Intermolecular Dehydrative Coupling and Intramolecular Cyclization of Ruthenium Vinylidene Complexes Formed from Aromatic Propynes Containing Carbonyl Functionalities

Article abstract of DOI:10.1002/asia.201801303

A remarkable intermolecular dehydrative coupling reaction with the formation of a C?C bond was found for the vinylidene complex 2 a, yielding the dinuclear bisvinylidene complex 4 a. Complex 2 a containing 1-hydroxyindan moiety was first formed from the reaction of o-propynyl benzaldehyde 1 a with [Ru]–Cl ([Ru]=Cp(PPh₃)₂Ru) by a cyclization process. For analogous aldehyde 1 b containing an additional 1,3-dioxolane group on the aryl ring, similar intermolecular coupling yields the dinuclear bisvinylidene complex 4 b. However, the fluoro group on the aryl ring in aldehyde 1 c inhibits the coupling reaction, giving only the vinylidene complex 2 c. For the reactions of [Ru]–Cl in MeOH with compounds 1 f, 1 g and 1 h, each with a ketone functionality, cyclization gives vinylidene complexes 2 f, 2 g and 2 h, respectively. However, no similar intermolecular coupling was observed, instead, the intramolecular dehydration yields 8 f, 8 g and 8 h, respectively. In CDCl₃, catalytic cyclization is observed for the o-propynylphenyl ketone 1 h with [Ru]–Cl at 50 °C giving the isochromene products 14 h. Furthermore, treatment of the o-propynylaryl α,β-unsaturated ketones 1 k–m and 1 n with [Ru]–Cl in MeOH affords the corresponding vinylidene complexes 10 k–m and 11 n each with 1-benzosuberone moiety in the presence of NH₄PF₆. These intramolecular cyclization products were formed by the addition of Cβ onto the terminal carbon of the alkene moiety. All these reaction products were characterized by spectroscopic methods. In addition, structures of complexes 4 a, and 10 l were confirmed by single crystal X-ray diffraction analysis.

Full text of DOI:10.1002/asia.201801303

CHEMISTRY
AN ASIAN JOURNAL
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Accepted Article
Title: Intermolecular Dehydrative Coupling and Intramolecular
Cyclization of Ruthenium Vinylidene Complexes Formed from
Aromatic Propynes Containing Carbonyl Functionalities
Authors: Pi-Yeh Chia, Cheng-Chen Kuo, Shou-Ling Huang, Yi-Hong
Liu, Ling-Kang Liu, and Ying Chih Lin
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10.1002/asia.201801303
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Intermolecular Dehydrative Coupling and Intramolecular Cyclization of
Ruthenium Vinylidene Complexes Formed from Aromatic Propynes
Containing Carbonyl Functionalities
Pi-Yeh Chia, [a] Cheng-Chen Kuo,[a] Shou-Ling Huang,[a] Yi-Hong Liu,[a] Ling-Kang Liu,[a] and Ying-Chih
Lin,*[a]
Dedication ((optional))
Abstract: A remarkable intermolecular dehydrative coupling reaction with
formation of a C-C bond was found for the vinylidene complex 2a, yielding
the dinuclear bisvinylidene complex 4a. Complex 2a containing 1-
hydroxyindan moiety was first formed from the reaction of o-propynyl
employing terminal alkynes.2a-e The nucleophilic addition of Cβ of the
vinylidene moiety onto a proper functional group2f is commonly
observed, even though addition of the electrophilic Cα of the vinylidene
moiety onto electron-rich atoms is also possible.2g Recently, metal
benzaldehyde 1a with [Ru]-Cl ([Ru] = Cp(PPh3)2Ru) by a cyclization process. complexes of gold, palladium, copper, and tungsten have been shown to
For analogous aldehyde 1b containing an additional 1,3-dioxolane group on
the aryl ring, similar intermolecular coupling yields the dinuclear
bisvinylidene complex 4b. However, the fluoro group on the aryl ring in
aldehyde 1c inhibits the coupling reaction, thus the reaction gives only the
vinylidene complex 2c. For the reactions of [Ru]-Cl in MeOH with
compounds 1f, 1g and 1h, each with a ketone functionality, cyclization gives
the vinylidene complexes 2f, 2g and 2h, respectively. However, no similar
intermolecular coupling was observed, instead, the intramolecular
dehydration yields 8f, 8g and 8h, respectively. In CDCl3, catalytic cyclization
is observed for the o-propynylphenyl ketone 1h with [Ru]-Cl at 50 °C giving
the isochromene products 14h. Furthermore, treatment of the o-propynylaryl
α,β-unsaturated ketones 1k-m and 1n with [Ru]-Cl in MeOH affords the
corresponding vinylidene complexes 10k-m and 11n each with 1-
benzosuberone moiety in the presence of NH4PF6. These intramolecular
cyclization products are formed by the addition of Cβ onto the terminal
carbon of the alkene moiety. All these reaction products are characterized by
spectroscopic methods. In addition, structures of complexes 4a, and 10l are
confirmed by single crystal X-ray diffraction analysis.
induce intramolecular cyclization of alkynes with oxygen-containing
functional groups, forming benzofuran rings.3 Saá and co-workers
reported Ru-catalyzed cycloisomerizations of aromatic homo- and bis-
homopropargylic alcohols affording benzofurans and isochromenes.4
We recently described the cyclization of terminal arylalkynes containing
aldehyde, ketone or hydroxyl functionality on the aryl ring induced by
ruthenium complex giving isochromene carbene, isobenzofuryl carbene
and cyclic oxocarbene complexes.5 The cascade cyclization reactions of
several aromatic 1,n-propargylic enynes (n = 7 or 8) catalyzed by
ruthenium via allenylidene and vinylidene intermediates forming
tricyclic compounds was also reported by us.6
In using terminal alkyne for these studies, it is common to see the
monosubstituted vinylidene ligand, instead of the disubstituted one.
Several methods for preparing disubstituted metal vinylidene complex
have been developed recently, for instance, electrophilic attack on C of
an acetylide complex by alkyl halide7, halogen8 or diazonium salt9, and
deprotonation of carbyne complex.10 Ishii and his co-workers reported
preparation of the disubstituted vinylidene metal complex directly from
internal alkyne via 1,2-migration of their carbon substituent.11 The
disubstituted vinylidene with a heteroatom bound to Cβ can also be
obtained from heteroatom-substituted internal alkyne.12 In addition, we
reported that the nucleophilic addition of propargyl Grignard reagent to
Cγ and subsequent Au(PR3)-catalyzed cyclization of the resulting diyne
yielded a vinylidene with the Cβ incorporated into a five-membered
ring.13
Saá and co-workers reported the intramolecular dehydrative
cyclization of vinylidene complexes of iridium, osmium and rhodium
obtained from alkynals.14a Compared to the well-established
intramolecular dehydration, the intermolecular dehydration is relatively
rare, while a few catalytic reactions had been reported.14b, c In recent
years, reaction of inexpensive and abundantly available alcohols (C-OH)
with a C-H bond of the other unactivated nucleophilic coupling partners,
leading to the construction of a C-C bond, has emerged as one of the
vital strategies since it is an atom-economical and environmentally
benign approach yielding only water as the by-product. Studies on the
transition metal-catalyzed dehydrative coupling have been reported
previously.15 The development of metal-free approach for the direct
dehydrative functionalization of the C-OH bond by Brønsted and Lewis
acid with various carbon nucleophile has gained significant attention.
Coupling of Csp3-OH with Csp3-H leading to a Csp3-Csp3 bond formation
Introduction
The development of effective strategies for the synthesis of cyclic
and heterocyclic compounds is an important challenge for modern
organic chemistry and natural products synthesis.1 Various transition
metal vinylidene complexes are found to serve as important
intermediates in these synthetically important organic transformations
[a]
P.-Y. Chia, C.-C. Kuo, Prof. Dr. L.-K. Liu, Prof. Dr. Y.-C. Lin, S.-L.
Huang, Y.-H. Liu
Department of Chemistry
National Taiwan University
Taipei, 106 (Taiwan)
E-mail: yclin@ntu.edu.tw
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has been explored for the dehydrative reaction of allylic, benzylic and
propargylic alcohols with 1,3-dicarbonyls by using Brønsted and Lewis
acids.16 The advantage of these coupling processes is the formation of
H2O as the only by-product. Compared with halide reagents, alcohols
are inexpensive and environmentally and friendly coupling reagents.
However, it is rare to see an alcohol employed as coupling agent,
because of the tendency to undergo energetically more favorable
alkoxylation or dehydrogenation reactions over the respective C-O bond
cleavage reaction.
Herein, we report the cyclization reactions of benzenefused o-
propynyl aldehyde or ketone induced by [Ru]-Cl ([Ru] = CpRu(PPh3)2)
yielding organometallic compounds. The cyclization proceeds by
formation of a vinylidene ligand followed by intramolecular addition of
the carbonyl carbon to Cβ to give the disubstituted vinylidene complexes
with a 1-hydroxyindan moiety. Depending on the type of carbonyl
substrates, reaction conditions, or solvents used, the vinylidene
complexes can undergo further reactions and proceed via inter-
molecular dehydrative coupling, intramolecular dehydration,
alkoxylation and demetallation reactions.
