (C) ppm. IR: ν = 3274, 3059, 3028, 2972, 2926, 2869,
˜
1627, 1582, 1535, 1496, 1476, 1449, 1376, 1268, 1239, 1205, 1127,
172.1, 188.8 (C) ppm. IR: ν = 3056, 3024, 2956, 2878, 1741, 1662, 1022, 758, 737, 696, 562, 541 cm–1. MS (EI): m/z (%) = 251 (10)
˜
1633, 1580, 1539, 1449, 1364, 1340, 1304, 1274, 1209, 1166, 1090,
[M+], 210 (8), 196 (55), 149 (18), 148 (16), 134 (12), 106 (30), 105
(55), 91 (100), 79 (38), 77 (41). HRMS: calcd. 251.13101, found:
1051, 1026, 1008, 991, 925, 893, 837, 758, 706, 621, 557 cm–1. MS
(EI): m/z (%) = 259 (45) [M+], 200 (100), 172 (34), 154 (58), 105 251.13111.
(70), 77 (54), 70 (36). HRMS: calcd. 259.12085, found: 259.12007.
Z-3k (C17H23NO): 51 mg (20%) yellow oil. 1H NMR (400 MHz,
1
Z-3f (C12H13NO): 100 mg (53%) yellow oil. H NMR (400 MHz,
CDCl3): δ = 0.98–1.21 (m, 6 H), 1.25 (d, J = 6.8 Hz, 3 H), 1.65–
1.79 (m, 5 H), 3.07 (dquint., J = 8.9, 6.6 Hz, 1 H), 5.67 (d, J =
7.4 Hz, 1 H), 6.96 (dd, J = 12.9, 7.4 Hz, 1 H), 7.34–7.43 (m, 3 H),
7.88 (dd, J = 7.6, 1.5 Hz, 2 H), 10.44 (br. s, 1 H, NH) ppm. 13C
NMR (100 MHz, DEPT, CDCl3): δ = 19.0 (CH3), 26.0 (CH2), 26.1
(CH2), 26.2 (CH2), 28.6 (CH2), 29.5 (CH2), 44.0 (CH), 60.5 (CH),
89.3 (CH), 127.0 (CH), 128.2 (CH), 130.7 (CH), 139.8 (C), 153.4
CDCl3): δ = 3.89 (tt, J = 5.6, 1.6 Hz, 2 H), 5.21 (dq, J = 10.2,
1.4 Hz, 1 H), 5.27 (dq, J = 17.1, 1.7 Hz, 1 H), 5.75 (d, J = 7.5 Hz,
1 H), 5.90 (ddt, J = 17.1, 10.3, 5.1 Hz, 1 H), 6.93 (dd, J = 12.8,
7.5 Hz, 1 H), 7.38–7.44 (m, 3 H), 7.88 (dd, J = 8.2, 1.4 Hz, 2 H),
10.3 (br. s, 1 H, NH) ppm. 13C NMR (100 MHz, DEPT, CDCl3):
δ = 51.0 (CH2), 90.7 (CH), 117.1 (CH2), 127.0 (CH), 128.2 (CH),
130.9 (CH), 134.2 (CH), 139.7 (C), 154.0 (CH), 190.1 (C) ppm. IR:
(CH), 189.5 (C) ppm. IR: ν = 3279, 3059, 3029, 2924, 2851, 1627,
˜
ν = 3271, 3059, 3027, 2921, 2855, 1627, 1582, 1541, 1499, 1476,
˜
1583, 1535, 1501, 1478, 1447, 1380, 1280, 1237, 1154, 1022, 759,
731, 697, 563. MS (EI): m/z (%) = 257 (20) [M+], 175 (15), 174
(100), 105 (29), 77 (10). HRMS: calcd. 257.17796, found:
257.17796.
1442, 1363, 1272, 1227, 1205, 1161, 1048, 1021, 988, 922, 867, 734,
699, 554 cm–1. MS (EI): m/z (%) = 187 (58) [M+], 186 (39), 105
(100), 82 (89), 77 (55). HRMS: calcd. 187.09972, found: 187.09941.
1
Z-3l (C19H18N2O): 32 mg (11%) yellow foam. 1H NMR (300 MHz,
CDCl3): δ = 3.03 (t, J = 6.8 Hz, 2 H), 3.55 (q, J = 6.6 Hz, 1 H),
5.61 (d, J = 7.4 Hz, 1 H), 6.79 (dd, J = 12.9, 7.4 Hz, 1 H), 7.01 (d,
J = 2.4 Hz, 1 H), 7.11 (td, J = 7.7, 1.0 Hz, 1 H), 7.19 (td, J = 7.9,
1.0 Hz, 1 H), 7.33 (d, J = 7.9 Hz, 1 H), 7.35–7.43 (m, 3 H), 7.56
(d, J = 7.8 Hz, 1 H), 7.85 (dd, J = 8.2, 1.5 Hz, 2 H), 8.19 (br. s, 1
H, NH), 10.40 (br. s, 1 H, NH) ppm. 13C NMR (75 MHz, DEPT,
CDCl3): δ = 27.2 (CH2), 49.6 (CH2), 90.0 (CH), 111.3 (CH), 111.9
(C), 118.4 (CH), 119.4 (CH), 122.1 (CH), 122.7 (CH), 126.9 (C),
127.0 (CH), 128.2 (CH), 130.8 (CH), 136.4 (C), 139.9 (C), 154.4
Z-3g (C15H17NO5): 143 mg (49%) yellow oil. H NMR (400 MHz,
CDCl3): δ = 2.88 (dd, J = 16.9, 7.4 Hz, 1 H), 2.99 (dd, J = 16.9,
5.2 Hz, 1 H), 3.72 (s, 3 H), 3.78 (s, 3 H), 4.31 (ddd, J = 9.4, 7.4,
5.2 Hz, 1 H), 5.81 (d, J = 7.7 Hz, 1 H), 6.96 (dd, J = 12.2, 7.8 Hz,
1 H), 7.38–7.46 (m, 3 H), 7.88 (dd, J = 8.0, 1.3 Hz, 2 H), 10.45 (t
br, J = 10.4 Hz, 1 H, NH) ppm. 13C NMR (100 MHz, DEPT,
CDCl3): δ = 37.5 (CH2), 52.2 (CH3), 52.9 (CH3), 57.9 (CH), 92.0
(CH), 127.2 (CH), 128.2 (CH), 131.2 (CH), 139.2 (C), 152.6 (CH),
170.3 (C), 170.4 (C), 190.6 (C) ppm. IR: ν = 3278, 3059, 3028,
˜
3003, 2954, 2849, 1733, 1631, 1584, 1549, 1500, 1476, 1437, 1368,
1270, 1204, 1164, 1045, 1019, 997, 849, 739, 700. MS (EI): m/z (%)
= 291 (12) [M+], 259 (12), 232 (20), 117 (24), 115 (42), 105 (100),
102 (24), 77 (48). HRMS: calcd. 291.11066, found: 291.11046.
Z-3h (C22H19NO): 122 mg (39%) yellow crystals. 1H NMR
(400 MHz, CDCl3): δ = 5.61 (d, J = 6.7 Hz, 1 H), 5.80 (d, J =
7.6 Hz, 1 H), 6.99 (dd, J = 12.6, 7.6 Hz, 1 H), 7.29–7.45 (m, 13 H),
7.88 (dd, J = 8.3, 1.7 Hz, 2 H), 11.00 (br. s, 1 H, NH) ppm. 13C
NMR (100 MHz, DEPT, CDCl3): δ = 66.3 (CH), 91.4 (CH), 127.2
(CH), 127.4 (CH), 127.8 (CH), 128.3 (CH), 128.9 (CH), 131.1
(CH), 189.9 (C) ppm. IR: ν = 3400, 3270, 3055, 2924, 2853, 1628,
˜
1581, 1526, 1503, 1480, 1453, 1340, 1275, 1228, 1009, 907, 737,
697. MS (EI): m/z (%) = 290 (4) [M+], 160 (18), 143 (100), 130 (78),
115 (21), 105 (23), 91 (22), 77 (46). HRMS: calcd. 290.14191,
found: 290.14114.
