Ring Expansion and Skeletal Rearrangement of Propargyl Alcohol Substituted Aziridines Induced by Ruthenium Complexes

Article abstract of DOI:10.1002/asia.201600907

The ring expansion and skeletal rearrangement of two types of propargyl alcohol substituted aziridines with or without cycloalkane moieties was induced by a ruthenium cyclopentadienyl phosphine complex. In the simple aziridine system with no cycloalkane, the unique cycloisomerization process altered the absolute connectivity of the two-carbon unit in the three-membered ring to give organometallic products with substituted pyridine or dihydropyridine ligands. For the aziridine on a cyclohexyl ring, the cycloisomerization process was controlled by an interchange process between vinylidene and allenylidene species, thus creating a better relative configuration of the aziridinyl and the alkynyl units. This determines the stereochemistry of the metal carbene products of the octahydroindole derivatives. The structures of five products were determined by X-ray diffraction analysis.

Full text of DOI:10.1002/asia.201600907

CHEMISTRY
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Accepted Article
Title: Ring Expansion and Skeletal Rearrangement of Propargyl Alcohol Substituted
Aziridines Induced by Ru Complexes
Authors: Shu-Hao Wan; Ying Chih Lin; Ling-Kang Liu; Yi-Hung Liu
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Chemistry - An Asian Journal
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Ring Expansion and Skeletal Rearrangement of Propargyl
Alcohol Substituted Aziridines Induced by Ru Complexes
Shu-Hao Wan, Ying-Chih Lin,* [a] Ling-Kang Liu and Yi-Hung Liu
Abstract: Ring expansion and skeletal rearrangement of two types
of propargyl-alcohol-substituted aziridines without or with cyclo-
alkane moieties are induced by ruthenium cyclopentadienyl
phosphine complex. In the simple aziridine system with no
cycloalkane, the unique cycloisomerization process alters the
absolute connectivity of the two-carbon unit in the three-membered
ring, giving organometallic products with substituted pyridine or
dihydropyridine ligands. For the aziridine on a cyclohexyl ring, the
cycloisomerization process is controlled by an interchange process
between vinylidene and allenylidene species, thus, creating a better
relative configuration of the aziridinyl and the alkynyl units. This
determines the stereochemistry of the metal carbene products of
octahydroindole derivatives. Structure of five products are
Scheme 1. Cycloisomerization of alkyne and propargyl alcohol substituted
determined by X-ray diffraction analysis.
aziridines.
In this paper, we report the synthesis of cationic ruthenium
complexes containing organic ligand resulted from skeletal
rearrangement under a sole reaction pathway.
Introduction
The aziridine functionality represents valuable intermediates in
organic chemistry and has attracted extensive attention as
starting materials in numerous applications.1 Their synthetic
utility is dominated by ring opening or expansion reactions. The
highly or often completely regio- and stereo-selective
transformations of this strain-loaded ring contribute a powerful
approach toward furnishing of various target products. Transition
metal catalyzed cycloisomerization of functionalized alkynes
containing an aziridine moiety provides a useful platform for the
access of substituted pyrroles2 and other structural motifs.3
Davies and his co-workers reported two skeletal rearrangement
pathways for the formation of 2,4-disubstituted pyrroles by gold
catalyzed cycloisomerization of alkynyl aziridines (Scheme 1).4
The two competing pathways coincidentally give rise to the
same isomer but with different connectivity. The mechanism is
based on a 1,2-aryl shift or a 1,2-(enamine-stabilized)-vinyl shift
in the 5- or 4-membered cyclic intermediates, respectively. We
explore new cycloisomerization reactions of propargyl-alcohol-
substituted-aziridines induced by ruthenium complexes
CpL2RuCl (Cp=η5-C5H5, L2 = (PPh3)2, 1, or dppe, 1’).
Results and Discussion
Various acrylates 2 are used for the preparation of several
propargyl alcohol substituted aziridines 7a-f. (see Scheme 2 and
Table 1) Addition of Br2 to the C=C double bond of the acrylate
affords the α,β-dibromoesters 3 which are treated with BnNH2 to
generate the corresponding ester-substituted aziridines 4.1f-h
Reduction of the ester group by LiAlH4 gives the primary
alcohols 5 which are converted to the corresponding aldehyde
substituted aziridines 6 via Swern oxidation.5a Treatment of the
aldehydes with the Grignard reagent HC≡CMgBr yields the
desired compounds 7a-e (MeC≡CMgBr for 7f).
[a]
Shu-Hao Wan, Ying-Chih Lin,* Ling-Kang Liu and Yi-Hung Liu
Department of Chemistry
National Taiwan University
No. 1, Sec. 4, Roosevelt Rd., Taipei 10617, Taiwan (R.O.C.)
E-mail: yclin@ntu.edu.tw
Supporting information for this article is given via a link at the end of
the document.
Scheme 2. Preparations of 7a-g. Reagents and conditions: (i) Br2, CH2Cl2, 0
ºC. (ii) BnNH2, MeOH, 0 ºC to rt. (iii) LiAlH4, Et2O, 0 ºC. (iv) (ClC=O)2, Me2SO,
CH2Cl2, -78 ºC; Et3N, -78 ºC to rt. (v) Grignard reagent MeC≡CMgBr, THF, -78
ºC to rt.
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The acrylate with a 1-naphthyl group 7d is prepared from the
corresponding aldehyde with trialkyl-phosphonoacetate via
Horner-Wadsworth-Emmons condensation.5b Similar compound
7g is prepared from ethyl vinyl ketone. Diastereomers of 7 are
observed, see experimental section. However, as described
below, none of the stereogenic center stays after
cycloisomerization.
Treatment of 7a with [Ru]-Cl (1, [Ru] = Cp(PPh3)2Ru) in the
presence of KPF6 in MeOH at room temperature overnight
affords only the cationic 3-pyridyl complex 8a as light brown
powders, which was purified by precipitation from Et2O (Table 1,
Entry 1). Interestingly, the reaction of 7b with 1 under the same
condition gives the analogous complex 8b as the major product
and the dihydropyridine complex 9b-OMe as a minor product
(Entry 2), which transforms to 8b by elimination of MeOH at 60
ºC.
consistent with the relatively higher nucleophilicity of water. For
7f, an internal alkyne, see Scheme 2, no reaction was observed
under the same condition, possibly due to weaker coordination
of the triple bond to the ruthenium center. In addition, no
organometallic complex is produced in the reaction of 7g, a
tertiary alcohol with 1.
Products 8 and 9 are characterized by spectroscopic methods
and four of which, 8a’, 8b’, 8c and 9e are confirmed by single
crystal X-ray diffraction analysis at room temperature. ORTEP
type views of these complexes are shown in part i - iv in Figure 1.