Attempted crystallization from a mixture of 2a and 4a in CH2Cl2
yielded only single crystals of 4a. Compound 2a was not observed in the
remaining solution, showing spontaneous dehydration of 2a to give 4a.
The structural assignment of 4a is based on 1H, 31P, 13C NMR data and
a single crystal X-ray diffraction analysis. The doublet 1H NMR
resonance at δ 3.88 is assigned to the OH group, which disappears upon
addition of D2O. Two sets of two doublet peaks are observed at δ 41.64,
39.56, 41.38 and 39.02 in the 31P NMR spectrum. Two characteristic
13Cα resonances for the vinylidene ligands appear at δ 341.8 and 338.9
both displaying doublet of doublet pattern. The solid state structure is
determined by a single crystal X-ray diffraction analysis confirming
formation of the dinuclear bisvinylidene complex. An ORTEP type view
of 4a is shown in Figure 1, with selected bond distances and angles. The
bond distance of 1.554(5) Å for the newly formed C10-C61 bond
indicates a typical single bond. The Ru1-C1, C1-C2, Ru2-C52 and C52-
C53 bond lengths of 1.850(4), 1.307(5), 1.860(4) and 1.301(5) Å, with
the Ru1-C1-C2 and Ru2-C52-C53 bond angles of 175.3(0)° and
175.5(3)°, respectively, showing two bonding skeletons of typical
vinylidene ligand.
Results and Discussion
Intermolecular Dehydrative Coupling. The reaction of [Ru]-Cl ([Ru] =
CpRu(PPh3)2) with o-propynyl benzaldehyde 1a in the presence of
NH4PF6 in MeOH at room temperature for 12 h yields the vinylidene
complex 3a with 1-methoxyindan moiety. The same reaction in CH2Cl2
for 12 h, gives a mixture of the cationic vinylidene complex 2a
containing a 1-hydroxyindan moiety and the dinuclear bisvinylidene
complex 4a in a ratio of 14:1, see Scheme 1. When the reaction is carried
out at reflux in CH2Cl2 for 1 day, only 4a is obtained in 82% yield. In
CH2Cl2 complex 3a is transformed slowly to 4a at room temperature.
The reactions of 2a and 3a in CDCl3 both giving 4a are faster at 40ºC.
Nevertheless, treatment of 1a with [Ru]-Cl and KF in MeOH afforded
the stable acetylide complex 5a, which was also obtained in high yield
by treating 2a with NaOMe. Transformation of 5a to 2a is achieved with
NH4PF6 or with other protic acids such as HBF4 in CH2Cl2. Acetic acid
promotes the dehydrative coupling reaction, but base inhibits the
reaction. In the presence of 5% of acid at 40 ºC, the transformation of 2a
to 4a is quantitative in 6 h and treatment of 2a with sodium methoxide
inhibits the dehydrative coupling.
Figure 1. An ORTEP drawing of 4a. Phenyl groups except Cipso atoms on the
phosphine ligands and PF6 have been omitted for clarity. Thermal ellipsoid is
-
set at the 35% probability level. Selected bond distances (Å) and bond angles
(deg): Ru1-C1, 1.850(4); C1-C2, 1.307(5); Ru2-C52, 1.860(4); C52-C53,
1.301(5); C10-C61, 1.554(5); O1-C3, 1.426(8); C2-C1-Ru1, 175.3(0); C3-C2-
C10, 108.8(3); C53-C52-Ru2, 175.53; C54-C53-C61, 108.4(3); C60-C61-C10,
113.4(3); O1-C3-C4, 117.0(4).
Intermolecular dehydrative coupling that involves activation of a
Csp3-H bond followed by a Csp3-Csp3 bond formation is rare. The coupling
reaction of 2a involves an unfavorable C-O bond cleavage. Metal-free
approaches for the direct dehydrative coupling of a Csp3-OH bond, such
as allylic, benzylic and propargylic alcohols, with Csp3-H bond of 1,3-
dicarbonyls derivatives catalyzed by Brønsted and Lewis acids have
been reported.17 These reactions are confined only to the use of 1,3-
dicarbonyl derivatives as carbon nucleophiles. Aminobenzannulation of
1a with various dialkylamines was reported to afford various 2-
aminonaphthalenes under metal-free condition.19
To further explore the reactivity of this unusual dimerization, two
similar aryl aldehydes 1b and 1c, with an electron-donating 1,3-
dioxolane group and with an electron-withdrawing fluoro group,
respectively, are synthesized. Different from 1a, both 1b and 1c react
Scheme 1. Reactions of 1a with [Ru]-Cl and intermolecular dehydrative
coupling of 2a.
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with [Ru]-Cl in CH2Cl2 in the presence of NH4PF6 giving complicated
crude products. Only in MeOH, treatment of 1b with [Ru]-Cl and
NH4PF6 affords the vinylidene complex 3b with a methoxy group, see
Scheme 2. Upon heating 3b in CDCl3 at 45 °C, a similar intermolecular
coupling process also yields the dinuclear bisvinylidene complex 4b in
81% yield. The reaction of 1c with [Ru]-Cl in MeOH also afforded the
vinylidene complex 3c, however, no further intermolecular coupling
reaction occurs, even when the solution of 3c is heated in CH2Cl2 or
CDCl3. The electron-withdrawing fluoro substituent on the aromatic
ring clearly inhibits the intermolecular dehydration,20 possibly by
hindering the elimination of OH or OR and destabilizing the carbocation
intermediate.
We propose a stepwise pathway for this dehydrative coupling
reaction, as shown in Scheme 3. In this process, the benzylic methylene
group of 2a could serve as an acid generating the zwtterionic C2 by
deprotonation, which protonates the hydroxyl group of the other 2a
inducing elimination of H2O to give intermediate C1 with a benzylic as
well as an allylic carbocation. Subsequent intermolecular C-C bond
formation occurs between the electrophilic and the nucleophilic benzylic
carbon atoms of C1 and C2, respectively, to yield the coupling product
4a. A concerted process by moving one 2a toward the other 2a via the
vinylidene ligand with the acidic proton of one 2a getting closer to the
hydroxyl group of the other 2a, followed by dehydration and formation
of a C-C bond to give 4a, is less likely. Because, approach of two sp3
carbon atoms would be difficult.
The reactions of 1d and 1e with o-oxo- and o-thio-propargyl
benzaldehydes with [Ru]Cl under the same reaction condition generate
the corresponding cyclization products 6d and 6e (Scheme 4) each with
a six-membered ring in CH2Cl2. In MeOH, along with 6d and 6e, relating
complexes 7d and 7e with methoxy groups are observed as a minor
product (6:1 in both cases). No intermolecular coupling is observed in
both 6 and 7, possibly because only one electrophilic benzylic carbon
exists.
Scheme 2. Reactions of two o-propynyl aryl aldehydes
Proposed mechanism for the formation of 4a from 1a on the basis
the above-mentioned observations is shown in Scheme 3. All reactions
of 1a yielding 2a, 3a, 4a and 5a are proposed to proceed via activation
of the triple bond forming the metal vinylidene complex A. In the
presence of KF, deprotonation of A generates 5a. For A to undergo
cyclization in CH2Cl2, transfer of a proton from CβH to the carbonyl
group forms the oxonium acetylide intermediate B. Subsequent
intramolecular C-C bond formation via attack of Cβ onto the carbonyl
carbon gives 2a with a five-membered ring. Coupling of the aldehyde
carbon with Cβ of the vinylidene ligand was previously reported.14 The
cationic character of 2a along with the presence of two benzylic and
allylic carbon atoms in the five-membered ring play crucial role in
stimulating the subsequent dehydrative coupling reaction.
Scheme 4. Reactions of 1d and 1e with [Ru]-Cl.
The Reaction of the o-Propynylphenyl Ketones. With this unique
dehydrative coupling process in mind, we carried out reactions of [Ru]-
Cl with five aryl propynes 1f-1j containing ortho-substituted keto
derivatives, see Scheme 5. These compounds display different reactions
depending on various functional groups on the keto part, see Scheme 5,
and the solvents used. The reactions of 1f-1j with [Ru]Cl in the presence
of NH4PF6 in CH2Cl2 first give corresponding complexes 2f-2j. Then for
2f-2h each with a hydrogen near the hydroxyl group, intramolecular
dehydration gives 8f-8h. Interestingly, for the reaction of 1h in MeOH,
a mixture of the MeO-substituted complex 3h and 8h (5:1) is observed
first, which is also converted to 8h (E/Z isomer ratio 3:1) in CH2Cl2. But
complexes 2i and 2j (R = t-Bu and Ph), with no such hydrogen, are stable,
as shown in Scheme 5.
Scheme 3. Proposed mechanism for the formation of 2a and subsequent
transformation to 4a.