Z-3m (C21H20N2O3): 59 mg (17%) yellow foam. 1H NMR
(400 MHz, CDCl3): δ = 3.21 (dd, J = 14.6, 8.3 Hz, 1 H), 3.41 (dd,
J = 14.6, 4.6 Hz, 1 H), 3.72 (s, 3 H), 4.17 (td, J = 8.6, 4.7 Hz, 1
H), 5.62 (d, J = 7.6 Hz, 1 H), 6.59 (dd, J = 12.6, 7.7 Hz, 1 H), 7.01
(d, J = 2.3 Hz, 1 H), 7.11 (td, J = 7.9, 1.0 Hz, 1 H), 7.18 (td, J =
7.0, 1.0 Hz, 1 H), 7.31 (d, J = 8.1 Hz, 1 H), 7.34–7.43 (m, 3 H),
7.57 (d, J = 8.4 Hz, 1 H), 7.84 (dd, J = 7.9, 1.0 Hz, 2 H), 8.27 (br.
s, 1 H, NH), 10.52 (br. dd, J = 12.2, 9.1 Hz, 1 H, NH) ppm. 13C
NMR (100 MHz, DEPT, CDCl3): δ = 30.0 (CH2), 52.6 (CH3), 62.0
(CH), 91.3 (CH), 109.3 (C), 111.4 (CH), 118.3 (CH), 119.5 (CH),
122.1 (CH), 123.9 (CH), 126.9 (C), 127.2 (CH), 128.2 (CH), 131.1
(CH), 136.2 (C), 139.5 (C), 152.5 (CH), 171.4 (C), 190.5 (C) ppm.
(CH), 139.6 (C), 141.2 (C), 152.8 (CH), 190.4 (C) ppm. IR: ν =
˜
3291, 3084, 3048, 3029, 1616, 1580, 1527, 1496, 1475, 1451, 1380,
1278, 1235, 1196, 1179, 1154, 1086, 1051, 1024, 986, 916, 882, 802,
737, 594, 650, 605, 576 cm–1. MS (EI): m/z (%) = 313 (42) [M+],
167 (100), 165 (40), 152 (25). HRMS: calcd. 313.14667, found:
313.14664.
Z-3i (C16H15NO): 60 mg (25%) yellow oil. 1H NMR (300 MHz,
CDCl3): δ = 4.41 (d, J = 6.2 Hz, 2 H), 5.74 (d, J = 7.5 Hz, 1 H),
6.98 (dd, J = 12.7, 7.5 Hz, 1 H), 7.16–7.43 (m, 8 H), 7.86 (dd, J =
8.2, 1.9 Hz, 2 H), 10.57 (br. s, 1 H, NH) ppm. 13C NMR (75 MHz,
DEPT, CDCl3): δ = 52.6 (CH2), 90.8 (CH), 127.0 (CH), 127.4
(CH), 127.7 (CH), 128.3 (CH), 128.7 (CH), 130.9 (CH), 137.6 (C),
IR: ν = 3397, 3282, 3056, 2950, 2924, 2852, 1736, 1627, 1582, 1533,
˜
1500, 1478, 1454, 1435, 1340, 1304, 1235, 1204, 1172, 1097, 1012,
908, 737, 699. MS (EI): m/z (%) = 348 (4) [M+], 218 (4), 201 (16),
169 (4), 158 (4), 143 (4), 130 (100), 117 (12), 115 (13), 105 (12), 91
(4), 77 (22). HRMS: calcd. 348.14739, found: 348.14738.
139.0 (C), 154.2 (CH), 190.1 (C) ppm. IR: ν = 3275, 3060, 3029,
˜
2860, 1631, 1581, 1539, 1495, 1450, 1360, 1275, 1204, 1050, 1025,
970, 836, 733, 695, 557. MS (EI): m/z (%) = 237 (8) [M+], 197 (10),
196 (12), 149 (8), 135 (24), 106 (60), 105 (12), 91 (100), 79 (22), 77
(24). HRMS: calcd. 237.11536, found: 237.11538.
1
Z-3n (C13H15NO3): 37 mg (16%) yellow oil. H NMR (400 MHz,
CDCl3): δ = 1.34 (d, J = 6.7 Hz, 3 H), 3.71 (s, 3 H), 3.77 (quint.,
J = 7.0, Hz, 1 H), 5.79 (d, J = 7.6 Hz, 1 H), 6.94 (dd, J = 12.6,
7.6 Hz, 1 H), 7.30 –7.41 (m, 3 H), 7.88 (dd, J = 7.8, 1.8 Hz, 2 H),
Z-3j (C17H17NO): 35 mg (14%) yellow oil. 1H NMR (400 MHz, 10.36 (t br, J = 11.8 Hz, 1 H, NH) ppm. 13C NMR (100 MHz,
CDCl3): δ = 1.61 (d, J = 6.9 Hz, 3 H), 4.52 (quint., J = 6.8 Hz, 1
H), 5.72 (d, J = 7.6 Hz, 1 H), 6.95 (dd, J = 12.8, 7.5 Hz, 1 H),
7.23–7.44 (m, 8 H), 7.88 (dd, J = 7.8, 1.4 Hz, 2 H), 10.68 (br. s, 1
DEPT, CDCl3): δ = 19.0 (CH3), 52.7 (CH3), 55.9 (CH), 91.3 (CH),
126.4 (CH), 128.1 (CH), 131.0 (CH), 139.2 (C), 152.3 (CH), 172.1
(C), 190.1 (C) ppm. IR: ν = 3293, 3061, 3029, 2983, 2952, 1739,
˜
2820
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© 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2007, 2815–2824

Catalysts for Transformations of Propargyl Alcohols
FULL PAPER
1632, 1582, 1537, 1449, 1377, 1205, 1159, 1064, 1024, 975, 910,
(CH), 124.7 (CH), 125.7 (CH), 125.8 (CH), 125.9 (C), 126.2 (CH),
847, 759, 729, 697, 550. MS (EI): m/z (%) = 233 (4) [M+], 192 (7), 127.4 (CH), 128.4 (CH), 131.2 (CH), 133.9 (C), 134.3 (C), 144.0
174 (7), 158 (22), 130 (22), 117 (44), 115 (100), 105 (60), 91 (77),
77 (55). HRMS: calcd. 233.10519, found: 233.10508.
(CH), 153.0 (C), 162.0 (CH) ppm.
General Procedure of Ligand Synthesis: 1 mmol of the correspond-
ing 4-hydroxycyclopent-4-ene-1,3-dione and 1 mmol diamine were
dissolved in 5 mL of methanol and refluxed for 2 h under argon.
After evaporation of the solvent chromatography of the crude
products on silica furnished the pure compounds. The procedure
was used for the synthesis of ligands 6aL, 6bL, 6cL, 6dL, 7cL, 7dL
and precursor 7bLЈ. Compounds 7cL and 7dL were obtained as an
inseparable mixture. Compound 5 L was prepared according to a
published procedure.[12a]
6aL (C21H20N2O): 297 mg (94%) violet foam. 1H NMR (400 MHz,
CDCl3): δ = 2.83 (s, 6 H), 3.34 (s, 4 H), 7.13–7.17 (m, 2 H), 7.26–
7.28 (m, 8 H) ppm. 13C NMR (100 MHz, DEPT, CDCl3): δ = 42.1
(CH3), 50.0 (CH2), 99.0 (C), 125.4 (CH), 127.2 (CH), 131.0 (CH),
Compounds 9–16 are known and the spectroscopic data was com-
pared with published results. Yields of compounds 9–11 depend on
the catalyst used and are given in Table 3.