The structure of 8a’ reveals a simple pyridyl ligand as shown in
part (i). Surprisingly, as shown in part (ii), the originally bonded
nitrogen and the methyl-substituted-carbon atoms in 7b are
separated in the pyridyl ligand in 8b’. This is also true for 8c and
9e-OMe shown in parts (iii) and (iv), respectively. The absence
1
of stereogenic center for 8 and 8’ as disclosed in their H- and
31P-NMR spectra indicates that none of the stereogenic centers
of 7 remains after opening of the aziridine ring.
Table 1. Reactions of 7 with [Ru]-Cl (1, [Ru] = Cp(PPh3)2Ru)[a]
Entry
Substrate
Products[b]
Yield[c]
1
7a: R1=R2=H
8a
8b
8c
8d
87
2
7b: R1=H; R2=Me
7c: R1=H; R2=Ph
7d: R1=H; R2=1-C10H7
9b-OMe
60:26
90
3
4
92
5
7e: R1=R2=Me, in MeOH
9e-OMe
89
7e: R1=R2=Me, in EtOH/H2O
6[d]
9e-OH
9e-OEt
41:44
[a] Typical condition: A mixture of 1 (0.14 mmol), 7 (0.21 mmol) and KPF6
(0.69 mmol) were stirred in MeOH under nitrogen at room temperature for 24
-
h. [b] Counter anion: PF6 and R3’s are shown after 9. [c] Isolated yield (%)
based on 1. [d] Azeotropic EtOH/H2O mixture was used.
Figure 1. ORTEP drawings of complexes 8a’ (i), 8b’ (ii), 8c (iii) and 9e-OMe
(iv). Phenyl groups except Cipso atoms on the phosphine ligands are omitted
for clarity. Thermal ellipsoids are set between 35-65 % probability level.
Moreover, reactions of the phenyl derivative 7c and 1-naphthyl-
substituted derivative 7d with 1 afford the analogous complexes
8c and 8d, respectively, as the only product (Entry 3-4).
Comparable dppe complexes 8a’, 8b’, 8c’ and 8d’ are similarly
prepared from reactions of [Ru’]-Cl (1’, [Ru’] = Cp(dppe)Ru) with
7a, 7b, 7c and 7d, respectively, with no dihydropyridine complex
observed (not shown in the Table). For the reaction of 1 with 7e
containing a geminal dimethyl substituted aziridine in MeOH,
only the dihydropyridine complex 9e-OMe as a dark brown
powder is isolated (Entry 5). The same reaction of 7e with 1 in
azeotropic EtOH/H2O mixture affords the homologous
complexes 9e-OH and 9e-OEt bearing a hydroxy and an ethoxy
group, respectively. (Entry 6) The azeotrope with a ratio of
EtOH:H2O = 95:5 results in two complexes in a ratio of 41:44,
To better understand the mechanism of this transformation,
7e[13C2] with two 25% 13C-labelled carbon atoms of the triple
bond is parepared by treating 6e with freshly prepared 13C-
enriched Me3Si13C≡13CLi followed by removal of the silyl group.
During the skeletal rearrangement (Scheme 3, Eq. (1)), no
cleavage of the triple bond is observed. So, skeletal
rearrangement should occur at two carbon atoms of the aziridine
ring. In addition, D-labelling at the methine group of the aziridine
in 7a is also used to investigate whether a similar skeletal
rearrangement occurs in the nonsubstituted substrate. The
preparation of 7a[D] via a simple deprotonation-deuteration
process at the α-position on the aziridinyl ester 4a, however,
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fails, most likely due to the occurrence of a highly competitive
Claisen condensation.6 The alternative synthetic method
proceeds through the addition of BnNH2 to ethyl 2-bromoacrylate
in the presence of CD3OD via the Gabriel–Cromwell process,7
see Supplementary Information. NMR results show that the
deuterium in 7a[D] ends up at the position para- to the Ru metal
moiety. Subsequent dehydration of E affords the dihydropyridine
complex 9. For reactions of 7a-d, the 1,2-MeOH elimination of 9
also gives rise to 8. Nevertheless, in the reaction of 7e, no
neighboring hydrogen is available for the formation of MeOH,
thus yielding 9e-OMe as the final product. In the reaction of 7g
bearing a tertiary alcohol, the poor migratory aptitude of the
center in 8a[D] with the same percentage of D-labelling (Eq. (2)). tertiary carbon in the transformation from C to D adequately
This is also true for 8a’[D], strongly indicating rearrangement of explains why there is no analogous product.
the two-carbon unit of the aziridine ring during the transformation. To explore more reactivities on similar skeleton, the propargyl
alcohol substituted aziridine 13 on cyclohexyl ring is
a
synthesized (Scheme 5). Iodination of the cyclohexenone 10
catalyzed by 4-(dimethylamino)pyridine (p-DMAP) through the
Baylis–Hillman9 type pathway affords the α-iodinated product 11
which is treated with BnNH2 to generate the corresponding cyclic
aziridinyl ketone 12.7 Treatment of 12 with the Grignard reagent
HC≡CMgBr yields a diastereomeric mixture of 13. The relative
configuration of the aziridine and propargyl alcohol in 13, unlike
that in 7, controls the cycloisomerization reaction. In order to
simplify the reaction, preparation of diastereomerically pure
substrate is carried out by the treatment of 12 with LiC≡CSiMe3,
followed by removal of the silyl group to give the desired product.
Only the anti-isomer 13* with the two functional groups in
different faces of the cyclohexyl ring is obtained and is used in
the following experiments. The reaction of 1 with 13* gives four
products which are difficult to purify. Hence, the dppe complex 1’
is used. Treatment of 13* with 1’ in the presence of KPF6 in
MeOH at room temperature for 3 days affords the cyclic
aminocarbene complex 14’ bearing a dimethyl ketal on a trans-
[4,3,0]-bicyclic skeleton as the major product and the
corresponding ketone isomer 15’ as the minor one (Scheme 5).
These two products are simultaneously obtained by precipitation
from Et2O.
Scheme 3. 13C- and D-labelling experiments.
Mechanism for this transformation is proposed on the basis of a
5-endo-dig
cyclization2d
followed
by
an
aza-pinacol
rearrangement including dehydration and MeOH addition, see
Scheme 4. Coordination of the triple bond gives A. Then
nucleophilic attack of nitrogen of the aziridine to the terminal
alkynyl carbon of A generates the [3,1,0]-bicyclic intermediate B
containing ammonium cation. The C-N bond cleavage gives C
bearing a carbenium ion with a five-membered ring.
Scheme 5. Synthesis and reaction of 13*. Reagents and conditions: (i) I2,
K2CO3, p-DMAP, THF/H2O. (ii) BnNH2, Cs2CO3, 1,10-phenanthroline, toluene,
reflux. (iii) HC≡CSiMe3, n-BuLi, THF, -78 ºC; then rt. (iv) KF, MeOH.