Scheme 5. Reactions of o-propynyl aryl ketone with no α,β-unsaturated olefin.
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The structures of these complexes are determined by NMR
spectroscopy. No further intermolecular coupling was observed for all
complexes 2f-2j derived from these keto derivatives, possibly because
of the preferred intramolecular process and the steric effect of the
substituted group near the hydroxyl group prohibiting the intermolecular
dehydration reaction. Maybe the steric effect inhibits replacement of the
OH group by an OMe group.
For 2g, with an allyl group, the dehydration process, giving 8g
containing an 1,4-diene moiety, is followed by an additional C-C bond
formation yielding the organic fluorene 9g at 50°C for 3 day in 27%
yield, Scheme 5. The cyclization of 8g proceeds via intramolecular
nucleophilic attack of the terminal unsaturated alkenes onto the
electrophilic Cα of the vinylidene moiety followed by demetallation.
Previously, we reported several ruthenium-catalyzed cyclizations of
aromatic 1,n-propargylic enynes (n = 7 or 8) via allenylidene and
vinylidene intermediates, and if the intermediate contains tethering
olefinic chain, cascade cyclization via intramolecular nucleophilic
addition of the double bond to Cα of the allenylidene or vinylidene
ligand would form tricyclic compounds.5
Ruthenium-catalyzed cyclizations or cycloisomerizations of terminal
alkynes commonly proceed via vinylidene intermediates followed by
nucleophilic attack at Cα of the vinylidene ligand.3,29 But the cyclization
of 1h occurs when the alkyne is π-coordinated to the Ru metal center
causing the nucleophilic attack of the carbonyl oxygen to occur at the
internal carbon Cβ of the η2-alkynyl ligand. An asymmetric synthesis of
chiral isochromenes catalyzed by Cu(II) phosphate with intramolecular
cyclization via 6-endo-dig cyclization and asymmetric transfer
hydrogenation sequence of o-alkynylaceto-phenone derivatives was
previously reported.28 Nevertheless, when 1a is treated with a catalytic
amount of [Ru]-Cl, no organic product other than 1a is isolated.
Interestingly, 1h displays solvent dependent reactivity, namely,
heating 1h in CDCl3 at 50°C for 6 h in the presence of 20 mol% of [Ru]-
Cl gives the isochromene 14h in 73% isolated yield. (Scheme 6) The
isochromene motif is commonly found in biologically active natural
products.25 Some derivatives of isochromene ring display significant
pharmacological potential exhibiting extensive range of biological
activities including anticancer and antibacterial activity.26 The proposed
mechanism for the formation of 14h is shown in Scheme 6. The triple
bond of 1h is activated electrophilically by [Ru]-Cl leading to formation
of the η2-coordinated species D. Then the 6-exo-dig cyclization via a
nucleophilic attack of the carbonyl oxygen to the internal carbon of the
η2-alkyne ligand generates E. This is followed by deprotonation and 1,3-
hydrogen shift to give F. In the presence of HCl, 14h is produced with
regeneration of [Ru]-Cl. On the basis of NMR spectrum only one isomer
was obtained.
Scheme 7. Reactions of o-propynyl aryl α,β-unsaturated ketone.
Interestingly, for several α,β-unsaturated ketones 1k-1n, a
different mode of cyclization is observed. Namely the C-C bond
formation occurs only between the internal carbon of the alkyne and the
terminal carbon of olefinic group yielding organometallic vinylidene
complexes with sevenycli-membered ring ligand. (Scheme 7) Treatment
of 1k-1m with [Ru]-Cl in the presence of NH4PF6 in MeOH affords the
vinylidene complexes 10k-10m respectively, each with 1-
benzosuberone moiety containing
a seven-membered ring. The
structures of 10k-10m are determined by NMR data. The vinylidene
complex with a five-membered ring similar to 2 or 3 is not observed.
The C-C bond formation occurs exclusively at the olefinic terminal
carbon giving a seven-membered ring, instead of at the carbonyl carbon.
This type of cyclization is also observed in the reactions of 1o, 1o’,
1p and 1p’ with [Ru]-Cl, producing corresponding complexes 12o, 12o’ ,
12p and 12p’ containing eight-membered heterocyclic ring. (see lower
part of Scheme 7) As also shown in the upper left part of Scheme 7,
treatment of 1n with [Ru]Cl in MeOH affords the vinylidene complex
11n with an enol ether. In this case, two terminal methyl groups may
limit the ring flipping, thus preventing transformation of the enol form
to give the keto form. Analogous product 11n’ with an OEt group is
obtained in EtOH. The structural assignment of 11n and 11n’ is based
1
on H, 31P, 13C NMR and other spectroscopic data. In the 1H NMR
spectrum of 11n, two singlet resonances at δ 3.02 and 5.56 are assigned
to the OMe group and to the olefinic hydrogen in the seven-membered
ring, respectively.
Single crystals of 10l are obtained from
a mixture of
CH2Cl2/toluene solution and the structure is determined by single crystal
Scheme 6. Formation of isochromene 14h and proposed mechanism
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X-ray diffraction analysis. An ORTEP type view of 10l is shown in
Figure 2 with selected bond distances and angles. The Ru1-C1 and C1-
C2 bond lengths of 1.860(4) and 1.312(5) Å and the linear Ru1-C1-C2
bond angle of 170.1(3)° show a typical Ru=C=C vinylidene bonding
skeleton. The bond distance of 1.210(6) Å for O1-C5 indicates a normal
C=O bond. Two bond distances of 1.545(7) and 1.510(7) Å for C3-C4
and C4-C5, respectively, indicate typical C-C single bonds.
In these cases, a C-C bond formation then takes place between Cβ and
the carbonyl carbon in B’ yielding 2. For aldehydes 1a and 1b, further
intermolecular coupling would generate dinuclear complexes 4a and 4b.
But for a ketone with no α,β-unsaturated group, intramolecular
dehydration generates 8 containing an exo alkene. In the case of α,β-
unsaturated ketones, the Micheal-addition of G leads to a C-C bond
formation between Cβ and the terminal carbon, as shown in Scheme 8,
yielding the di-substituted vinylidene enol intermediate H.
Tautomerization then gives the cyclic ketone complex 10k.
The favored C-C bond formation of the olefinic carbon over the
carbonyl group is also shown in the cyclization reaction of the aryl
alkyne 1q with an ortho-substituted α,β-unsaturated ketone but
containing internal alkene and terminal aldehyde, Scheme 9.
Figure 2. An ORTEP drawing of 10l. Phenyl groups except the Cipso atoms on
the phosphine ligands and PF6- have been omitted for clarity. Thermal ellipsoid
is set at the 35% probability level. Selected bond distances (Å) and bond angles
(deg): Ru1-C1, 1.860(4); C1-C2, 1.312(5); O1-C5, 1.210(6); C3-C13, 1.530(7);
C2-C1-Ru1, 170.1(3); C2-C3-C4, 111.1(4); O1-C5-C4, 120.0(5); C13-C3-C4,
108.7(4)
Scheme 9. Michael addition reaction of α,β-unsaturated aldehyde 1q with
[Ru]Cl and addition of water to 1j catalyzed by [Ru]Cl.
The reaction of 1q with [Ru]-Cl in MeOH yields 13q keeping the
aldehyde group. These results show that the Michael type addition is a
favored pathway. The C-C bond formation takes place between Cβ of
the alkyne and the internal alkene group. Attempted cyclization
reactions of ketones 1j in the presence of water cause addition of water
to the terminal alkyne yielding the diketone compounds 15j. (Scheme 9)
These reactions are made catalytic by the use of 20 mole percent of
[Ru]Cl.
Proposed mechanism for the overall cyclization processes of various
o-propynyl aryl aldehydes and ketones induced by [Ru]-Cl is shown in
Scheme 8. The first step is the formation of the vinylidene intermediate
A’, see also Scheme 3, followed by a proton transfer of CβH to the
carbonyl oxygen forming the acetylide intermediate B’ for an aldehyde
or a ketone with no unsaturated C=C double bond.
Conclusions
A new intermolecular dehydrative coupling reaction is observed
in our systematic studies on the ruthenium complex mediated cyclization
reactions of aryl propynes with ortho-substituted aldehyde or ketone
groups. This dehydrative coupling reaction of the two specific
vinylidene complexes 2a and 2b involves unfavorable C-O bond
cleavage and activation of a Csp3-H bond. The cyclizations of aryl
propynes with aldehyde or with simple ketone on the aryl ring would
proceed by formation of vinylidene ligand. Then transfer of the
vinylidene hydrogen to the oxygen atom assists formation of an
acetylide complex with oxonium group. Subsequent coupling of the
carbonyl carbon with Cβ atom gives the disubstituted vinylidene
complexes with
a
1-hydroxyindan moiety. The subsequent
intermolecular dehydrative coupling reaction, giving the dinuclear bis-
vinylidene complexes, occurs only for two starting substrates 1a and 1b
with aldehyde group, and the coupling is promoted by heat or weak
protic acid such as acetic acid. Conversely, in the reaction of aryl alkynes
with ketone groups, the intramolecular dehydration takes place if nearby
Scheme 8. Proposed mechanism for the overall cyclization of o-propynyl aryl
carbonyl compounds induced by [Ru]-Cl.