1
9 (C15H15NO): Yellow crystals. H NMR (200 MHz, CDCl3): δ =
3.24 (t, J = 6.0 Hz, 2 H), 3.59 (t, J = 6.0 Hz, 2 H), 3.72 (br., NH),
6.61–6.78 (m, 3 H), 7.09–7.21 (m, 2 H), 7.39–7.58 (m, 3 H), 7.93
(dd, J = 8.2, 1.2 Hz, 2 H) ppm. 13C NMR (50 MHz, DEPT,
CDCl3): δ = 37.6 (CH2), 38.7 (CH2), 113.0 (CH), 117.5 (CH), 128.0
(CH), 128.6 (CH), 129.3 (CH), 133.2 (CH), 136.7 (C), 147.7 (C),
199.2 (C) ppm.
10 (C15H15NO): Yellow crystals. 1H NMR (400 MHz, CDCl3): δ =
1.47 (d, J = 6.9 Hz, 3 H), 4.66 (br. s, NH), 5.12 (q, J = 6.9 Hz, 1
H), 6.67 (dd, J = 8.6, 1.0 Hz, 2 H), 6.71 (t, J = 7.3 Hz, 1 H), 7.17
(dd, J = 8.5, 7.4 Hz, 2 H), 7.49 (t, J = 7.8 Hz, 2 H), 7.60 (tt, J =
7.4, 1.3 Hz, 1 H), 8.00 (dd, J = 8.6, 1.4 Hz, 2 H) ppm. 13C NMR
(100 MHz, DEPT, CDCl3): δ = 19.5 (CH3), 53.3 (CH), 113.4 (CH),
117.9 (CH), 128.4 (CH), 128.8 (CH), 129.4 (CH), 133.6 (CH), 134.6
(C), 146.5 (C), 200.6 (C) ppm.
133.6 (C), 150.9 (C), 195.2 (C) ppm. IR: ν = 2926 (w), 2860 (w),
˜
2798 (w), 1586 (s), 1493 (m), 1439 (m), 1409 (m), 1352 (s), 1244
(m), 1175 (w), 1113 (m), 1068 (m), 1025 (w), 942 (m), 914 (w), 839
(w), 804 (w), 774 (m), 727 (m), 698 (s), 648 (m) cm–1. MS (EI): m/z
(%) = 316 [M+] (42), 273 (18), 227 (100), 203 (28), 105 (38), 77 (40).
HRMS: calcd. 316.15753, found: 316.15754.
6bL (C31H24N2O): 300 mg (68%) violet powder, poorly soluble: IR:
11 (C13H11NO): White solid. 1H NMR (300 MHz, CDCl3): δ =
7.12–7.19 (m, 3 H), 7.30–7.35 (m, 2 H), 7.39–7.42 (m, 3 H), 7.82–
7.85 (m, 2 H), 8.38 (s, 1 H) ppm. 13C NMR (75 MHz, DEPT,
CDCl3): δ = 121.0 (CH), 126.1 (CH), 128.9 (CH), 128.9 (CH), 129.3
(CH), 131.5 (CH), 136.3 (C), 152.2 (C), 160.6 (CH) ppm.
ν = 3049 (w), 2928 (w), 1659 (m), 1604 (m), 1575 (s), 1492 (s), 1431
˜
(m), 1410 (m), 1356 (s), 1276 (m), 1202 (s), 1132 (w), 1075 (m),
1015 (w), 968 (m), 910 (w), 843 (w), 805 (m), 775 (m), 761 (m), 738
(s), 693 (s), 621 (m) cm–1. MS (EI): m/z (%) = 440 [M+] (100), 411
(12), 335 (18), 178 (20). HRMS: calcd. 440.18886, found:
440.18867.
6cL (C15H16N2O): 235 mg (98%) dark red foam. 1H NMR
(400 MHz, CDCl3): δ = 2.73 (s, 3 H), 2.94 (s, 3 H), 3.26–3.34 (m,
4 H), 4.36 (s, 1 H), 7.15 (tt, J = 7.2, 1.4 Hz, 1 H), 7.19–7.22 (m, 2
H), 7.25–7.30 (m, 3 H) ppm. 13C NMR (100 MHz, DEPT, CDCl3):
δ = 39.7 (CH3), 41.8 (CH3), 48.7 (CH2), 50.5 (CH2), 84.3 (CH),
101.0 (C), 125.8 (CH), 127.5 (CH), 131.4 (CH), 133.9 (C), 148.4
12 (C15H13N): 116 mg (56%) white solid. 1H NMR (200 MHz,
CDCl3): δ = 7.04–7.25 (m, 5 H), 7.29–7.42 (m, 5 H), 7.48–7.56 (m,
2 H), 8.27 (d, J = 7.2 Hz, 1 H) ppm. 13C NMR (50 MHz, DEPT,
CDCl3): δ = 120.9 (CH), 126.1 (CH), 127.4 (CH), 128.5 (CH), 128.9
(CH), 129.1 (CH), 129.6 (CH), 135.5 (C), 144.0 (CH), 151.6 (CH),
161.6 (CH) ppm.
13 (C30H24O2): 127 mg (61%) yellow foam. 1H NMR (400 MHz,
CDCl3): δ = 2.8 (br., 2 H), 5.92 (d, J = 15.8 Hz, 1 H), 6.77 (d, J =
15.8 Hz, 1 H), 7.12–7.35 (m, 16 H), 7.56 (d, J = 7.1 Hz, 2 H) ppm.
13C NMR (100 MHz, DEPT, CDCl3): δ = 74.6 (C), 79.1 (C), 85.1
(C), 93.2 (C), 108.8 (CH), 126.0 (CH), 126.9 (CH), 127.5 (CH),
127.6 (CH), 128.1 (CH), 128.2 (CH), 144.9 (C), 145.0 (C), 148.4
(C), 158.0 (C), 197.0 (C) ppm. IR: ν = 2920 (w), 2856 (w), 1659
˜
(w), 1588 (s), 1493 (m), 1443 (m), 1409 (m), 1363 (m), 1299 (m),
1232 (m), 1215 (m), 1145 (m), 1112 (m), 1070 (m), 983 (m), 927
(m), 837 (w), 773 (s), 726 (m), 705 (s), 678 (m), 657 (s) cm–1. MS
(EI): m/z (%) = 241 [M+ + 1] (18), 240 [M+] (100), 239 [M+ – 1]
(30), 197 (24). HRMS: [M+] calcd. 240.12626, found: 240.12620,
[M+ – 1] calcd. 239.11844, found: 239.11836.
(CH) ppm. IR: ν = 3542 (w), 3402 (br.) , 3058 (w), 3026 (w), 3026
˜
(w), 2973 (w), 2874 (w), 1598 (w), 1490 (m), 1446 (m), 1158 (w),
1030 (m), 1001 (m), 907 (m), 756 (m), 732 (m), 695 (s), 641 (w)
cm–1. MS (EI): m/z (%) = 416 [M+] (5), 398 (10), 382 (12), 293 (20),
215 (35), 105 (100), 77 (40).
6dL (C23H24N2O3): 332 mg (88%) dark violet crystals, poorly solu-
ble: IR: ν = 3610 (w), 3356 (br.) , 3052 (w), 2931 (w), 1713 (m),
˜
1649 (w), 1604 (m), 1549 (s), 1494 (s), 1443 (m), 1405 (m), 1358
(m), 1296 (m), 1156 (m), 1072 (m), 1055 (m), 968 (w), 950 (w), 917
(w), 800 (m), 766 (m), 729 (m), 695 (s), 591 (m), 569 (m) cm–1. MS
(EI): m/z (%) = 376 [M+] (100), 346 (35), 332 (30), 301 (64). HRMS:
calcd. 376.17869, found: 376.17847.