The 1H13C-HSQC spectrum of the mixture displays similar
patterns for 14’ and 15’, revealing the same carbon skeleton.
Moreover, the 1H13C-HMBC spectrum of 14’ displays the
correlation between two methoxy H resonances at δ 2.88 and
2.49 with the quaternary carbon resonance at δ 99.87, strongly
Scheme 4. Proposed mechanism for reactions of 7 with 1.
Subsequent 1,2-alkyl shift, an aza-pinacol rearrangement,8
causes ring expansion to afford D containing an iminium group.
The final dehydration step may proceed by two pathways: in
path a, a direct dehydration process, possibly driven by
aromaticity, gives 8 and, in path b, MeOH is added to the
iminium carbon to generate E bearing a hemiaminal ether
1
indicating
a
dimethyl ketal moiety. (see Supplementary
Information) Single crystals of 15’ are obtained from a mixture of
CH2Cl2/toluene and the structure is determined by an X-ray
diffraction analysis. An ORTEP type view of 15’ is shown in
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Figure 2. The Ru(1)–C(1) and C(1)–N(1) distances of 2.048(4)
and 1.325(5) Å are considered as a long Ru=C double bond and
a short C-N single bond, respectively, suggesting delocalization
of the positive charge. Moreover, the C(4)-O(1) distance of
1.178(7) Å represents a typical C=O double bond. A trans-
configuration is observed in the bicyclic skeleton around two
bridge head atoms C(3) and C(8).
Due to this spatial restriction, only the γ-hydroxyl vinylidene
intermediate F is generated and is transformed into the
allenylidene intermediate G by dehydration. This linear ligand
would not assist intramolecular nucleophilic addition of the
nitrogen onto the electrophilic Cα or Cγ. Instead, addition of
MeOH to Cγ of G proceeds via two possible directions. For
addition from the more hindered face, the γ-methoxy vinylidene
intermediate anti-H with the same configuration as F resulted.
No further cyclization would occur and anti-H undergoes MeOH
elimination to give back G. Alternatively, addition from the less
hindered face generates the vinylidene intermediate syn-H with
an opposite configuration. Cyclization now takes place due to
the closeness of Cα and the aziridine in syn-H. Nucleophilic
addition of nitrogen to Cα gives rise to the fused tricyclic
intermediate J containing an ammonium cation.
A second MeOH selectively attacks at the bridged carbon of J to
release ring strain producing the [3,3,1]-bicyclic K. Subsequently,
the reaction may proceed through two possible pathways,
shown in the Scheme. In path a, semipinacol rearrangement11
results in a 1,2-Cβ migration to generate M bearing an oxonium
cation on the [4,3,0]-bicyclic skeleton. This transformation
results in cleavage of the Cβ-Cγ bond and was rarely found in
reactions of propargyl alcohols. Alternatively, in path b, the
Figure 2. An ORTEP drawing of 15’. Phenyl groups except Cipso atoms on
the dppe ligand are omitted for clarity. Thermal ellipsoid is set at the 35 %
probability level.
ruthenium induced cyclopropanation,12
a metal carbenoid
assisted process, is accompanied with removal of the methoxy
group on the bridge to generate another fused tricyclic species L.
Then, lone pair electrons in the methoxy group induce ring
opening reaction of the cyclopropyl13 moiety also to give M.
Subsequent MeOH addition to the carbon atom near the
oxonium ion followed by a proton transfer to Cβ affords 14’
bearing a dimethyl ketal moiety. In the presence of water, which
was generated from F to G, hydrolysis of this functional group
gives rise to the corresponding ketone product identified as 15’.
Nevertheless, if water is added to M to form the corresponding
hemiketal species, inherent reactivity of which leads to MeOH
elimination to afford also 15’.
As shown in Scheme 6, mechanism for the formation of 14’ and
15’ from 13* is proposed on the basis of an interchange process
between vinylidene and allenylidene species10 followed by
nucleophilic cyclization and subsequent rearrangement process.
Even with high electrophilicity via π-coordination, the triple bond
and the aziridine would not undergo cyclization reaction because
the two are not in proximity.
Reaction of the homologous propargyl alcohol containing an
aziridine moiety on a five-membered cyclopentyl ring with [Ru’]-
Cl (1’) is also explored. Different from simple results of 13*
described above, a complicated mixture beyond characterization
is obtained under the same condition. Following the mechanism
of 13* described above, higher reactivity of
a tricyclic
intermediate similar to L but with a much higher ring strain
results in lower selectivity to produce isolable product.
Conclusions
In summary, ring expansion reactions of several propargyl
alcohol substituted aziridines induced by CpL2RuCl (Cp=η5-C5H5,
L2 = (PPh3)2 or (dppe)) are explored for two types of substrates 7
and 13* without and with cycloalkane skeleton, respectively. For
7, the two carbon unit of the aziridine ring rearranged in the ring
expansion process via a unique reaction pathway with complete
selectivity giving complexes with substituted pyridine or dihydro-
pyridine ligand. The mechanism is proposed on the basis of a 5-
endo-dig cyclization followed by an aza-pinacol rearrangement.
Scheme 6. Proposed mechanism for reactions of 13* with 1’.
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77.64, H 7.56, N 6.91. Data for 7c. syn:anti = 5.7:1. syn-isomer: 1H-NMR
In contrast, reactivity of 13* with a cyclohexyl moiety, may be
affected by the inhibited free rotation of the bond between the
propargyl and the aziridinyl groups. As a result, transformation
pathways were dictated by the relative configuration of these two
functional groups. Mechanism of the reaction of 13* is proposed
on the basis of an interchange of vinylidene and allenylidene
species accompanied with configurational change at the
propargyl position. This is followed by the bond formation
between nitrogen of the aziridine ring and Cα and succeeding
semipinacol rearrangement, or a metal carbenoid assisted
cyclopropanation process gives carbene complexes with
octahydroindole derivatives. Ring size of the cycloalkane unit
plays a significant role during this later transformation.
2
(δ, CDCl3): 7.45-7.21 (m, 10H, Ph), 3.90, 3.62 (2d, JHH = 13.3 Hz, 2H,
3
CH2), 3.85-3.79 (m, 1H, CH), 2.94 (d, JHH = 6.2 Hz, 1H, NCH), 2.37 (d,
3
4JHH = 2.2 Hz, 1H, CH), 2.25 (dd, JHH = 8.4, 6.2 Hz, 1H, NCH), 1.79 (s,
1H, OH). 13C-NMR (δ, CDCl3): 138.74 (C), 136.29 (C), 128.72 (CH),
128.65 (CH), 128.62 (CH), 128.04 (CH), 127.56 (CH), 127.53 (CH),
83.66 (C), 73.67 (CH), 64.20 (CH2), 60.78 (CH), 50.39 (CH), 46.23 (CH).