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2.40 (s, 1H, OH); 1.55 (s, 3H, CH3); 13C NMR (δ, CDCl3): 352.03 (t, 3JCP = 15.5
Hz, Cα); 147.17-127.21 (Ph and Cβ); 94.26 (Cp); 84.50 (CCH3); 30.76 (CH3);
hydrogen is available. For the α,β-unsaturated ketone, the intramolecular
attack of Cβ onto the alkene moiety gives vinylidene complexes with a
1-benzosuberone moiety. Furthermore, demetallation of disubstituted
vinylidene complex is achieved in the reaction of o-propynylphenyl β,γ-
unsaturated ketone. Subsequent intramolecular nucleophilic addition of
the terminal double bond to Cα of the vinylidene ligand gives fluorene
as the unique organic product. In addition, we demonstrated the
cyclization via nucleophilic attack of the carbonyl oxygen to the alkyne
moiety in the presence of ruthenium catalyst to afford the corresponding
isochromene derivatives. For aryl propynes with ortho-substituted
aldehyde or ketone with either terminal or internal α,β-unsaturated
olefinic groups, the C-C bond formation favorably takes place on the
olefinic, instead of the carbonyl group.
2
30.56 (CH2); 31P NMR (δ, CDCl3): 42.22, 42.02 (2d, JPP = 27.5 Hz, PPh3). MS
(ESI+) m/z: 849.1981 (M)+. Spectroscopic data of 8f: 1H NMR (δ, CDCl3): 7.52-
7.04 (m, 34H, Ph); 5.70, 4.93 (s, 1H, =CH2); 5.32 (s, 5H, Cp); 3.88 (s, 2H, CH2);
3
13C NMR (δ, CDCl3): 359.6 (t, JCP = 15.3 Hz, Cα); 140.6-120.3 (Ph and Cβ);
139.4 (=C); 105.2 (=CH2); 94.4 (Cp); 30.8 (CH2); 31P NMR (δ, CDCl3): 41.82 (s,
PPh3). MS (ESI+) m/z: 831.1911 (M)+. No analysis data were obtained.
Synthesis of 2i. The synthesis of 2i from 1i (0.106 g, 0.53 mmol) and [Ru]-Cl
(0.36 g 0.50 mmol) for 20 h followed the standard procedure as the synthesis of
2a. The final product can be obtained as a pink powder identified as 2i (0.40 g,
77%). Spectroscopic data of 2i: 1H NMR (δ, CDCl3): 7.44-6.80 (m, 34H, Ph); 5.05
(s, 5H, Cp); 3.95, 3.43 (2d, 2H, CH2); 1.06 (s, 9H, C(CH3)3); 0.47 (s, 1H, OH);
13C NMR (δ, CDCl3): 345.58, 345.39 (dd, 3JCP = 12.5 Hz, Cα); 144.16-124.55 (Ph
and Cβ); 94.80 (Cp); 92.94 (CC(CH3)3); 40.73 (C(CH3)3); 32.2 (CH2); 25.40
2
((CH3)3C); 31P NMR (δ, CDCl3): 41.61, 41.05 (2d, JPP = 26.1 Hz, PPh3). MS
(ESI+) m/z: 891.2458 (M)+. Elemental analysis calcd (%) for C55H51F6OP3Ru: C,
63.76; H, 4.96; found: C, 63.60; H, 4.89.
Experimental Section
Synthesis of 2j. The synthesis of complex 2j (0.33 g, 81%) from 1j (0.086 g, 0.39
mmol) and [Ru]-Cl (0.28 g 0.39 mmol) for 20 h followed the standard procedure
as the synthesis of 2i. The final product can be obtained as a pink powder.
General procedures: Manipulations were performed under an atmosphere of dry
nitrogen by using vacuum-line and standard Schlenk techniques unless mentioned
otherwise. All reagents were obtained from commercial suppliers and were used
without further purification. Solvents were dried by standard methods and were
distilled under nitrogen before use. NMR spectra were recorded on Brucker
AVIII-400, DMX-500 or on AVIII-800 FT-NMR spectrometer at room
temperature and were reported in units of δ with residual protons in the solvents
as a standard. Electrospray ionization mass spectrometry, elemental analyses and
X-ray diffraction studies were carried out at the Regional Center of Analytical
Instrument located at National Taiwan University. The ruthenium complex
Cp(PPh3)2RuCl30 and compound 1a-1q19 were prepared by following the method
reported in the literature.
Synthesis of 2a and Conversion to 4a. A mixture of [Ru]-Cl (0.30 g, 0.41 mmol),
1a (0.066 g, 0.46 mmol), and NH4PF6 (0.074 g, 0.45 mmol), in CH2Cl2 (40 mL)
was stirred at ambient temperature under nitrogen for 12 h. The resulting red
solution was filtered through Celite to remove the insoluble salts, and the pad was
eluted with CH2Cl2 until the eluent was colorless, then the solvent of the filtrate
were removed under vacuum and the solid residue was extracted with a small
volume of CH2Cl2 followed by re-precipitation by adding to a stirring mixture of
50/50 diethyl ether/hexane (100 mL). Precipitates thus formed were collected in a
glass frit, washed with diethyl ether and dried under vacuum. The final product
can be obtained as a pink powder containing a mixture of 2a and 4a (0.33 g) in a
ratio of 14:1 determined by NMR. Spectroscopic data of 2a: 1H NMR (δ, acetone-
1
Spectroscopic data of 2j: H NMR (δ, CDCl3): 7.55-6.85 (m, 39H, Ph); 4.73 (s,
5H, Cp); 4.31, 4.21 (2d, 2H, CH2); 2.02 (s, 1H, OH); 13C NMR (δ, CDCl3): 355.63
3
(t, JCP = 15.9 Hz, Cα); 147.49-124.07 (Ph and Cβ); 93.78 (Cp); 88.33 (CPh);
31.80 (CH2); 25.40 ((CH3)3C); 31P NMR (δ, CDCl3): 41.11, 40.98 (2d, 2JPP = 27.5
Hz, PPh3). MS (ESI+) m/z: 911.2145(M)+. Elemental analysis calcd (%) for
C57H47F6OP3Ru: C, 64.83; H, 4.49; found: C, 64.67; H, 4.68.
Synthesis of 3a. A mixture of [Ru]-Cl (0.32 g, 0.44 mmol), 1a (0.065 g, 0.45
mmol), and NH4PF6 (0.075 g, 0.46 mmol), in MeOH (40 mL) was stirred at
ambient temperature for 12 h. Then the solvent was removed under vacuum and
3 mL of CH2Cl2 was used to extract the crude product. The solution was filtered
through celite to remove the insoluble salts, and the pad was eluted with CH2Cl2
until the eluent was colorless, then the solvent of the filtrate were removed under
vacuum and the solid residue was extracted with a small volume of CH2Cl2
followed by re-precipitation by adding to a stirring solution (50 mL) of diethyl
ether hexane (1:1). Precipitates thus formed were collected in a glass frit, washed
with diethyl ether and dried under vacuum. The final product can be obtained as a
pink powder identified as 3a (0.35 g, 75%). Spectroscopic data of 3a: 1H NMR (δ,
CDCl3): 7.30-6.97 (m, 34H, Ph); 6.01 (s, 1H, CH); 5.15 (s, 5H, Cp); 4.47, 3.80
(2d, 2H,2JHH = 18.7 Hz, CH2); 3.18 (s, 3H, OCH3); 13C NMR (δ, CDCl3): 344.43
(t, 3JCP = 15.7 Hz, Cα); 140.42-123.87 (Ph and Cβ); 94.32 (Cp); 83.79 (CH); 51.99
2
(OCH3); 32.33 (CH2); 31P NMR (δ, CDCl3): 43.54, 42.41 (2d, JPP = 26.4 Hz,
PPh3). MS (ESI+) m/z: 849.1989 (M)+. Elemental analysis calcd (%) for
C52H45F6OP3Ru: C, 62.84; H, 4.56; found: C, 62.69; H, 4.64.