7bLЈ (C13H15NO): 175 mg (87%) green foam: 13C NMR (50 MHz,
DEPT, CDCl3): δ = 47.6 (CH2), 49.9 (CH2), 51.8 (CH2), 53.9
(CH2), 56.5 (CH2), 59.8 (CH2), 63.0 (CH2), 98.0 (C), 116.3 (C),
127.3 (CH), 128.1 (CH), 130.3 (CH), 132.9 (C), 162.3 (C), 197.4
(C) ppm.
14 (C17H14O2): White foam. 1H NMR (400 MHz, CDCl3): δ = 2.17
(s, 3 H), 2.99 (s, 1 H), 7.27 (t, J = 7.4 Hz, 2 H), 7.33 (t, J = 7.6 Hz,
4 H), 7.52 (d, J = 7.1 Hz, 4 H) ppm. 13C NMR (100 MHz, DEPT,
CDCl3): δ = 21.8 (CH3), 78.0 (CH), 79.0 (C), 82.3 (C), 126.1 (CH),
128.0 (CH), 128.3 (CH), 142.0 (C), 168.2 (C) ppm.
1
15 (C21H17N): 130 mg (46%) yellow crystals. H NMR (400 MHz,
CDCl3): δ = 7.06 (d,J = 8.6 Hz, 2 H), 7.08 (d, J = 9.3 Hz, 1 H),
7.16 (t, J = 7.4 Hz, 1 H), 7.28–7.44 (m, 12 H), 8.13 (d, J = 9.4 Hz,
1 H) ppm. 13C NMR (100 MHz, DEPT, CDCl3): δ = 121.0 (CH),
126.0 (CH), 127.3 (CH), 128.1 (CH), 128.3 (CH), 128.4 (CH), 128.7
(CH), 129.1 (CH), 129.2 (CH), 130.5 (CH), 138.3 (C), 140.7 (C),
151.9 (C), 154.3 (C), 160.4 (CH) ppm.
7cL (C12H16N2O3): 229 mg (84% as 1:1 mixture with 7dL) red
1
foam. H NMR (200 MHz, CDCl3): δ = 1.32 (t, J = 7.1 Hz, 3 H),
2.90 (s, 3 H), 3.08 (s, 3 H), 3.32 (br. s, 4 H), 4.22 (q, J = 7.1 Hz, 2
H), 4.46 (s, 1 H) ppm. 13C NMR (50 MHz, DEPT, CDCl3): δ =
14.3 (CH3), 39.2 (CH3), 43.1 (CH3), 47.1 (CH2), 49.1 (CH2), 60.0
1
16 (C19H15N): 134 mg (52%) yellow crystals. H NMR (200 MHz,
CDCl3): δ = 7.03 (d, J = 16.2 Hz, 1 H), 7.24 (dd, J = 16.0, 8.0 Hz,
1 H), 7.32–7.87 (m, 10 H), 8.30 (d, J = 7.9 Hz, 1 H) ppm. 13C (CH2), 90.1 (CH), 92.1 (C), 154.2 (C), 159.8 (C), 164.3 (C), 192.3
NMR (50 MHz, DEPT, CDCl3): δ = 112.8 (CH), 118.8 (CH), 123.8
(C) ppm.
Eur. J. Org. Chem. 2007, 2815–2824
© 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
2821

E. Haak
FULL PAPER
7dL (C15H20N2O5): 229 mg (84% as 1:1 mixture with 7cL) red (m) cm–1. MS (EI): m/z (%) = 359 [M+] (38), 267 (100), 240 (30).
1
foam. H NMR (200 MHz, CDCl3): δ = 1.32 (t, J = 7.2 Hz, 6 H), HRMS: calcd. 359.16339, found: 359.16297.
3.24 (s, 6 H), 3.58 (s, 4 H), 4.22 (q, J = 7.0 Hz, 4 H) ppm. 13C
8bL (C26H23N3O2): 373 mg (91%) violet foam. 1H NMR
NMR (50 MHz, DEPT, CDCl3): δ = 14.9 (CH3), 43.6 (CH3), 49.7
(400 MHz, CDCl3): δ = 2.70 (s, 3 H), 3.25 (dd, J = 6.4, 5.7 Hz, 2
(CH2), 60.5 (CH2), 92.6 (C), 157.4 (C), 164.2 (C), 187.3 (C) ppm.
H), 3.48 (dd, J = 6.4, 5.6 Hz, 2 H), 3.65 (s, 3 H), 7.27–7.30 (m, 3
Synthesis of Ligands 7aL and 7bL: 1 mmol of the ligand precursor
(6cL for 7aL and 7bLЈ for 7bL) was dissolved in 3 mL of pyridine.
After addition of a catalytic amount of DMAP and 1.5 equiv. (for
7aL) or 3.5 equiv. (for 7bL) benzoyl chloride the reaction mixture
was stirred at room temp. under argon for 24 h. Aqueous workup
and chromatography on silica furnished the ligands 7aL and 7bL.
7aL (C22H20N2O2): 357 mg (97%) dark red foam. 1H NMR
(400 MHz, CDCl3): δ = 2.61 (s, 3 H), 3.17 (s, 3 H), 3.19 (t, J =
6.3 Hz, 2 H), 3.48 (t, J = 6.0 Hz, 2 H), 7.08–7.32 (m, 8 H), 7.67 (d,
J = 6.9 Hz, 2 H) ppm. 13C NMR (100 MHz, DEPT, CDCl3): δ =
41.4 (CH3), 44.2 (CH3), 48.5 (CH2), 50.2 (CH2), 98.4 (C), 104.3
(C), 126.2 (CH), 127.0 (CH), 127.1 (CH), 129.8 (CH), 130.8 (CH),
131.0 (CH), 132.2 (C), 140.8 (C), 147.6 (C), 164.5 (C), 187.6 (C),
H), 7.34–7.38 (m, 2 H), 7.41–7.50 (m, 3 H), 7.53 (d, J = 8.2 Hz, 1
H), 7.80 (d, J = 7.9 Hz, 1 H), 8.32 (t, J = 7.6 Hz, 2 H), 11.14 (s,
NH) ppm. 13C NMR (100 MHz, DEPT, CDCl3): δ = 41.7 (CH3),
45.3 (CH3), 48.5 (CH2), 50.1 (CH2), 90.2 (C), 103.4 (C), 117.5
(CH), 121.8 (CH), 122.9 (CH), 125.6 (CH), 125.8 (CH), 125.9
(CH), 126.3 (C), 126.8 (CH), 127.6 (CH), 128.2 (CH), 131.2 (CH),
132.2 (C), 134.1 (C), 134.8 (C), 149.1 (C), 161.6 (C), 161.7 (C),
195.5 (C) ppm. IR: ν = 3049 (w), 2921 (w), 2855 (w), 2065 (w),
˜
1982 (w), 1643 (m), 1573 (s), 1531 (s), 1496 (s), 1451 (m), 1397 (s),
1357 (s), 1339 (m), 1254 (s), 1206 (w), 1156 (w), 1100 (m), 1070
(w), 1025 (w), 990 (w), 970 (m), 894 (w), 837 (m), 795 (s), 776 (s),
732 (s), 702 (s) cm–1. MS (EI): m/z (%) = 409 (38) [M+], 267 (95),
240 (75), 169 (100), 141 (37), 140 (34). HRMS: calcd. 409.17903,
found: 409.17905.