1
anti-isomer: H-NMR (δ, CDCl3): 7.45-7.21 (m, 10H, Ph), 3.90, 3.62 (2d,
2JHH = 13.3 Hz, 2H, CH2), 3.68-3.62 (m, 1H, CH), 3.02 (d, 3JHH = 6.7 Hz,
4
3
1H, NCH), 2.40 (d, JHH = 2.0 Hz, 1H, CH), 2.33 (dd, JHH = 7.9, 6.7 Hz,
1H, NCH), 1.79 (s, 1H, OH). MS ESI (m/z) calculated for C18H17NO:
263.1310; found: 264.1389 (M+1)+. Elemental analysis (%) calculated for
C18H17NO: C 82.10, H 6.51, N 5.32; found: C 82.21, H 6.57, N 5.27.
Synthesis of 7a[D] and 7e[13C2] and data for 7d, 7e, 7f and 7g are given
in the Supplementary Information.
Synthesis of 8a. An aliquot of MeOH (25 mL) was added to a Schlenk
flask charged with [Ru]-Cl (0.300g, 0.414 mmol), 7a (0.116 g, 0.62 mmol)
and KPF6 (0.190 g, 1.03 mmol) under nitrogen. The resulting mixture was
stirred at room temperature. Consumption of the ruthenium complex was
monitored by 31P-NMR spectra. Then the solvent was removed under
reduced pressure. Solid residue was extracted with CH2Cl2 and mixture
was filtered through a bed of Celite to remove insoluble salts. The filtrate
was concentrated under reduced pressure into a small volume followed
by reprecipitation by addition to a solution of Et2O under vigorous stirring.
Precipitates thus formed were collected in a glass frit, washed with Et2O,
and dried under vacuum to give 8a (0.309 g, 87 % yield based on 1).
Other compounds 8 and 9 were prepared similarly.
Experimental Section
General Procedures. Manipulations were performed under an
atmosphere of dry nitrogen by using a vacuum line and standard Schlenk
techniques. Solvents were dried by standard methods and distilled under
nitrogen before use. The ruthenium complex Cp(PPh3)2RuCl (1)14 and
Cp(dppe)RuCl (1’),15 compounds 2-6,5 11,9 127 and the corresponding
cyclopentyl homologue of 13* were prepared by following the method
reported in the literature, see Supplementary Information). Mass spectra
were recorded with a Mass Spectrometer (ESI). The C, H and N
analyses and the X-ray diffraction study were carried out at the Regional
Center of Analytical Instrument at the National Taiwan University. The
1H- and 13C-NMR spectra, recorded with a 400 or a 500 MHz FT-NMR
spectrometer at room temperature were obtained in CDCl3 or acetone-d6
at ambient temperature. Proton chemical shifts are referenced to δ 7.26
(CHCl3) or δ 2.09 (acetone) and carbon chemical shifts are referenced to
δ 77.36 (CDCl3) or δ 205.87 (acetone). 31P-NMR (161 MHz) spectra were
measured relative to external 85 % phosphoric acid. Both 13C- and 31P-
NMR spectra were proton decoupled.
3
Data for 8a. 1H-NMR (δ, acetone-d6): 8.68 (d, JHH = 7.9 Hz, 1H, CH),
3
7.99 (d, JHH = 5.5 Hz, 1H, CH), 7.92 (s, 1H, CH), 7.50-6.95 (35H, Ph),
7.05, 7.04 (dd, 3JHH = 7.9, 5.5 Hz, 1H, CH), 5.05 (s, 2H, CH2), 4.58 (s, 5H,
2
Cp). 13C-NMR (δ, acetone-d6): 170.66 (t, JPC = 16.4 Hz, C, Ru-C),
161.72 (CH), 153.85 (CH), 134.43 (CH), 122.75 (CH), 137.78-127.73
(Ph), 87.52 (Cp), 63.30 (CH2). 31P-NMR (δ, acetone-d6): 50.01 (s, PPh3).
MS ESI (m/z) calculated for C53H46NP2Ru: 860.2149; found: 860.2158
(M+). Elemental analysis (%) calculated for C53H46F6NP3Ru: C 63.35, H
4.61, N 1.39; found: C 63.52, H 4.64, N 1.38. Data for 8a’. 1H-NMR (δ,
Synthesis of 7a. Ethynylmagnesium bromide (0.5 M in THF, 80.0 mL,
40.0 mmol) was added to a solution of 6a (3.2 g, 20.0 mmol) in THF at -
78 ºC under nitrogen. The mixture was warmed to room temperature and
stirred for 24 h. Then the reaction was quenched with a saturated
aqueous solution of NH4Cl, and Et2O was used to extract the crude
product. The combined organic layer was washed with brine, dried over
anhydrous MgSO4, filtered and further dried under reduced pressure. The
residue was purified by column chromatography using EA/hexane 1/4 as
the eluent to give 7a. (3.1 g, 84 % yield) Compounds 7b – 7g are
similarly prepared in 84 – 88% yields.
3
3
acetone-d6): 7.85 (d, JHH = 5.4 Hz, 1H, CH), 7.80 (d, JHH = 7.8 Hz, 1H,
CH), 7.58 (s, 1H, CH), 7.60-7.34 (m, 25H, Ph), 6.64, 6.63 (dd, 3JHH = 7.8,
3
5.4 Hz, 1H, CH), 4.50 (s, 2H, CH2), 4.83 (s, 5H, Cp), 2.57 (t, JHH = 9.5
Hz, 4H, CH2). 13C-NMR (δ, acetone-d6): 170.59 (t, 2JPC = 15.3 Hz, C, Ru-
C), 161.49 (CH), 152.88 (CH), 133.43 (CH), 122.04 (CH), 142.18-128.71
(Ph), 85.47 (Cp), 63.07 (CH2), 27.79 (t, 1JPC = 23.0 Hz, CH2). 31P-NMR (δ,
acetone-d6): 90.26 (s, dppe). MS ESI (m/z) calculated for C43H40NP2Ru:
734.1679; found: 734.1696 (M+). Elemental analysis (%) calculated for
C43H40F6NP3Ru: C 58.77, H 4.59, N 1.59; found: C 58.83, H 4.61, N 1.58.
1
Data for 8b. H-NMR (δ, acetone-d6): 8.34 (s, 1H, CH), 8.02 (s, 1H, CH),
7.89 (s, 1H, CH), 7.54-7.14 (35H, Ph), 5.29 (s, 2H, CH2), 4.57 (s, 5H, Cp),
1.92 (s, 3H, CH3). 13C-NMR (δ, acetone-d6): 168.67 (br, C, Ru-C), 162.52
(CH), 151.31 (CH), 135.68 (CH), 132.37 (C), 137.93-128.02 (Ph), 87.22
(Cp), 63.10 (CH2), 17.38 (CH3). 31P-NMR (δ, acetone-d6): 50.04 (s, PPh3).