3
d6): 7.69-7.17 (m, 34H, Ph); 6.29 (d, 1H, JHH = 10.5 Hz, CH); 5.42 (s, 5H, Cp);
5.16 (d, 1H, 3JHH = 10.5 Hz, OH); 4.52, 4.10 (2d, 2H, 2JHH = 18.6 Hz, CH2); 13
C
Synthesis of 3b. The synthesis of 3b from [Ru]-Cl (0.46 g, 0.63 mmol) and 1b
(0.124 g, 0.66 mmol) followed the standard procedure as the synthesis of 3a for 1
day. The final product can be obtained as a pale pink powder identified as 3b
(0.57g, 87%). Spectroscopic data of 3b: 1H NMR (δ, CDCl3): 7.43-6.57 (m, 32H,
Ph); 5.96 (s, 1H, CH); 5.95 (s, 2H, CH2); 5.18 (s, 5H, Cp); 4.43, 3.72 (2d, 2H, 2JHH
= 18.3 Hz, CH2); 3.23 (s, 3H, OCH3); 13C NMR (δ, CDCl3): 344.09 (t, 3JCP = 15.8
Hz, Cα); 149.36-104.18 (Ph and Cβ); 101.40 (CH2); 94.11 (Cp); 83.11 (CH);
3
NMR (δ, CDCl3): 349.1 (t, JCP = 15.6 Hz, Cα); 134.8-124.3 (Ph and Cβ); 94.4
(Cp); 76.9 (CH); 31.4 (CH2); 31P NMR (δ, CDCl3): 44.25, 42.71 (2d, 2JPP = 27.1
Hz, PPh3). MS (ESI+) m/z: 835.1833 (M)+. When the reaction time of [Ru]-Cl
(0.31 g, 0.43 mmol) with 1a (0.066 g, 0.46 mmol), was extended for 1 day at 40 °C,
the final product can be obtained as a pink powder identified as 4a (0.34 g, 82%).
Spectroscopic data of 4a: 1H NMR (δ, CD2Cl2): 7.73-7.33 (m, 68H, Ph); 5.78 (d,
1H, 3JHH = 9.8 Hz, CH); 4.73 (d, 1H, 3JHH = 17.3 Hz, CH); 4.62 (s, 1H, CH); 4.61
(s, 5H, Cp); 4.45 (s, 5H, Cp); 4.40 (d, 1H, CH); 3.88 (d, 1H, 3JHH = 9.8 Hz, OH);
3.50 (d, 1H, 2JHH = 17.3 Hz, CH), 13C NMR (δ, CD2Cl2): 341.8 (dd, 3JCP=12.2 Hz,
2
51.21 (OCH3); 31.77 (CH2); 31P NMR (δ, CDCl3): 43.28, 42.12 (2d, JPP = 26.8
Hz, PPh3). MS (ESI+) m/z: 893.1887 (M)+. Elemental analysis calcd (%) for
C53H45F6O3P3Ru: C, 61.33; H, 4.37; found: C, 61.43; H, 4.64.
3
Cα1); 338.9 (dd, JCP=12.6 Hz, Cα2); 144.7-125.5 (Ph, Cβ1 and Cβ2); 94.8 (Cp);
Synthesis of 3c. The synthesis of 3c from [Ru]-Cl (0.42 g, 0.58 mmol) and 1c
(0.097 g, 0.60 mmol) for 12 h followed the standard procedure as the synthesis of
3a. The final product can be obtained as a brown powder identified as 3c (0.46 g,
78%). Spectroscopic data of 3c: 1H NMR (δ, CDCl3): 7.38-6.79 (m, 33H, Ph);
5.93 (s, 1H, CH); 5.15 (s, 5H, Cp); 4.47, 3.75 (2d, 2H, 2JHH = 19.0 Hz, CH2); 3.17
94.5 (Cp); 74.1 (CH); 54.9 (CH); 54.7 (CH); 33.5 (CH2); 31P NMR (δ, CD2Cl2):
2
2
41.64, 39.56 (2d, JPP = 26.9 Hz, PPh3) 41.38, 39.02 (2d, JPP = 27.4 Hz, PPh3).
MS (ESI+) m/z: 826.1781 (M)+2
Elemental analysis calcd (%) for
.
C102H84F12OP6Ru2: C, 63.09; H, 4.36; found: C, 63.36; H, 4.61.
Reaction of 1f with [Ru]-Cl giving mixture of 2f/8f. The reaction of 1f (0.063
g, 0.40 mmol) with [Ru]-Cl (0.28 g, 0.39 mmol), for 16 h in CH2Cl2 giving
mixture of 2f/8f (0.30 g) followed the same procedure as the synthesis of 2a/4a.
The final product can be obtained as a pale pink powder identified as a mixture of
2f and 8f in a ratio of 2:1 as determined by NMR. Spectroscopic data of 2f: H
NMR (δ, CDCl3): 7.57-7.02 (m, 34H, Ph); 5.14 (s, 5H, Cp); 4.06 (s, 2H, CH2);
3
(s, 3H, OCH3); 13C NMR (δ, CDCl3): 344.04 (t, JCP = 15.5 Hz, Cα); 165.14-
111.25 (Ph and Cβ); 101.40 (CH2); 94.36 (Cp); 82.67 (CH); 51.85 (OCH3); 31.85
2
(CH2); 31P NMR (δ, CDCl3): 43.23, 42.27 (2d, JPP = 27.1 Hz, PPh3). MS (ESI+)
m/z: 867.1671 (M)+. Elemental analysis calcd (%) for C52H44F7OP3Ru: C, 61.72;
H, 4.38; found: C, 62.01; H, 4.60.
1
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10.1002/asia.201801303
Chemistry - An Asian Journal
FULL PAPER
Synthesis of 3f and 8f. A mixture of [Ru]-Cl (0.32 g, 0.44 mmol), 1f (0.071 g,
0.45 mmol), and KPF6 (0.083 g, 0.45 mmol), in MeOH (40 mL) was used
following the procedure described in the synthesis of 2a at ambient temperature
for 12h. The final product was obtained as a pale pink powder containing a mixture
Elemental analysis calcd (%) for C51H42OP2Ru: C, 74.36; H, 5.08; found: C,
74.43; H, 5.24.
Synthesis of 6d. The synthesis of 6d from 1d (0.066 g, 0.41 mmol) and [Ru]-Cl
(0.28 g 0.38 mmol) followed the standard procedure as the synthesis of 2a for 16
h. The final product can be obtained as a pale pink powder identified as 6d (0.28
g, 73%). Spectroscopic data of 6d: 1H NMR (δ, CDCl3): 7.72-6.82 (m, '34H, Ph);
5.28 (s, 5H, Cp); 5.23 (s, CH); 4.93, 4.60 (2d, 2H, 1JHH = 11.7 Hz, CH2); 3.65 (s,
1
of 3f and 8f (total weight 0.35 g) in a ratio of 3:1. Spectroscopic data of 3f: H
NMR (δ, CDCl3): 7.50-6.96 (m, 34H, Ph); 5.16 (s, 5H, Cp); 4.18, 3.90 (2s, 2H,
CH2); 3.01 (s, 3H, OCH3); 1.58 (s, 3H, CH3); 13C NMR (δ, CDCl3): 348.93 (t, 3JCP
= 16.1 Hz, Cα); 142.81-120.33 (Ph and Cβ); 34.36 (Cp); 91.33 (CCH3); 31.71
(CH2); 30.77 (CH3); 31P NMR (δ, CDCl3): 43.05, 41.78 (2d, 2JPP = 27.6 Hz, PPh3).
MS (ESI+) m/z: 863.2157 (M)+. The synthesis of pure 8f from 1f is achieved if the
reaction was carried out for 1 day at 40 °C. The final product can be obtained as a
pale pink powder identified as 8f (86%).
3
1H, OH); 13C NMR (δ, CDCl3): 338.1 (t, JCP = 15.0 Hz, Cα); 153.77(O-Ph);
134.59-116.79 (Ph and Cβ); 94.39 (Cp); 61.27 (CH2); 57.85 (CH); 31P NMR (δ,
CDCl3): 42.48, 40.73 (2d, 2JPP = 25.6 Hz, PPh3). MS (ESI+) m/z: 851.1776 (M)+.
Elemental analysis calcd (%) for C51H43F6O2P3Ru: C, 61.51; H, 4.35; found: C,
61.55; H, 4.31.
Synthesis of 2g and 8g. The synthesis of 2g (0.29 g, 71%) from 1g (0.083 g, 0.45
mmol) and [Ru]-Cl (0.29 g, 0.40 mmol) followed the standard procedure as the
synthesis of 2a for 8 h. The final product was obtained as a pale yellow powder.
Spectroscopic data of 2g: 1H NMR (δ, CDCl3): 7.42-7.04 (m, 34H, Ph); 5.71 (m,
1H, HC=); 5.17 (s, 5H, Cp); 5.13, 5.04 (2d, 2H, =CH2); 4.11, 3.89 (2d, 2H, CH2);
2.70, 2.66, 2.58, 2.55 (2dd, 2H, CH2); 1.86 (s, 1H, OH); 13C NMR (δ, Acetone-
d6): 350.60 (t, 3JCP = 15.1 Hz, Cα); 133.82 (=CH), 117.54(=CH2), 146.11-123.75
(Ph and Cβ); 94.35 (Cp); 86.81 (CCH2); 48.03 (CH2); 31.25 (CH2); 31P NMR (δ,
CDCl3): 41.83, 41.41 (2d, 2JPP = 26.8 Hz, PPh3). MS (ESI+) m/z: 875.2146(M)+.