191.2 (C) ppm. IR: ν = 2929 (w), 1647 (w), 1606 (s), 1581 (s), 1547
˜
8cL (C22H27N3O2): 325 mg (89%) violet foam. 1H NMR
(400 MHz, CDCl3): δ = 1.16–1.27 (m, 3 H), 1.30–1.41 (m, 2 H),
1.52–1.57 (m, 1 H), 1.66–1.72 (m, 2 H), 1.88–1.94 (m, 2 H), 2.73
(s, 3 H), 3.30 (dd, J = 6.3, 4.3 Hz, 2 H), 3.51 (dd, J = 6.4 Hz, 2 H),
3.60 (s, 3 H), 7.19–7.23 (m, 3 H), 7.29–7.33 (m, 2 H), 8.30 (d, J =
8.0 Hz, 1 H) ppm. 13C NMR (100 MHz, DEPT, CDCl3): δ = 24.7
(CH2), 25.7 (CH2), 33.1 (CH2), 41.7 (CH3), 44.9 (CH3), 47.2 (CH),
48.6 (CH2), 50.0 (CH2), 89.7 (C), 102.8 (C), 126.4 (CH), 127.4
(CH), 131.0 (CH), 132.4 (C), 148.6 (C), 160.4 (C), 162.7 (C), 195.3
(s), 1498 (w), 1445 (m), 1426 (s), 1403 (s), 1364 (s), 1340 (m), 1270
(m), 1250, (m), 1172 (w), 1117 (w), 1074 (w), 1050 (w), 1012 (w),
926 (m), 907 (s), 833 (m), 798 (m), 765 (s), 745 (m), 732 (m), 703
(s), 655 (s) cm–1. MS (EI): m/z (%) = 344 (90) [M+], 253 (100),
105 (40). HRMS (ESI, MeOH): [M+]+Na calcd. 367.14225, found:
367.14208.
7bL (C38H32N2O6): 570 mg (93%) dark red foam. 1H NMR
(400 MHz, CDCl3): δ = 3.56 (t, J = 5.8 Hz, 2 H), 3.58 (t, J =
5.0 Hz, 2 H), 3.80 (t, J = 5.6 Hz, 2 H), 4.10 (t, J = 5.2 Hz, 2 H),
4.33 (t, J = 4.9 Hz, 2 H), 4.59 (t, J = 5.1 Hz, 3 H), 7.17–7.23 (m,
3 H), 7.28 (t, J = 7.5 Hz, 2 H), 7.32 (t, J = 7.7 Hz, 2 H), 7.39–7.45
(m, 5 H), 7.55–7.59 (m, 2 H), 7.65 (dd, J = 8.4, 1.4 Hz, 2 H), 7.93
(C) ppm. IR: ν = 3519 (w), 3294 (w), 2933 (m), 2855 (w), 2231 (w),
˜
1617 (s), 1573 (s), 1518 (s), 1451 (m), 1412 (m), 1358 (m), 1250 (m),
1180 (w), 1113 (m), 1071 (m), 965 (w), 926 (w), 868 (w), 337 (m),
758 (m), 792 (m), 758 (m), 729 (m), 709 (m), 644 (m), 614 (m) cm–1.
MS (EI): m/z (%) = 365 [M+] (60), 268 (100), 241 (71). HRMS:
calcd. 365.21033, found: 365.21027.
(dd, J = 8.2, 1.4 Hz, 2 H), 8.00 (dd, J = 8.2, 1.4 Hz, 2 H) ppm. 13
C
NMR (100 MHz, DEPT, CDCl3): δ = 47.9 (CH2), 50.8 (CH2), 51.0
(CH2), 54.7 (CH2), 61.1 (CH2), 61.5 (CH2), 98.9 (C), 104.67 (C),
127.1 (CH), 127.4 (CH), 127.7 (CH), 128.5 (CH), 128.6 (CH), 129.4
(C), 129.5 (C), 129.5 (CH), 129.6 (CH), 129.7 (CH), 131.1 (CH),
131.2 (CH), 132.0 (C), 133.3 (CH), 133.4 (CH), 141.0 (C), 146.6
(C), 163.3 (C), 166.0 (C), 166.1 (C), 189.1 (C), 191.4 (C) ppm. IR:
General Procedure of Complex Synthesis: 150 mg dodecacarbon-
yltriruthenium (C12O12Ru3, 0.23 mmol) and 0.7 mmol of the corre-
sponding ligand were dissolved in 5 mL toluene (for complexes 8d
and 7b 1 mL MeOH was added) and refluxed for 4–12 h (TLC
control). The solvent was evaporated and chromatography on silica
furnished the complexes 2 and 5–8.
ν = 3058 (w), 2927 (w), 2854 (w), 1716 (s), 1668 (w), 1601 (s), 1577
˜
(s), 1551 (m), 1495 (w), 1450 (m), (1422 (m), 1360 (m), 1313 (w),
1265 (s), 1175 (m), 1110 (s), 1097 (s), 1069 (m), 1026 (m), 914 (m),
818 (w), 768 (w), 700 (s), 658 (m), 617 (w) cm–1. MS (EI): m/z (%)
= 612 [M+] (10), 490 (55), 149 (33), 122 (50), 105 (100), 77 (47).
HRMS: calcd. 612.22604, found: 612.22728.
2a (C32H20O4Ru): 394 mg (98%) white powder. 1H NMR
(300 MHz, CDCl3): δ = 6.99–7.04 (m, 6 H), 7.08–7.11 (m, 4 H),
7.14–7.17 (m, 6 H), 7.39–7.42 (m, 4 H) ppm. 13C NMR (75 MHz,
DEPT, CDCl3): δ = 82.0 (C), 107.8 (C), 127.4 (CH), 127.9 (CH),
128.0 (CH), 128.5 (CH), 129.8 (C), 130.7 (CH), 131.5 (C), 132.0
Synthesis of Ligands 8aL, 8bL and 8cL: 1 mmol of 6cL was dis-
solved in 5 mL of DCM. After addition of 1.1 equiv. of the corre-
sponding isocyanate the reaction mixture was stirred at room temp.
under argon for 24 h. Aqueous workup and chromatography on
silica furnished the ligands 8aL, 8bL and 8cL.
8aL (C22H21N3O2): 352 mg (98%) violet foam. 1H NMR
(400 MHz, CDCl3): δ = 2.75 (s, 3 H), 3.31 (dd, J = 6.4, 5.7 Hz, 2
H), 3.53 (dd, J = 6.4, 5.6 Hz, 2 H), 3.64 (s, 3 H), 6.98 (tt, J = 7.4,
1.1 Hz, 1 H), 7.23–7.28 (m, 5 H), 7.31–7.35 (m, 2 H), 7.59–7.62 (m,
2 H), 10.54 (s, 1 H) ppm. 13C NMR (100 MHz, DEPT, CDCl3): δ
= 41.7 (CH3), 45.3 (CH3), 48.5 (CH2), 50.1 (CH2), 89.8 (C), 103.3
(C), 119.6 (CH), 122.4 (CH), 126.7 (CH), 127.6 (CH), 128.7 (CH),
131.0 (CH), 132.1 (C), 139.7 (C), 148.8 (C), 161.4 (C), 161.6 (C),
(CH), 173.9 (C), 194.4 (CO) ppm. IR: ν = 3060, 2075, 2018, 1997,
˜
1633, 1601, 1497, 1445, 1388, 1202, 1185, 1075, 1028, 840, 801,
753, 736, 692, 637, 577, 552, 537 cm–1. MS (EI): m/z (%) = 573,
572, 571, 570, 569, 568, 567, 564 [1:5:2:10:6:4:4:2, distribution of
M+ isotopes] (18), 542 (22), 514 (65), 486 (100), 458 (55), 278 (30).
2b (C22H16O4Ru): 300 mg (95%) white powder. 1H NMR
(400 MHz, C6D6): δ = 1.92 (s, 6 H), 6.83–6.84 (m, 6 H), 6.95–6.98
(m, 4 H) ppm. 13C NMR (100 MHz, DEPT, C6D6): δ = 10.7 (CH3),
77.3 (C), 108.5 (C), 128.2 (CH), 128.5 (CH), 130.7 (C), 131.6 (CH),
176.1 (C), 196.0 (CO) ppm. IR: ν = 3058, 2066, 2011, 1989, 1767,
˜
1688, 1642, 1501, 1451, 1396, 1180, 1134, 1078, 1036, 1021, 972,
758, 720, 698, 586, 549, 531 cm–1. MS (EI): m/z (%) = 449, 448,
447, 446, 445, 444, 443, 440 [1:5:2:10:6:4:4:2, distribution of M+
isotopes] (10), 418 (40), 362 (100), 332 (35), 328 (30), 260 (25).