MS ESI (m/z) calculated for C54H48NP2Ru: 874.2305; found: 874.2324
(M+). Data for 9b. 1H-NMR (δ, acetone-d6): 8.22 (s, 1H, CH), 7.54-7.14
Data for 7a. syn:anti = 12.5:1. syn-isomer: 1H-NMR (δ, CDCl3): 7.38-7.25
(m, 5H, Ph), 4.17-4.11 (m, 1H, CH), 3.57, 3.49 (2d, JHH = 13.2 Hz, 2H,
2
CH2), 3.15 (s, 1H, OH), 2.38 (d, 4JHH = 2.2 Hz, 1H, CH), 2.03-1.98 (m, 1H,
NCH), 1.92 (d, 3JHH = 3.4 Hz, 1H, NCH), 1.53 (d, 3JHH = 6.3 Hz, 1H, NCH).
13C-NMR (δ, CDCl3): 138.69 (C), 128.78 (CH), 128.64 (CH), 127.71 (CH),
83.45 (C), 73.06 (CH), 63.93 (CH2), 61.63 (CH), 43.38 (CH), 31.16 (CH2).
anti-isomer: 1H-NMR (δ, CDCl3): 7.38-7.25 (m, 5H, Ph), 4.48 (s, 1H, CH),
3
(35H, Ph), 6.83 (d, JHH = 5.9 Hz, 1H, CH), 4.81 (s, 2H, CH2), 4.42 (d,
3JHH = 2.7 Hz, 1H, CH), 4.39 (s, 5H, Cp), 3.39 (s, 3H, CH3O), 2.55 (br, 1H,
3.65, 3.41 (2d, 2JHH = 13.4 Hz, 2H, CH2), 2.93 (s, 1H, OH), 2.41 (d, 4JHH
=
3
3
CH), 0.57 (d, JHH = 7.4 Hz, 3H, CH3). 13C-NMR (δ, acetone-d6): 175.32
2.2 Hz, 1H, CH), 2.08 (d, JHH = 3.4 Hz, 1H, NCH), 2.03-1.98 (m, 1H,
3
(CH), 160.91 (CH), 138.47 (br, C, Ru-C), 137.93-128.02 (Ph), 90.35 (CH),
86.26 (Cp), 61.85 (CH2), 57.81 (CH3), 37.52 (C), 15.55 (CH3). 31P-NMR
NCH), 1.56 (d, JHH = 6.3 Hz, 1H, NCH). MS ESI (m/z) calculated for
C12H13NO: 187.0997; found: 188.1075 (M+1)+. Elemental analysis (%)
calculated for C12H13NO: C 76.98, H 7.00, N 7.48; found: C 77.05, H 7.07,
N 7.41. Data for 7b. Spectroscopic data are complicated for analysis
because of the existence of four pairs of diastereomers. MS ESI (m/z)
calculated for C13H15NO: 201.1154; found: 224.1051 (M+23)+. Elemental
analysis (%) calculated for C13H15NO: C 77.58, H 7.51, N 6.96; found: C
2
(δ, acetone-d6): 49.03, 48.72 (2d, JPP = 34.4 Hz, PPh3). MS ESI (m/z)
calculated for C55H52NOP2Ru: 906.2568; found: 906.2554 (M+). Data for
1
8b’. H-NMR (δ, acetone-d6): 7.77 (s, 1H, CH), 7.51 (s, 1H, CH), 7.47 (s,
1H, CH), 7.61-7.33 (25H, Ph), 5.01 (s, 2H, CH2), 4.86 (s, 5H, Cp), 2.62-
2.45 (m, 4H, CH2), 1.77 (s, 3H, CH3). 13C-NMR (δ, acetone-d6): 168.93 (t,
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2JPC = 16.1 Hz, C, Ru-C), 162.96 (CH), 150.27 (CH), 133.28 (CH),
aqueous layer was further extracted with Et2O. The combined organic
layers were dried over anhydrous MgSO4, filtered and concentrated
under reduced pressure to afford the colorless liquid identified as 13*
(4.85 g, 82 % yield over two steps from 12).
131.71 (C), 142.23-128.73 (Ph), 85.24 (Cp), 62.99 (CH2), 27.87 (t, 1JPC
=
23.0 Hz, CH2), 17.30 (CH3). 31P-NMR (δ, acetone-d6): 89.83 (s, dppe).
MS ESI (m/z) calculated for C44H42NP2Ru: 748.1836; found: 748.1815
(M+). Elemental analysis (%) calculated for C44H42F6NP3Ru: C 59.19, H
4.74, N 1.57; found: C 59.25, H 4.78, N 1.56. Data for 8c. 1H-NMR (δ,
acetone-d6): 8.67 (s, 1H, CH), 8.37 (s, 1H, CH), 8.26 (s, 1H, CH), 7.48-
7.06 (40H, Ph), 5.54 (s, 2H, CH2), 4.62 (s, 5H, Cp). 13C-NMR (δ,
acetone-d6): 170.68 (t, 2JPC = 15.2 Hz, C, Ru-C), 160.40 (t, 3JPC = 5.3 Hz,
CH), 152.07 (CH), 136.26 (C), 132.93 (CH), 138.02-125.87 (Ph), 86.91
(Cp), 63.36 (CH2). 31P-NMR (δ, acetone-d6): 49.69 (s, PPh3). MS ESI
(m/z) calculated for C59H50NP2Ru: 936.2462; found: 936.2508 (M+).
Elemental analysis (%) calculated for C59H50F6NP3Ru: C 65.55, H 4.66, N
1
Data for 13-TMS. H-NMR (δ, CDCl3): 7.30-7.18 (m, 5H, Ph), 3.73, 3.23
2
(2d, JHH = 13.6 Hz, 2H, CH2), 3.01 (s, 1H, OH), 2.18 (d, 3JHH = 6.2 Hz,
1H, NCH), 2.02-1.97 (m, 1H, NCH), 1.84-1.27 (m, 6H, CH2), 0.14 (s, 9H,
CH3). 13C-NMR (δ, CDCl3): 139.29 (C), 128.81 (CH), 128.12 (CH), 127.52
(CH), 108.82 (C), 88.16 (C), 65.05 (C), 64.07 (CH2), 47.92 (CH), 42.67
(CH), 37.18 (CH2), 23.61 (CH2), 17.02 (CH2), 0.31 (CH3). MS ESI (m/z)
calculated for C18H25NOSi: 299.1705; found: 300.1782 (M+1)+. Data for
2
13*. 1H-NMR (δ, CDCl3): 7.35-7.24 (m, 5H, Ph), 3.68, 3.36 (2d, JHH
=
1
13.5 Hz, 2H, CH2), 3.04 (s, 1H, OH), 2.49 (s, 1H, CH), 2.23 (d, 3JHH = 6.3
Hz, 1H, NCH), 2.08-2.03 (m, 1H, NCH), 1.90-1.34 (m, 6H, CH2). 13C-
NMR (δ, CDCl3): 139.13 (C), 128.85 (CH), 128.19 (CH), 127.60 (CH),
87.22 (C), 71.94 (CH), 64.71 (C), 64.07 (CH2), 47.69 (CH), 42.52 (CH),
36.97 (CH2), 23.52 (CH2), 16.94 (CH2). MS ESI (m/z) calculated for
C15H17NO: 227.1310; found: 228.1387 (M+1)+. Elemental analysis (%)
calculated for C15H17NO: C 79.26, H 7.54, N 6.16; found: C 79.30, H 7.61,
N 6.10.