Elemental analysis calcd (%) for C54H47F6OP3Ru: C, 63.59; H, 4.64; found: C,
63.50; H, 4.38. The reaction of 1g (0.17 g, 0.92 mmol) with [Ru]-Cl (0.61 g, 0.84
mmol) for one day followed the standard procedure as the synthesis of 3a. The
final product 8g (0.69 g, 82%) was obtained as a pale green powder. Spectroscopic
data of 8g: 1H NMR (δ, CDCl3): 7.51-6.97 (m, 35H, Ph and HC=); 6.49 (d, 1H,
HC=); 5.63 (s, 5H, Cp); 4.94, 4.78 (2d, 2H, =CH2); 3.95 (s, 2H, CH2); 13C NMR
Synthesis of 6e. The synthesis of 6e from 1e (0.074g, 0.42 mmol) and [Ru]-Cl
(0.29 g 0.40 mmol) followed the standard procedure as the synthesis of 2a for 16h.
The final product was obtained as a pale pink powder identified as 6e (0.26 g,
64%) by NMR. Spectroscopic data of 6e: 1H NMR (δ, CDCl3): 7.09-6.88 (m, 34H,
Ph); 5.49 (s, 1H, CH); 5.26 (s, 5H, Cp); 4.06, 3.06 (2d, 2H , 1JHH = 12.6 Hz , CH2);
3
3.77 (s, 1H, OH); 13C NMR (δ, CDCl3): 340.16 (t, JCP = 15.9 Hz, Cα); 136.17-
120.01 (Ph and Cβ); 94.72 (Cp); 63.29 (CH); 19.2 (CH2); 31P NMR (δ, CDCl3):
42.61, 41.80 (2d, 2JPP = 26.6 Hz, PPh3). MS (ESI+) m/z: 867.1548 (M)+. Elemental
analysis calcd (%) for C51H43F6OP3RuS: C, 60.53; H, 4.28; found: C, 60.51; H,
4.31
Synthesis of 6d and 7d. A mixture of [Ru]-Cl (0.32 g, 0.44 mmol), 1d (0.064 g,
0.40 mmol), and KPF6 (0.085 g, 0.46 mmol), in MeOH (40 mL) was used
following the procedure described in the synthesis of 2a at ambient temperature
for 16h. The final product was obtained as a pale pink powder containing a mixture
of 6d and 7d (total weight 0.30 g, ca. 75%) in a ratio of 6:1. Spectroscopic data of
7d: 1H NMR (δ, CDCl3): 7.44-6.85 (m, 34H, Ph); 5.10 (s, 5H, Cp); 4.94 (s, 1H,
CH); 4.82, 4.67 (2d, 2H , 1JHH = 11.15 Hz , CH2); 3.58 (s, 3H, CH3); 31P NMR (δ,
CDCl3): 42.55, 41.31 (2d, 2JPP = 25.5 Hz, PPh3). MS (ESI+) m/z: 865.1933 (M)+
Synthesis of 6e and 7e. A mixture of [Ru]-Cl (0.30 g, 0.41 mmol), 1e (0.077 g,
0.44 mmol), and KPF6 (0.085 g, 0.46 mmol), in MeOH (30 mL) was used
following the procedure described in the synthesis of 2a at ambient temperature
for 12h. The final product was obtained as a pale pink powder containing a mixture
of 6e and 7e (total weight 0.27 g, ca. 70%) in a ratio of 6:1. Spectroscopic data of
7e: 1H NMR (δ, CDCl3): 7.35-6.91 (m, 34H, Ph); 5.30 (s, 5H, Cp); 4.94 (s, 1H,
CH);; 4.06, 3.20 (2d, 2H , 1JHH = 9.92 Hz , CH2) ; 3.56 (s, 3H, CH3); 31P NMR (δ,
CDCl3): 42.94, 41.07 (2d, 2JPP = 26.3 Hz, PPh3 ). MS (ESI+) m/z: 881.1705 (M)+
Synthesis of fluorene 9g. The synthesis of 8g and fluorene 9g from 1g (0.081 g,
0.44 mmol) and [Ru]-Cl (0.31 g 0.43 mmol) followed the standard procedure as
the synthesis of 2a for 3 days but in MeOH at 50 °C. The green precipitates thus
formed was filtered and washed with diethyl ether and dried under vacuum to give
green powder identified as 8g. The filtrate was evaporated to dryness under
vacuum and the crude product purified by column chromatography (SiO2,
EA/hexane, 1:10) to afford organic product fluorene 9g (0.019 g, 27%).
Spectroscopic data of 9g: 1H NMR (δ, CDCl3): 7.83-7.31 (m, 8H, Ph); 3.92 (s, 2H,
CH2); 13C NMR (δ, CDCl3): 143.2-119.8 (Ph); 36.9 (CH2). MS (ESI+) m/z:
167.0622(M+1)+
3
(δ, Acetone-d6): 362.34 (t, JCP = 15.4 Hz, Cα); 133.82 (=CH); 127.37 (=CH),
134.9-124.732 (Ph and Cβ); 119.81 (C=CH); 116.81(=CH2); 94.90 (Cp); 30.27
(CH2); 31P NMR (δ, CDCl3): 41.45 (s, PPh3). MS (ESI+) m/z: 857.2040(M)+.
Elemental analysis calcd (%) for C54H45F6P3Ru: C, 64.73; H, 4.53; found: C,
64.51; H, 4.81
Synthesis of 3h and 8h. The synthesis of mixture of 3h and 8h from 1h in MeOH
followed the standard procedure as the synthesis of 3a for 12 h. The final product
was obtained as a pale yellow powder identified as a mixture of 3h and 8h (5:1)
as determined by NMR. Spectroscopic data of 3h: 1H NMR (δ, CDCl3): 7.69-6.23
(m, 39H, Ph); 5.15 (s, 5H, Cp); 4.16, 4.01 (2d, 2H, 2JHH = 18.3 Hz, CH2); 3.34,
2.82 (2d, 2H, 2JHH = 13.7 Hz, CH2); 3.08 (s, 3H, OCH3); 13C NMR (δ, CDCl3):
3
347.89 (t, JCP = 14.9 Hz, Cα); 142.3-123.770 (Ph and Cβ); 93.82 (Cp); 94.29
(COCH3); 52.04 (OCH3); 49.27 (CH2); 31.36 (CH2); 31P NMR (δ, CDCl3): 43.09,
41.78 (2d, 2JPP = 27.6 Hz, PPh3). MS (ESI+) m/z: 939.2455(M)+.
Synthesis of 4b. A solution of 3b (0.050 g, 0.048 mmol) in CDCl3 (3 mL) in a
Schlenk tube was warmed under nitrogen to 45°C for 12h. The final product was
obtained as red crystal identified as 4b (0.040g, 81%). Spectroscopic data of 4b:
1H NMR (δ, CD2Cl2): 7.49-6.67 (m, 64H, Ph); 6.24, 6.08 (2s, CH2); 6.19, 6.06 (2s,
CH2); 5.78 (d, 1H,3JHH = 9.8 Hz, CH); 5.02 (s, 5H, Cp); 4.93 (s, 5H, Cp); 4.68 (s,
2
3
1H, CH); 4.04 (d, 1H, JHH = 16.9 Hz, CH); 3.91 (d, 1H, JHH = 9.93 Hz, CH);
3.64 (d, 1H,3JHH = 9.93 Hz, CH); 3.22 (d, 1H, 2JHH =16.9 Hz, CH); 3.00 (s, 3H,
OCH3); 13C NMR (δ, CD2Cl2): 340.93 (t, Cα1 and Cα2, overlap); 148.48-105.37
(Ph, Cβ1 and Cβ2); 102.92 (CH2); 102.45 (CH2); 95.11 (Cp1 and Cp2, overlap);
81.5179 (CH); 56.64 (OCH3); 54.56 (CH); 51.18 (CH); 31.30 (CH2); 31P NMR (δ,
CD2Cl2): 41.11, 40.08 (2d, 2JPP = 24.3 Hz, PPh3) 41.54, 39.03 (2d, 2JPP = 25.1 Hz,
Synthesis of 8h. The synthesis of 8h (0.38 g, 82%) from 1h (0.122 g, 0.50 mmol)
and [Ru]-Cl (0.32 g 0.44 mmol) in CH2Cl2 followed the standard procedure as the
synthesis of 3a for one day. The final product was obtained as a green powder
identified as 8h. Spectroscopic data of 8h (major): 1H NMR (δ, CDCl3): 7.39-6.76
(m, 40H, Ph and CH=); 5.33 (s, 5H, Cp); 3.90 (s, 2H, CH2); 13C NMR (δ, CDCl3):
PPh3). MS (ESI+) m/z: 876.6722 (M)+2
.