195.2 (C) ppm. IR: ν = 3326 (w), 3230 (w), 3124 (w), 3052 (w),
˜
3025 (w), 2929 (w), 2851 (w), 1658 (m), 1625 (m), 1596 (m), 1569
(s), 1531 (s), 1497 (s), 1436 (s), 1408 (m), 1361 (s), 1305 (m), 1244
(s), 1156 (m), 1111 (w), 1070 (m), 1034 (w), 998 (w), 973 (m), 910
5
(C24H16O8Ru): 338 mg (90%) yellow powder. 1H NMR
(w), 884 (w), 834 (w), 795 (w), 778 (w), 753 (s), 728 (s), 698 (s), 618 (400 MHz, CDCl3): δ = 3.69 (s, 6 H), 7.20–7.26 (m, 10 H) ppm.
2822
www.eurjoc.org
© 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2007, 2815–2824

Catalysts for Transformations of Propargyl Alcohols
FULL PAPER
13C NMR (100 MHz, DEPT, CDCl3): δ = 52.6 (CH3), 71.0 (C), 561, 560, 557 [1:4:2:8:4:3:2:1, distribution of (M+ + H) isotopes]
109.1 (C), 128.1 (CH), 128.6 (C), 129.2 (CH), 130.9 (CH), 165.5
(40), 535 [M+ + H – CO] (40), 507 [M+ + H – 2 CO] (28).
(C), 170.5 (C), 191.5 (CO) ppm. IR: ν = 3064 (w), 2953 (w), 2101
˜
7a (C25H20N2O5Ru): 254 mg (68%) yellow powder. 1H NMR
(400 MHz, CDCl3): δ = 2.12 (s, 3 H), 2.23 (s, 3 H), 2.48–2.54 (m,
1 H), 2.59–2.64 (m, 1 H), 3.23–3.29 (m, 1 H), 3.39–3.45 (m, 1 H),
7.14–7.41 (m, 8 H), 7.67 (d, J = 7.1 Hz, 2 H) ppm. 13C NMR
(100 MHz, DEPT, CDCl3): δ = 42.8 (CH3), 43.5 (CH3), 49.7 (CH2),
50.2 (CH2), 69.0 (C), 70.9 (C), 114.3 (C), 114.9 (C), 126.7 (CH),
127.7 (CH), 128.2 (CH), 128.3 (CH), 128.7 (CH), 129.7 (CH), 131.4
(C), 132.6 (CH), 133.4 (CH), 136.7 (C), 169.8 (C), 171.9 (C), 193.2
(s), 2035 (s), 1735 (s), 1707 (s), 1675 (s), 1501 (w), 1436 (m), 1414
(w), 1377 (w), 1347 (s), 1200 (s), 1173 (s), 1123 (m), 1103 (m), 1032
(w), 995 (m), 786 (m), 776 (m), 762 (w), 698 (s), 652 (w), 626 (w),
599 (s), 586 (m) cm–1. MS (EI): m/z (%) = 538, 537, 536, 535, 534,
533, 532, 529 [1:4:2:8:4:3:3:1, distribution of (M+ + H) isotopes]
(100), 507 [M+ + H – CO] (39), 479 [M+ + H – 2 CO] (98).
6a (C24H20N2O4Ru): 256 mg (72%) yellow powder. 1H NMR
(400 MHz, CDCl3): δ = 2.08 (s, 6 H), 2.52 (ddd, J = 16.2, 6.6,
4.2 Hz, 2 H), 3.30 (ddd, J = 15.9, 6.9, 4.0 Hz, 2 H), 7.18–7.31 (m,
6 H), 7.39–7.41 (m, 4 H) ppm. 13C NMR (100 MHz, DEPT,
CDCl3): δ = 43.5 (CH3), 50.0 (CH2), 69.5 (C), 116.6 (C), 127.6
(CO) ppm. IR: ν = 2927 (w), 2858 (w), 2057 (s), 1978 (s), 1627 (s),
˜
1581 (s), 1498 (m), 1447 (m), 1401 (m), 1359 (m), 1263 (m), 1211
(w), 1071 (m), 1026 (m), 914 (m), 839 (w), 787 (w), 734 (s), 695 (s)
cm–1. MS (ESI, TBME): m/z (%) = 534, 533, 532, 531, 530, 529,
(CH), 128.3 (CH), 132.2 (C), 132.7 (CH), 171.9 (C), 196.2 (CO) 528, 525 [1:4:2:8:4:3:3:1, distribution of (M+ + H) isotopes] (8), 497
ppm. IR: ν = 2957 (w), 2927 (w), 2866 (w), 2809 (w), 2046 (s), 1963
[M+ – 2 CO + Na] (5), 469 [M+ – 3 CO + Na] (4), 367 [M+
–
˜
(s), 1638 (m), 1530 (m), 1493 (m), 1442 (m), 1411 (m), 1359 (m), Ru(CO)3 + Na] (40).
1264 (w), 1183 (w), 1115 (w), 1074 (w), 1046 (w), 1004 (w), 946
7b (C41H32N2O9Ru): 360 mg (64%) yellow powder. 1H NMR
(400 MHz, CDCl3): δ = 2.51–2.57 (m, 1 H), 2.66–2.72 (m, 1 H),
2.84–2.90 (m, 1 H), 2.92–2.97 (m, 1 H), 3.12–3.19 (m, 2 H), 3.66–
3.75 (m, 3 H), 4.00–4.07 (m, 2 H), 4.15–4.19 (m, 1 H), 7.18–8.04
(m, 20 H) ppm. 13C NMR (100 MHz, DEPT, CDCl3): δ = 48.1
(CH2), 48.4 (CH2), 52.9 (CH2), 53.8 (CH2), 61.4 (CH2), 61.8 (CH2),
(m), 848 (w), 753 (m), 723 (m), 697 (s), 655 (w), 606 (m) cm–1. MS
(ESI, TBME): m/z (%) = 506, 505, 504, 503, 502, 501, 500, 497
[1:3:2:7:4:3:2:1, distribution of (M+ + H) isotopes] (97), 475 [M+
+
H – CO] (86), 317 [M+ + H – Ru(CO)3] (100).
6b (C34H24N2O4Ru): 330 mg (75%) yellow powder. 1H NMR
(400 MHz, CDCl3): δ = 3.76–3.82 (m, 2 H), 3.87–3.93 (m, 2 H), 70.1 (C), 70.2 (C), 111.6 (C), 114.5 (C), 128.2 (C), 128.3 (CH),
6.85–7.00 (m, 16 H), 7.43–7.47 (m, 4 H) ppm. 13C NMR (100 MHz,
DEPT, CDCl3): δ = 50.9 (CH2), 71.9 (C), 110.7 (C), 124.7 (CH),
128.4 (CH), 128.5 (CH), 128.6 (CH), 128.7 (CH), 128.8 (CH), 129.0
(C), 129.6 (CH), 129.9 (CH), 131.1 (C), 132.9 (CH), 133.2 (CH),
125.3 (CH), 126.4 (CH), 127.4 (CH), 128.7 (CH), 130.8 (CH), 132.4 133.4 (CH), 133.7 (CH), 136.6 (C), 166.0 (C), 166.1 (C), 169.7 (C),
(C), 144.1 (C), 171.0 (C), 195.9 (CO) ppm. IR: ν = 3057 (w), 3020 170.2 (C), 192.2 (CO) ppm. IR: ν = 3060 (w), 2928 (w), 2855 (w),
˜
˜
(w), 2925 (w), 2877 (w), 2044 (s), 1983 (s), 1965 (s), 1646 (s), 1595 2064 (s), 1985 (s), 1718 (s), 1603 (m), 1580 (s), 1496 (w), 1452 (s),
(m), 1485 (s), 1438 (m), 1392 (w), 1360 (m), 1306 (m), 1221 (w), 1362 (m), 1316 (w), 1267 (s), 1177 (m), 1111 (s), 1071 (s), 1028 (m),
1157 (w), 1125 (w), 1073 (w), 973 (w), 827 (w), 807 (w), 752 (m), 820 (w), 710 (s) cm–1. MS (ESI, TBME): m/z (%) = 802, 801, 800,
737 (m), 719 (m), 690 (s), 627 (w) cm–1. MS (ESI, TBME): m/z (%)
= 630, 629, 628, 627, 626, 625, 624, 621 [1:5:2:10:6:4:4:2, distribu-
tion of (M+ + H) isotopes] (70), 599 [M+ + H – CO] (100), 571
[M+ + H – 2 CO] (22), 543 [M+ + H – 3 CO] (13), 441 [M+ + H –
Ru(CO)3].