1.30; found: C 65.64, H 4.69, N 1.29. Data for 8c’. H-NMR (δ, acetone-
d6): 8.18 (s, 1H, CH), 7.97 (s, 1H, CH), 7.63 (s, 1H, CH), 7.66-6.89 (30H,
Ph), 5.24 (s, 2H, CH2), 4.90 (s, 5H, Cp), 2.72-2.53 (m, 4H, CH2). 13C-
NMR (δ, acetone-d6): 170.74 (t, 2JPC = 15.1 Hz, C, Ru-C), 158.56 (t, 3JPC
= 4.5 Hz, CH), 151.97 (CH), 135.07 (C), 131.28 (CH), 142.06-127.15
(Ph), 85.15 (Cp), 63.18 (CH2), 27.90 (t, 1JPC = 22.4 Hz, CH2). 31P-NMR (δ,
acetone-d6): 89.59 (s, dppe). MS ESI (m/z) calculated for C49H44NP2Ru:
810.1992; found: 810.1996 (M+). Elemental analysis (%) calculated for
C49H44F6NP3Ru: C 61.63, H 4.64, N 1.47; found: C 61.74, H 4.67, N 1.46.
Synthesis of 14’ and 15’. MeOH (25 mL) was added to a Schlenk flask
charged with [Ru’]-Cl (0.10 g, 0.17 mmol), aziridinyl propargylic alcohol
13* (0.057 g, 0.25 mmol), and KPF6 (0.15 g, 0.83 mmol) under nitrogen.
The resulting mixture was stirred at room temperature. Then the solvent
was removed under reduced pressure after consumption of [Ru’]-Cl as
monitored by 31P-NMR spectra. Solid residue was extracted with CH2Cl2
and the mixture was filtered through a bed of Celite to remove insoluble
salts. The filtrate was concentrated under reduced pressure to a small
volume followed by reprecipitation by addition to a solution of Et2O under
vigorous stirring. Precipitates thus formed were collected in a glass frit,
washed with Et2O, and dried under vacuum. (65 % yield for 14’ and 22 %
for 15’)
1
Data for 9e-OMe. H-NMR (δ, CDCl3): 7.77 (s, 1H, CH), 7.40-6.94 (35H,
2
Ph), 6.21 (s, 1H, CH), 4.66, 4.62 (2d, JHH = 15.5 Hz, 2H, CH2), 4.21 (s,
1H, CH), 4.12 (s, 5H, Cp), 3.39 (s, 3H, CH3O), 0.58 (s, 3H, CH3), 0.56 (s,
3H, CH3). 13C-NMR (δ, CDCl3): 173.53 (CH), 165.48 (t, JPC = 5.4 Hz,
3
CH), 137.74 (br, C, Ru-C), 138.56-128.24 (Ph), 95.47 (CH), 85.72 (Cp),
61.89 (CH3), 58.78 (CH2), 40.27 (C), 24.27 (CH3), 19.32 (CH3). 31P-NMR
(δ, CDCl3): 49.25, 48.96 (2d, JPP = 34.3 Hz, PPh3). MS ESI (m/z)
2
calculated for C56H54NOP2Ru: 920.2724; found: 920.2774 (M+).
Elemental analysis (%) calculated for C56H54F6NOP3Ru: C 63.15, H 5.11,
N 1.32; found: C 63.23, H 5.12, N 1.32. Data for 9e-OH. 1H-NMR (δ,
CDCl3): 7.60 (s, 1H, CH), 7.45-6.91 (35H, Ph), 6.42 (s, 1H, CH), 5.15 (br,
1H, OH), 4.76, 4.70 (2d, 2JHH = 15.3 Hz, 2H, CH2), 4.31 (s, 1H, CH), 4.09
(s, 5H, Cp), 0.81 (s, 3H, CH3), 0.52 (s, 3H, CH3). 13C-NMR (δ, CDCl3):
172.38 (CH), 164.99 (s, CH), 136.78 (br, C, Ru-C), 138.43-128.30 (Ph),
86.07 (Cp), 85.86 (CH), 58.07 (CH2), 39.59 (C), 24.72 (CH3), 20.23 (CH3).
Data for 14’. 1H-NMR (δ, CDCl3): 7.77-6.92 (25H, Ph), 4.98, 4.03 (2d,
2
2JHH = 15.9 Hz, 2H, CH2), 4.66 (s, 5H, Cp), 3.08 (t, JHH = 11.5 Hz, 1H,
CH), 3.02-2.71 (m, 4H, CH2), 2.88 (s, 3H, CH3O), 2.49 (s, 3H, CH3O),
2.39 (dd, JHH = 16.8 Hz, JHH = 5.8 Hz, 1H, CH2), 2.09 (dd, JHH = 15.9 Hz,
JHH = 5.8 Hz, 1H, CH2), 1.81-0.73 (m, 6H, CH2), 0.89-0.80 (m, 1H, CH).
31P-NMR (δ, CDCl3): 49.54, 49.14 (2d, JPP = 33.6 Hz, PPh3). MS ESI
(m/z) calculated for C55H52NOP2Ru: 906.2568; found: 906.2581 (M+).