3
Synthesis of 5a. A mixture of [Ru]-Cl (0.30 g, 0.41 mmol), 1a (0.066 g, 0.45
mmol), and KF (0.048 g, 0.83 mmol), in MeOH (40 mL) was stirred at ambient
temperature for 2 days. Then the solvent was removed under vacuum and 3 mL of
CH2Cl2 was used to extract the crude product. The light-yellow solution was
filtered through celite to remove the insoluble salts, and the pad was eluted with
CH2Cl2 until the eluent was colorless, then the solvent of the filtrate were removed
under vacuum to give light-yellow complex 5a. (0.30 g, 87%). Spectroscopic data
of 5a: 1H NMR (δ, CD2Cl2): 10.61 (s, 1H, O=CH); 7.88-7.06 (m, 34H, Ph); 4.27
(s, 5H, Cp); 4.21 (s, 2H, CH2); 13C NMR (δ, CD2Cl2): 193.10 (C=O); 145.22-
126.62 (Ph); 107.86 (Cβ); 99.3. (t, 3JCP = 24.7 Hz, Cα); 85.40 (Cp); 27.21 (CH2);
31P NMR (δ, CD2Cl2): 50.66 (s, PPh3). MS (ESI+) m/z: 835.1833 (M+1)+.
361.27 (t, JCP = 15.9 Hz, Cα); 142.36-120.01 (Ph, HC=C and Cβ); 94.37 (Cp);
30.31 (CH2); 31P NMR (δ, CDCl3): 41.27 (s,PPh3). MS (ESI+) m/z: 907.2197(M)+.
Elemental analysis calcd (%) for C58H47F6P3Ru: C, 66.22; H, 4.50; found: C,
66.06; H, 4.48.
Synthesis of Complex 10k. The synthesis of 10k (0.38 g, 86%) from 1k (0.082
g, 0.48 mmol) and [Ru]-Cl (0.32 g 0.44 mmol) followed the standard procedure
as the synthesis of 1a and 2a but in MeOH for 12 h. The final product can be
obtained as a pink powder identified as 10k. Spectroscopic data of 10k: 1H NMR
(δ, CDCl3): 7.97- 6.51 (m, 34H, Ph); 5.00 (s, 5H, Cp); 3.75, 3.67 (2d, 2H, 2JHH
=
16.8 Hz, CH2); 3.10 (m, 1H, CH); 2.74 (m, 2H, CH2); 1.35 (d, 3H, 3JHH = 6.7 Hz,
3
CH3); 13C NMR (δ, CDCl3): 349.8 (t, JCP = 15.1 Hz, Cα); 202.0 (C=O); 141.4-
123.8 (Ph and Cβ); 94.2 (Cp); 49.4 (CH2); 27.8 (CH); 26.6 (CH2); 22.4 (CH3); 31
P
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10.1002/asia.201801303
Chemistry - An Asian Journal
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2
NMR (δ, CDCl3): 43.32, 41.55 (2d, JPP = 26.0 Hz, PPh3). MS (ESI+) m/z:
(t, 2H, 3JHH = 6.9 Hz, CH2); 3.32 (s, 2H, SCH2); 2.56 (t, 2H, 3JHH = 6.9 Hz , CH2);
3
861.1942(M)+.
13C NMR (δ, CDCl3): 343.36 (t, JCP = 12.0 Hz, Cα); 203.05 (C=O); 142.93-
Synthesis of 10l. The synthesis of 10l (0.25 g, 81%) from 1l (0.061 g, 0.33 mmol)
and [Ru]-Cl (0.22 g 0.30 mmol) followed the standard procedure as the synthesis
of 3a for 12h. The final product was obtained as a pink powder identified as 10l
(0.31 g, 85%). Spectroscopic data of 10l: 1H NMR (δ, CDCl3): 7.97- 6.51 (m, 34H,
Ph); 5.00 (s, 5H, Cp); 3.75, 3.67 (2d, 2H, 2JHH = 16.8 Hz, CH2); 3.10 (m, 1H, CH);
2.74 (m, 2H, CH2); 1.35 (d, 3H, 3JHH = 6.7 Hz, CH3); 13C NMR (δ, CDCl3): 349.77
119.29 (Ph and Cβ); 94.67 (Cp); 40.29 (CH2); 30.94 (SCH2); 22.65 (CH2); 31P
NMR (δ, CDCl3): 40.79 (s, PPh3). MS (ESI+) m/z: 893.1730(M)+ Elemental
analysis calcd (%) for C53H45F6OP3RuS: C, 61.33; H, 4.37; found: C, 62.37; H,
4.39. The synthesis of complex 12p’ (0.23 g, 64%) from 1p’ (0.11g, 0.51 mmol)
and [Ru]-Cl (0.25 g, 0.30 mmol) followed the standard procedure as the synthesis
of 5a in methanol for one day. Spectroscopic data of 12o: 1H NMR (δ, CDCl3):
8.45-6.71 (m, 34H, Ph); 5.04 (m, 1H, CH); 4.69 (s, 5H, Cp); 3.21 (m, 2H, OCH2);
2.31 (m, 2H, CH2); 1.15 (d, 3H, 3JHH = 5.0 Hz, CH2); 13C NMR (δ, CDCl3): 343.71
3
(t, JCP = 15.1 Hz, Cα); 202.01 (C=O); 141.44-123.77 (Ph and Cβ); 94.17 (Cp);
49.36 (CH2); 27.83 (CH); 26.63 (CH2); 22.41 (CH3); 31P NMR (δ, CDCl3): 43.32,
2
3
41.55 (2d, JPP = 26.0 Hz, PPh3). MS (ESI+) m/z: 875.2146(M)+. Elemental
(t, JCP = 11.9 Hz, Cα); 206.02 (C=O); 142.50-120.83 (Ph and Cβ); 94.67 (Cp);
analysis calcd (%) for C54H47F6OP3Ru: C, 63.59; H, 4.64; found: C, 63.53; H, 4.55.
Synthesis of 10m. The synthesis of 10m (0.32 g, 88%) from 1m (0.075 g, 0.41
mmol) and [Ru]-Cl (0.26 g 0.36 mmol) followed the standard procedure as the
synthesis of 3a for 12 h. The final product can be obtained as a pink powder
identified as 10m. Spectroscopic data of 10m: 1H NMR (δ, CDCl3): 7.89-6.76 (m,
34H, Ph); 5.02 (s, 5H, Cp); 3.81, 3.73 (2d, 2H, 2JHH = 16.7 Hz, CH2); 3.19, 2.19
(m, 2H, CH2); 3.13 (m, 1H, CH); 1.14 (d, 3H, 3JHH = 6.1 Hz, CH3); 13C NMR (δ,
42.46 (SCH2); 31.22 (CH2); 30.71 (CH2); 16.58 (CH3); 31P NMR (δ, CDCl3):
40.85 (dd, PPh3). MS (ESI+) m/z: 907.1866(M)+. Elemental analysis calcd (%) for
C54H47F6OP3RuS: C, 61.65; H, 4.50; found: C, 61.47; H, 4.45.
Synthesis of isochromene 14h. A mixture of [Ru]-Cl (0.20 g, 0.28 mmol), 1h
(0.33 g, 1.40 mmol) and CDCl3 (3 mL) in a tube was heated at 50 °C for 6 h under
nitrogen. Then CDCl3 was removed in vacuo and CH2Cl2 (1 mL) was used to
extract the product. Then diethyl ether (10 mL) was added to the extract. The pale-
orange precipitates thus formed were filtered and washed with diethyl ether and
dried under vacuum to give [Ru]-Cl. The filtrate was evaporated to dryness under
vacuum and the crude product purified by column chromatography (SiO2,
EA/hexane, 1:10) to afford compound 14h (0.24 g, 73%) as yellow oil.
Spectroscopic data of 14h: 1H NMR (δ, CDCl3): 7.72-6.93 (m, 9H, Ph); 6.12
(=CH); 5.67 (=CH); 2.12 (s, 3H, CH3); 13C NMR (δ, CDCl3): 151.9 (=C); 149.3
(=C); 136.0-122.5 (Ph); 101.2 (=CH); 100.8 (=CH); 19.3 (CH3). MS (ESI+) m/z:
calcd: 234.1045 (M)+; expt: 235.1123(M+1)+.
3
CDCl3): 349.32 (t, JCP = 15.4 Hz, Cα); 204.90 (C=O); 142.00-124.13 (Ph and
Cβ); 93.99 (Cp); 43.91 (CH); 29.66 (CH2); 28.70 (CH2); 15.28 (CH3); 31P NMR
(δ, CDCl3): 43.61, 41.96 (2d,2JPP = 26.6 Hz, PPh3). MS (ESI+) m/z: 875.2151(M)+.
Elemental analysis calcd (%) for C54H47F6OP3Ru: C, 63.59; H, 4.64; found: C,
63.76; H, 4.84.