799, 798, 797, 796, 793 [1:3:2:6:4:3:2:1, distribution of (M+ + H)
isotopes] (90), 771 [M+ + H – CO] (30), 743 [M+ + H – 2 CO] (10),
715 [M+ + H – 3 CO] (42), 613 [M+ + H – Ru(CO)3] (100).
7c (C15H16N2O6Ru): 134 mg (45%) yellow powder. 1H NMR
(400 MHz, CD3OD): δ = 1.23 (t, J = 7.1 Hz, 3 H), 2.49 (s, 3 H),
2.51 (s, 3 H), 2.56–2.67 (m, 2 H), 3.29–3.40 (m, 2 H), 4.12–4.25 (m,
6c (C18H16N2O4Ru): 268 mg (89%) yellow powder. 1H NMR
(400 MHz, CDCl3): δ = 2.12 (s, 3 H), 2.57 (s, 3 H), 2.59–2.65 (m, 2 H), 4.35 (s, 1 H) ppm. 13C NMR (100 MHz, DEPT, CD3OD): δ
2 H), 3.35–3.46 (m, 2 H), 4.23 (s, 1 H), 7.29 (t, J = 7.2 Hz, 1 H),
= 14.4 (CH3), 39.5 (CH3), 43.4 (CH3), 48.0 (CH), 48.9 (CH2), 51.9
(CH2), 63.1 (CH2), 64.1 (C), 109.9 (C), 123.1 (C), 167.6 (C), 168.9
7.36 (t, J = 7.1 Hz, 2 H), 7.42 (d, J = 8.0 Hz, 2 H) ppm. 13C NMR
(100 MHz, DEPT, CDCl3): δ = 39.3 (CH3), 43.6 (CH3), 45.5 (CH), (C), 196.1 (CO) ppm. IR: ν = 2962 (w), 2923 (w), 2873 (w), 2810
˜
48.1 (CH2), 51.0 (CH2), 73.0 (C), 111.2 (C), 121.2 (C), 127.6 (CH), (w), 2056 (s), 1987 (s), 1718 (m), 1638 (s), 1592 (s), 1544 (s), 1446
128.4 (CH), 131.9 (C), 132.5 (CH), 170.6 (C), 196.0 (CO) ppm. IR: (m), 1416 (s), 1326 (s), 1311 (m), 1267 (m), 1214 (s), 1176 (s), 1115
ν = 2959 (w), 2929 (w), 2870 (w), 2805 (w), 2047 (s), 1966 (s), 1621
(m), 1044 (s), 941 (m), 856 (w), 792 (w), 739 (m), 706 (m), 641 (w),
˜
(s), 1568 (m), 1538 (s), 1496 (m), 1445 (m), 1412 (m), 1361 (m), 565 (s) cm–1. MS (EI): m/z (%) = 422 [M+] (5), 397, 396, 395, 394,
1311 (w), 1268 (w), 1202 (w), 1112 (m), 927 (w), 758 (m), 732 (m),
700 (s), 642 (m) cm–1. MS (EI): m/z (%) = 429, 428, 427, 426, 425,
424, 423, 420 [1:5:2:10:6:4:4:2, distribution of M+ isotopes] (2), 398
(3) [M+ – CO], 370 (10) [M+ – 2 CO], 342 (15) [M+ – 3 CO], 240
(100) [M+ – Ru(CO)3].
393, 392, 391, 388 [1:5:2:10:5:4:4:1, distribution of (M+ – CO) iso-
topes], 236 [M+ – 3 CO].
7d (C18H20N2O8Ru): 157 mg (45%) yellow powder. 1H NMR
(400 MHz, CD3OD): δ = 1.23 (t, J = 7.1 Hz, 6 H), 2.51 (s, 6 H),
2.67 (dd, J = 6.8, 3.7 Hz, 1 H), 2.71 (dd, J = 6.4, 4.0 Hz, 1 H), 3.36
(dd, J = 6.8, 4.0 Hz, 1 H), 3.41 (dd, J = 6.8, 3.7 Hz, 1 H), 4.19 (q,
J = 7.1 Hz, 1 H), 4.20 (q, J = 7.1 Hz, 1 H) ppm. 13C NMR
(100 MHz, DEPT, CD3OD): δ = 14.3 (CH3), 42.8 (CH3), 50.7
(CH2), 62.4 (C), 63.3 (CH2), 115.0 (C), 167.1 (C), 170.0 (C), 195.5
6d (C26H24N2O6Ru): 368 mg (93%) yellow powder. 1H NMR
(400 MHz, CD3OD): δ = 2.23–2.31 (m, 2 H), 2.54–2.68 (m, 1 H),
2.80–2.88 (m, 3 H), 3.05–3.17 (m, 1 H), 3.28–3.35 (m, 2 H), 3.45–
3.56 (m, 1 H), 3.61–3.68 (m, 2 H), 3.82–3.91 (m, 1 H), 7.13–7.50
(m, 10 H) ppm. 13C NMR (100 MHz, DEPT, CD3OD): δ = 49.3 (CO) ppm. IR: ν = 2981 (w), 2932 (w), 2873 (w), 2064 (s), 1986 (s),
˜
(CH2), 57.4 (CH2), 60.3 (CH2), 72.1 (C), 118.2 (C), 129.2 (CH),
1710 (s), 1643 (s), 1538 (m), 1515 (m), 1415 (m), 1381 (m), 1361
129.7 (CH), 133.1 (C), 134.2 (CH), 171.6 (C), 197.0 (CO) ppm. IR: (m), 1324 (m), 1265 (m), 1208 (m), 1176 (m), 1088 (m), 1055 (m),
ν = 3335 (br.) , 3058 (w), 2962 (w), 2926 (w), 2875 (w), 2052 (s), 1018 (m), 974 (m), 844 (w), 755 (w), 699 (w), 617 (m) cm–1. MS
˜
1971 (s), 1603 (m), 1540 (s), 1495 (m), 1437 (m), 1355 (m), 1260 (EI): m/z (%) = 494 [M+] (5), 469, 468, 467, 466, 465, 464, 463, 460
(m), 1158 (w), 1044 (s), 1028 (s), 910 (w), 799 (m), 752 (m), 725 (s), [1:5:9:5:4:3:2:1, distribution of (M+ – CO) isotopes] (71), 308 [M+
697 (s) cm–1. MS (ESI, TBME): m/z (%) = 566, 565, 564, 563, 562, Ru(CO)3] (100).