Data for 9e-OEt. 1H-NMR (δ, CDCl3): 7.86 (s, 1H, CH), 7.45-6.91 (35H,
2
2
13C-NMR (δ, CDCl3): 249.71 (t, JPC = 13.6 Hz, Ru=C), 141.84-126.27
2
Ph), 6.16 (s, 1H, CH), 4.66, 4.62 (2d, JHH = 14.5 Hz, 2H, CH2), 4.40 (s,
3
(Ph), 99.87 (C), 84.62 (Cp), 69.93 (CH), 58.01 (t, JPC = 7.4 Hz, CH2),
1H, CH), 4.15 (s, 5H, Cp), 3.80-3.72, 3.65-3.57 (m, 2H, CH2), 1.16 (t,
3JHH = 7.0 Hz, 3H, CH3), 0.59 (s, 3H, CH3), 0.56 (s, 3H, CH3). 13C-NMR (δ,
CDCl3): 173.68 (CH), 165.48 (s, CH), 137.83 (br, C, Ru-C), 138.43-
128.30 (Ph), 94.35 (CH), 85.56 (Cp), 70.03 (CH2), 58.07 (CH2), 40.02 (C),
24.35 (CH3), 19.20 (CH3), 15.53 (CH3). 31P-NMR (δ, CDCl3): 49.34, 48.71
55.78 (CH2), 52.14 (CH), 49.47 (CH3), 48.05 (CH3), 31.68 (CH2), 30.51
(dd, 1JPC = 33.9 Hz, 2JPC = 14.8 Hz, CH2), 27.82 (CH2), 27.64 (dd, 1JPC
=
29.5 Hz, 2JPC = 14.4 Hz, CH2), 21.14 (CH2). 31P-NMR (δ, CDCl3): 86.60,
2
82.93 (2d, JPP
= 19.4 Hz, dppe). MS ESI (m/z) calculated for
C48H52NO2P2Ru: 838.2517; found: 838.2505 (M+). Data for 15’. H-NMR
(δ, CDCl3): 7.77-6.92 (25H, Ph), 5.15, 4.24 (2d, 2JHH = 16.7 Hz, 2H, CH2),
4.64 (s, 5H, Cp), 2.97-2.88 (m, 1H, CH), 3.02-2.71 (m, 4H, CH2), 2.26 (dd,
JHH = 17.1 Hz, JHH = 5.7 Hz, 1H, CH2), 1.95-1.88 (m, 1H, CH2), 2.13-2.05,
1.99-1.92 (m, 2H, CH2), 1.80-1.71 (m, 1H, CH), 1.88-0.73 (m, 4H, CH2).
1
2
(2d, JPP = 34.1 Hz, PPh3). MS ESI (m/z) calculated for C57H56NOP2Ru:
934.2881; found: 934.2905 (M+).
Synthesis of 13*. To a solution of HC≡CSiMe3 (7.40 ml, 52.0 mmol) in
THF was added BuLi (2.5 M in hexane, 20.8 mL, 52.0 mmol) at -78 ºC
under nitrogen. The resulting solution was stirred at the same
temperature for 30 minutes. After that, 12 (5.23 g, 26.0 mmol) in THF
was added at -78 ºC. The mixture was warmed to room temperature and
stirred for 24 h. Then the reaction was quenched with a saturated
aqueous solution of NH4Cl, and Et2O was used to extract the crude
product. The combined organic layer was washed with brine, dried over
anhydrous MgSO4, filtered and further dried under reduced pressure. The
residue was purified by recrystallization to give 13-TMS as white solid. To
a solution of 13-TMS in MeOH was added KF (3.02 g, 52.0 mmol). The
resulting solution was stirred overnight. After that, the solvent was
removed under reduced pressure. The resulting suspension was
extracted with Et2O and brine. The organic layer was separated and the
2
13C-NMR (δ, CDCl3): 251.61 (t, JPC = 13.2 Hz, Ru=C), 206.11 (C=O),
141.84-126.27 (Ph), 85.33 (Cp), 71.84 (CH), 56.07 (CH2), 54.24 (CH),
54.17 (CH2), 39.63 (CH2), 30.51 (dd, 1JPC = 33.9 Hz, 2JPC = 14.8 Hz, CH2),
27.93 (CH2), 27.64 (dd, 1JPC = 29.5 Hz, 2JPC = 14.4 Hz, CH2), 23.97 (CH2).
2
31P-NMR (δ, CDCl3): 89.85, 85.74 (2d, JPP = 17.3 Hz, dppe). MS ESI
(m/z) calculated for C46H46NOP2Ru: 792.2098; found: 792.2188 (M+).
Single crystal X-ray diffraction analysis: Single crystals suitable for X-
ray diffraction study were glued to glass fibers and mounted on a SMART
CCD diffractometer. The diffraction data were collected by using a 3 kW
sealed-tube MoKα radiation source (T = 295(2) K for 8a’ and 9e-OMe; T =
150(2) K for 8b’, 8c and 15’). Exposure time was 5 s per frame. SADABS
absorption correction16 was applied, and decay was negligible. Data were
For internal use, please do not delete. Submitted_Manuscript

Chemistry - An Asian Journal
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FULL PAPER
processed and structures were solved and refined by using SHELXTL.17
Crystal data are given in the Supplementary Information.
[9]
S. J. Calvin, D. Mangan, I. Miskelly, T. S. Moody, P. Stevenson, J. Org.
Process Res. Dev. 2012, 16, 82−86.
[10] a) H. Katayama, F. Ozawa, Coord. Chem. Rev. 2004, 248, 1703−1715;
b) S. Rigaut, D. Touchard, P. H. Dixneuf, Coord. Chem. Rev. 2004, 248,
1585−1601; c) H.-W. Ma, Y.-C. Lin, S.-L. Huang, Org. Lett. 2012, 14,
3846−3849; d) C.-C. Chen, P.-C. Cheng, S.-L. Huang, Y.-C. Lin, Y.-H.
Liu, Chem. Asian J. 2011, 6, 3122−3131; e) C.-P. Chung, C.-C. Chen,
Y.-C. Lin, Y.-H. Liu, Y. Wang, J. Am. Chem. Soc. 2009, 131,
18366−18375.
Acknowledgements
Financial support from the Ministry of Science and Technology
of Taiwan, ROC, under the grant number of MOST 103-2113-M-
002-004 is appreciated.
[11] a) B. Wang, Y. -Q. Tu, Acc. Chem. Res. 2011, 44, 1207−1222; b) Z.-L.
Song, C.-A. Fan, Y.-Q. Tu, Chem. Rev. 2011, 111, 7523−7556; c) T. J.
Snape, Chem. Soc. Rev. 2007, 36, 1823−1842; d) B. Crone, S. F.
Kirsch, Chem. Eur. J. 2008, 14, 3514−3522; e) J. T. Binder, B. Crone, S.
F. Kirsch, C. Liébert, H. Menz, Eur. J. Org. Chem. 2007, 1636−1647; f)
V. N. Korotchenko, M. R. Gagné, J. Org. Chem. 2007, 72, 4877−4881;
g) S. F. Kirsch, J. T. Binder, C. Liébert, H. Menz, Angew. Chem. Int. Ed.
2006, 45, 5878−5880; h) L. E. Overman, L. D. Pennington, J. Org.
Chem. 2003, 68, 7143−7157; i) L. E. Overman, J. P. Wolfe, J. Org.
Chem. 2002, 67, 6421−6429; j) F. Cohen, D. W. C. MacMillan, L. E.