Synthesis of 11n. The synthesis of 11n (0.21 g, 81%) from 1n (0.065g, 0.33
mmol) and [Ru]-Cl (0.18 g 0.25 mmol) followed the standard procedure as the
synthesis of 3a for 16 h. The final product can be obtained as a pink powder
identified as 11n. Spectroscopic data of 11n: 1H NMR (δ, CDCl3): 8.39-6.97 (m,
34H, Ph); 5.65 (s, 1H, HC=); 5.26 (s, 5H, Cp); 3.72 (s, 2H, CH2); 3.02 (s, 3H,
Synthesis of isochromene 13q. The synthesis of complex 13q (0.21 g, 75%) from
1q (0.063 g, 0.34 mmol) and [Ru]-Cl (0.20 g, 0.28 mmol) followed the standard
procedure as the synthesis of 2a in methanol for one day. Spectroscopic data of
12o: 1H NMR (δ, CDCl3): 10.02 (s, 1H, CHO); 7.71-6.71 (m, 34H, Ph); 5.25 (s,
5H, Cp); 4.72, 4.41 (2d, 2H, OCH2 ) 4.23 (d, 1H, CH); 3.54, 2.78 (2d, 2H, CH2);
3
OCH3); 1.22 (s, 6H, (CH3)2C); 13C NMR (δ, CDCl3): 361.03 (t, JCP = 15.7 Hz,
Cα); 137.05 (C=); 129.77 (HC=); 142.65-127.31 (Ph and Cβ); 94.39 (Cp); 75.66
(C(CH3)2); 50.33 (OCH3); 30.05 (CH2); 27.55 (CH3); 31P NMR (δ, CDCl3): 41.29
(s, PPh3). MS (ESI+) m/z: 903.2458(M)+. Elemental analysis calcd (%) for
C56H51F6OP3Ru: C, 64.18; H, 4.91; found: C, 63.98; H, 4.79.
3
13C NMR (δ, CDCl3): 340.47 (t, JCP = 14.7 Hz, Cα); 201.64 (C=O); 154.18-
116.95 (Ph and Cβ); 94.92 (Cp); 57.94 (OCH2); 51.22 (CH2); 27.88 (CH); 31P
2
Synthesis of 11n’. The synthesis of 11n’ from 1n (0.077g, 0.39 mmol) and [Ru]-
Cl (0.26 g 0.36 mmol) followed the standard procedure as the synthesis of 3a in
ethanol for one day. The final product was obtained as a pink powder identified
as 11n’ (0.28 g, 68%). Spectroscopic data of 11n’: 1H NMR (δ, CDCl3): 8.47-6.97
(m, 34H, Ph); 5.70 (s, 1H, HC=); 5.27 (s, 5H, Cp); 3.72 (s, 2H, CH2); 3.23 (q, 2H,
3JHH = 7.0 Hz, OCH2); 1.24 (s, 6H, (CH3)2C); 1.00 (t, 3H, 3JHH = 7.0 Hz, CH3);
13C NMR (δ, CDCl3): 361.17 (t, 3JCP = 15.5 Hz, Cα); 136.91 (C=); 130.84 (HC=);
142.40-124.12 (Ph and Cβ); 94.18 (Cp); 74.90 (C(CH3)2); 57.87 (OCH2); 29.83
(CH2); 27.82 (CH3); 15.77 (CH3);31P NMR (δ, CDCl3): 41.34 (s,PPh3). MS (ESI+)
m/z: 917.2615(M)+. Elemental analysis calcd (%) for C57H53F6OP3Ru: C, 64.46;
H, 5.03; found: C, 64.67; H, 4.89.
NMR (δ, CDCl3): 43.38, 40.18 (2d, JPP = 25.7 Hz, PPh3). MS (ESI+) m/z:
877.1935 (M)+. Elemental analysis calcd (%) for C53H45F6O2P3Ru: C, 62.29; H,
4.44; found: C, 62.32; H, 4.35.
Synthesis of 15j. The synthesis of 15j (0.08 g, 74%) from 1j (0.1 g, 0.45 mmol)
and [Ru]-Cl (0.016 g, 0.022 mmol) followed the standard procedure as the
synthesis of 14h in CDCl3 for 10h. Spectroscopic data of 15j: 1H NMR (δ, CDCl3):
7.78-7.25 (m, 9H, Ph); 3.95 (s, 2H, CH2); 2.16 (s, 3H, CH3); 13C NMR (δ, CDCl3):
205.46 (O=C); 198.20 (O=C); 137.88-126.34 (Ph); 48.11 (CH2); 29.84 (CH3). MS
(ESI+) m/z: calcd: 238.0994 (M)+; expt: 239.1003(M+1)+.
Single-crystal X-ray diffraction analyses: Single crystals of complexes 4a and
10l suitable for X-ray diffraction study were grown as mentioned above. Single
crystals were glued to a glass fiber and mounted on a SMART CCD diffractometer.
The diffraction data were collected by using a 3-kW sealed-tube Mo Kα radiation
(T = 295 K). Exposure time was 5 s per frame (Siemens area detector absorption).
SADABS37 absorption correction was applied, and decay was negligible. Data
were processed and the structure was solved and refined by the SHELXTL38
program. Hydrogen atoms were placed geometrically by using a riding model with
thermal parameters set to 1.2 times that for the atoms to which they are attached
and 1.5 times for the methyl hydrogen atoms.
Synthesis of 12o, 12o’, 12p and 12p’. The synthesis of complex 12o (0.21 g,
68%) from 1o (63 mg, 0.34 mmol) and [Ru]-Cl (0.22 g, 0.30 mmol) followed the
standard procedure as the synthesis of 3a in methanol for one day. Spectroscopic
data of 12o: 1H NMR (δ, CDCl3): 8.27-6.57 (m, 34H, Ph); 4.66 (s, 5H, Cp); 4.40
(s, 2H, OCH2); 3.21 (t, 2H, 3JHH = 6.9 Hz, CH2); 2.58 (t, 2H, 3JHH = 6.9 Hz, CH2);
3
13C NMR (δ, CDCl3): 339.56 (t, JCP = 14.2 Hz, Cα); 201.31 (C=O); 157.93-
119.29 (Ph and Cβ); 94.75 (Cp); 70.61 (OCH2); 41.74 (CH2); 22.40 (CH2); 31P
NMR (δ, CDCl3): 41.07 (s, PPh3). MS (ESI+) m/z: 877.1922(M)+. Elemental
analysis calcd (%) for C53H45F6O2P3Ru: C, 62.29; H, 4.44; found: C, 62.37; H,
4.39. The synthesis of complex 12o’ (0.35 g, 59 %) from 1o’ (0.15g, 0.63 mmol)
and [Ru]-Cl (0.40 g, 0.55 mmol) followed the standard procedure as the synthesis
of 5a in methanol for one day. Spectroscopic data of 12o’: 1H NMR (δ, CDCl3):
Acknowledgements
8.84-6.87 (m, 38H, Ph); 4.61 (s, 5H, Cp); 4.54 (s, 2H, OCH2); 3.21 (t, 2H, 3JHH
=
6.8 Hz, CH2); 2.64 (t, 2H, 3JHH = 6.8 Hz, CH2); 13C NMR (δ, CDCl3): 341.40 (t,
3JCP = 14.4 Hz, Cα); 204.74 (C=O); 156.98-120.15 (Ph and Cβ); 94.61 (Cp); 70.30
(OCH2); 44.00 (CH2); 22.51 (CH2); 31P NMR (δ, CDCl3): 41.26 (s, PPh3). MS
(ESI+) m/z: 927.2094(M)+. Elemental analysis calcd (%) for C53H45F6O2P3Ru: C,
63.87; H, 4.42; found: C, 63.57; H, 4.39. Synthesis of complex 12p (0.16 g, 59%)
in methanol from 1p (61 mg, 0.30 mmol) and [Ru]-Cl (0.19 g, 0.26 mmol)
followed the standard procedure as the synthesis of 5a for one day. Spectroscopic
data of 12p: 1H NMR (δ, CDCl3): 8.49-6.86 (m, 34H, Ph); 4.74 (s, 5H, Cp); 3.73
We thank the Ministry of Science and Technology, Taiwan, for financial
support.
Keywords: Ruthenium, vinylidene, cyclization, dehydrative coupling,
intramolecular dehydration.
This article is protected by copyright. All rights reserved.

10.1002/asia.201801303
Chemistry - An Asian Journal
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10.1002/asia.201801303
Chemistry - An Asian Journal
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Author(s), Pi-Yeh Chia, [a] Cheng-Chen
Kuo,[a] Shou-Ling Huang,[a] Yi-Hong
Liu,[a] Ling-Kang Liu,[a] and Ying-Chih
Lin,*[a]
A number of Ru vinylidene complexes
were obtained by metal mediated
cyclization of aryl propynes with ortho-
substituted aldehyde or ketone groups.
With either terminal or internal α,β-
unsaturated olefinic groups on the
carbonyl group, the C-C bond formation
occurs on the olefinic group. An unusual
intermolecular dehydrative coupling was
observed for the aryl propyne with simple
ortho-substituted aldehyde group.
Page No. – Page No.
Title. Intermolecular Dehydrative
Coupling and Intramolecular
Cyclization of Ruthenium
Vinylidene Complexes Formed from
Aromatic Propynes Containing
Carbonyl Functionalities
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Title
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