–
Eur. J. Org. Chem. 2007, 2815–2824
© 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
2823

E. Haak
FULL PAPER
8a (C25H21N3O5Ru): 380 mg (99%) yellow powder. 1H NMR
(400 MHz, CDCl3): δ = 2.15 (s, 3 H), 2.61 (ddd, J = 12.0, 10.4,
2.9 Hz, 1 H), 3.01 (dt, J = 13.3, 3.0 Hz, 1 H), 3.14 (dt, J = 12.0,
1256 (w), 1108 (m), 1069 (m), 1026 (m), 957 (w), 770 (s), 734 (m),
698 (w), 622 (m) cm–1. MS (ESI, TBME): m/z (%) = 556, 555, 554,
553, 552, 551, 550, 547 [1:4:3:8:6:4:4:1, distribution of (M+ + 2 H)
3.0 Hz, 1 H), 3.15 (s, 3 H), 3.56 (ddd, J = 13.2, 10.3, 2.9 Hz, 1 H), isotopes] (100), 525 [M+ + 2 H – CO] (78), 495 [M+ – 2 CO] (12),
7.05 (t, J = 7.4 Hz, 1 H), 7.26–7.30 (m, 3 H), 7.36–7.43 (m, 4 H),
7.61–7.64 (m, 2 H), 11.55 (s, 1 H) ppm. 13C NMR (100 MHz,
DEPT, CDCl3): δ = 42.4 (CH3), 47.7 (CH3), 48.7 (CH2), 50.4
(CH2), 54.7 (C), 72.7 (C), 114.9 (C), 118.6 (C), 120.1 (CH), 123.6
(CH), 128.3 (CH), 128.8 (CH), 128.8 (CH), 131.1 (C), 132.5 (CH),
367 [M+ + 2 H – Ru(CO)3] (45).
Acknowledgments
Constant support by Prof. Dr. Dr. h. c. H. Hopf and by the Fonds
der Chemischen Industrie is gratefully acknowledged.
138.7 (C), 164.3 (C), 170.7 (C), 194.2 (CO) ppm. IR: ν = 3028 (w),
˜
2927 (w), 2858 (w), 2058 (s), 1982 (s), 1676 (m), 1588 (s), 1536 (s),
1495 (s), 1443 (s), 1410 (m), 1359 (s), 1331 (m), 1309 (w), 1252 (m),
1117 (w), 1069 (w), 1028 (w), 962 (w), 890 (w), 850 (w), 754 (s),
732 (s), 693 (s), 626 (w) cm–1. MS (ESI, TBME): m/z (%) = 549,
548, 547, 546, 545, 544, 543, 540 [1:4:2:8:4:3:3:2, distribution of
(M+ + H) isotopes] (100), 518 [M+ + H – CO] (45), 490 [M+ + H –
2 CO] (22), 462 [M+ + H – 3 CO] (50).
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B. A. Persson, M. L. Ray, J.-E. Bäckvall, J. Am. Chem. Soc.
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[8] a) Y. Shov, D. Czarkie, J. Am. Chem. Soc. 1986, 108, 7400–
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8b (C29H23N3O5Ru): 177 mg (42%) yellow powder. 1H NMR
(300 MHz, CDCl3): δ = 2.11 (s, 3 H), 2.60 (ddd, J = 12.0, 10.5,
2.7 Hz, 1 H), 2.99 (dt, J = 13.2, 2.9 Hz, 1 H), 3.10 (dt, J = 12.0,
3.0 Hz, 1 H), 3.17 (s, 3 H), 3.56 (ddd, J = 13.2, 10.4, 2.8 Hz, 1 H),
7.42–7.49 (m, 8 H), 7.61 (d, J = 8.2 Hz, 1 H), 7.79–7.82 (m, 1 H),
8.18–8.21 (m, 1 H), 8.38 (dd, J = 7.6, 1.1 Hz, 1 H), 12.07 (s, 1 H)
ppm. 13C NMR (75 MHz, DEPT, CDCl3): δ = 42.4 (CH3), 47.6
(CH3), 48.8 (CH2), 50.4 (CH2), 55.0 (C), 72.8 (C), 115.3 (C), 118.4
(C), 118.5 (CH), 121.5 (CH), 124.2 (CH), 125.7 (CH), 125.8 (CH),
126.1 (C), 126.3 (CH), 128.3 (CH), 128.4 (CH), 128.9 (CH), 131.2
(C), 132.7 (CH), 133.7 (C), 134.0 (C), 164.7 (C), 171.1 (C), 194.3
(CO) ppm. IR: ν = 3052 (w), 2957 (w), 2924 (w), 2855 (w), 2059
˜
(s), 1982 (s), 1679 (s), 1535 (s), 1500 (s), 1442 (m), 1407 (m), 1359
(s), 1330 (m), 1255 (w), 1118 (w), 1058 (w), 1028 (w), 960 (w), 796
(s), 770 (s), 732 (s), 696 (s) cm–1. MS (ESI, TBME): m/z (%) = 599,
598, 597, 596, 595, 594, 593, 590 [1:4:2:8:5:4:3:1, distribution of
(M+ + H) isotopes] (100), 568 [M+ + H – CO] (35), 540 [M+ + H –
2 CO] (42), 512 [M+ + H – 3 CO] (37).
[9] a) Y. Blum, Y. Shvo, D. F. Chodosh, Inorg. Chim. Acta 1985,
97, C25–C26; b) Y. Blum, Y. Shvo, D. Czarkie, Y. Rahamim,
Organometallics 1985, 4, 1459–1461; c) Y. Blum, Y. Shvo, Isr.
J. Chem. 1984, 24, 144–148.
8c (C25H27N3O5Ru): 132 mg (34%) yellow powder. 1H NMR
(400 MHz, CD3OD): δ = 1.25–1.31 (m, 3 H), 1.32–1.45 (m, 2 H),
1.55–1.62 (m, 1 H), 1.68–1.74 (m, 2 H), 1.86–1.90 (m, 2 H), 2.06
(s, 3 H), 2.60 (ddd, J = 12.5, 9.5, 3.2 Hz, 1 H), 2.98 (s, 3 H), 3.01
(dt, J = 13.3, 3.3 Hz, 1 H), 3.26 (dt, J = 12.4, 3.7 Hz, 1 H), 3.54
(ddd, J = 12.8, 9.6, 3.3 Hz, 1 H), 3.78–3.85 (m, 1 H), 7.40–7.44 (m,
5 H) ppm. 13C NMR (100 MHz, DEPT, CD3OD): δ = 25.4 (CH2),
25.5 (CH2), 26.7 (CH2), 33.3 (CH2), 33.6 (CH2), 43.0 (CH3), 45.2
(CH3), 49.5 (CH), 50.7 (CH2), 51.1 (CH2), 58.6 (C), 73.8 (C), 115.6
(C), 120.6 (C), 129.4 (CH),129.8 (CH), 132.7 (C), 134.0 (CH), 166.6
[10] E. Haak, Synlett 2006, 1847–1848.
[11] a) B. Eistert, A. J. Thommen, Chem. Ber. 1971, 104, 3048–3061;
b) R. Gompper, H. Glöckner, Angew. Chem. 1984, 96, 48–49.
[12] a) V. Cadierno, M. P. Gamasa, J. Gimeno, Eur. J. Inorg. Chem.
2001, 571–591; b) V. Cadierno, J. Diez, M. P. Gamasa, J. Gi-
meno, E. Lastra, Coord. Chem. Rev. 1999, 193–195, 147–205;c)
M. I. Bruce, Chem. Rev. 1998, 98, 2797–2858; d) G. Esquius, J.
Pons, R. Yanes, J. Ros, R. Mathieu, N. Lugan, B. Donnadieu,
J. Organomet. Chem. 2003, 667, 126–134; e) E. Bustelo, M.
Jimenez-Tenorio, M. C. Puerta, P. Valerga, Eur. J. Inorg. Chem.
2001, 2391–2398.
(C), 171.0 (C), 196.3 (CO) ppm. IR: ν = 2928 (m), 2853 (w), 2056
˜
Received: January 24, 2007
(s), 1975 (s), 1649 (s), 1612 (s), 1575 (s), 1435 (s), 1411 (s), 1357 (s),
Published Online: April 11, 2007
2824
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