Overman, A. Romero, Org. Lett. 2001, 3, 1225−1228.
Keywords: ruthenium • propargyl alcohol • aziridine • ring
expansion • rearrangement
[1]
a) S. Stanković, M. D’hooghe, S. Catak, H. Eum, M. Waroquier, V. Van
Speybroeck, N. De Kimpe, H.-J. Ha, Chem. Soc. Rev. 2012, 41,
643−665; b) I. D. G. Watson, L. Yu, A. K. Yudin, Acc. Chem. Res. 2006,
39, 194−206; c) J. B. Sweeney, Chem. Soc. Rev. 2002, 31, 247−258;
d) W. McCoull, F. A. Davis, Synthesis 2000, 10, 1347−1365; e) A.
Padwa, S. S. Murphree, Arkivoc 2006, 3, 6−33; f) G. S. Singh, M.
D’hooghe, N. De Kimpe, Chem. Rev. 2007, 107, 2080−2135; g) H. M. I.
Osborn, J. Sweeney, Tetrahedron Asymmetry 1997, 8, 1693-1894; h) D.
Tanner, Angew. Chem. Int. Ed. 1994, 33, 599−619.
[12] a) E. Soriano, J. Marco-Contelles, Acc. Chem. Res. 2009, 42,
1026−1036; b) E. Jiménez-Núñez, A. M. Echavarren, Chem. Rev. 2008,
108, 3326−3350; c) A. M. Echavarren, C. Nevado, Chem. Soc. Rev.
2004, 33, 431−436; d) S. F. Kirsch, J. T. Binder, B. Crone, A. Duschek,
T. T. Haug, C. Liébert, H. Menz, Angew. Chem. Int. Ed. 2007, 46,
2310−2313; e) A. K. Buzas, F. M. Istrate, F. Gagosz, Angew. Chem. Int.
Ed. 2007, 46, 1141−1144; f) C. Nieto-Oberhuber, M. P. Muñoz, S.
López, E. Jiménez-Núñez, C. Nevado, E. Herrero-Gómez, M. Raducan,
A. M. Echavarren, Chem. Eur. J. 2006, 12, 1677−1693; g) F. Gagosz,
Org. Lett. 2005, 7, 4129−4132; h) C. Nieto-Oberhuber, M. P. Muñoz, E.
Buñuel, C. Nevado, D. J. Cárdenas, A. M. Echavarren, Angew. Chem.
Int. Ed. 2004, 43, 2402−2406; i) V. Mamane, T. Gress, H. Krause, A.
Fürstner, J. Am. Chem. Soc. 2004, 126, 8654−8655.
[2]
a) M. Yoshida, Y. Maeyama, M. Al-Amin, K. Shishido, J. Org. Chem.
2011, 76, 5813−5820; b) A. Blanc, A. Alix, J.-M. Weibel, P. Pale, Eur. J.
Org. Chem. 2010, 1644−1647; c) X. Du, X. Xie, Y. Liu, J. Org. Chem.
2010, 75, 510−513; d) X. Zhao, E. Zhang, Y.-Q. Tu, Y.-Q. Zhang, D.-Y.
Yuan, K. Cao, C.-A. Fan, F.-M. Zhang, Org. Lett. 2009, 11, 4002−4004;
e) M. Yoshida, M. Al-Amin, K. Shishido, Synthesis 2009, 14,
2454−2466; f) D.-D. Chen, X.-L. Hou, L.-X. Dai, Tetrahedron Lett. 2009,
50, 6944−6946.
[3]
a) A. Kulshrestha, N. Salehi-Marzijarani, K. D. Ashtekar, R. Staples, B.
Borhan, Org. Lett. 2012, 14, 3592−3595; b) X. Du, S. Yang, J. Yang, Y.
Liu, Chem. Eur. J. 2011, 17, 4981−4985; c) C.-H. Ding, L.-X. Dai, X.-L.
Hou, Tetrahedron 2005, 61, 9586−9593; d) R. J. Madhushaw, C.-C. Hu,
R.-S. Liu, Org. Lett. 2002, 4, 4151−4153.
[13] a) J.-M. Tang, S. Bhunia, S. Md. A. Sohel, M.-Y. Lin, H.-Y. Liao, S.
Datta, A. Das, R.-S. Liu, J. Am. Chem. Soc. 2007, 129, 15677−15683;
b) X.-G. Huang, L.-M. Zhang, J. Am. Chem. Soc. 2007, 129,
6398−6399; c) E. Jiménez-Núñez, C. K. Claverie, C. Nieto-Oberhuber,
A. M. Echavarren, Angew. Chem. Int. Ed. 2006, 45, 5452−5455; d) L.
Zhang, S. A. Kozmin, J. Am. Chem. Soc. 2004, 126, 11806−11807.
[14] M. I. Bruce, R. C. Wallis, Aust. J. Chem. 1979, 32, 1471-1485.
[15] G. S. Ashby, M. I. Bruce, I. B. Tomkins, R. C. Wallis, Aust. J. Chem.
1979, 32, 1003-1016.
[4]
[5]
a) P. W. Davies, N. Martin, N. Spencer, Beilstein J. Org. Chem. 2011, 7,
839−846; b) P. W. Davies, N. Martin, J. Organomet. Chem. 2011, 696,
159−164; c) P. W. Davies, N. Martin, Org. Lett. 2009, 11, 2293−2296.
a) J. M. Andrés, N. de Elena, R. Pedrosa, A. Pérez-Encabo,
Tetrahedron 1999, 55, 14137−14144; b) X. Fan, H.-S. Zhang, L. Chen,
Y.-Q. Long, Eur. J. Med. Chem. 2010, 45, 2827−2840.
[16] The SADABS program is based on the method developed by Blessing,
see: R. H. Blessing, Acta Crystallogr. Sect. A 1995, 51, 33-38.
[6]
[7]
[8]
A. P. Patwardhan, V. R. Pulgam, Y. Zhang, W. D. Wulff, Angew. Chem.
Int. Ed. 2005, 44, 6169−6172.
[17] SHELXTL: Structure Analysis Program, version 5.04; Siemens
Industrial Automation Inc., Madison, 1995.
M. T. Barros, C. D. Maycock, M. R. Ventura, Tetrahedron Lett. 2002, 43,
4329−4331.
a) Y. Sugihara, S. Iimura, J. Nakayama, Chem. Commun. 2002,
134−135; b) H. Razavi, R. Polt, J. Org. Chem. 2000, 65, 5693−5706.
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Shu-Hao Wan, Ying-Chih Lin,* Ling-
Kang Liu and Yi-Hung Liu
Page No. – Page No.
Ring Expansion and Skeletal
Rearrangement of Propargyl Alcohol
Substituted Aziridines Induced by Ru
Complexes
Text for Table of Contents
For internal use, please do not delete. Submitted_Manuscript