Ruthenium-catalysed synthesis of functional conjugated dienes from propargylic carbonates and silyl diazo compounds

Article abstract of DOI:10.1002/chem.201203796

The reactions of propargylic carbonates with silyl diazo compounds in the presence of [Cp*RuClACHTUNGTRENUNG(cod)] as a catalyst precursor. Copyright

Full text of DOI:10.1002/chem.201203796

DOI: 10.1002/chem.201203796
Ruthenium-Catalysed Synthesis of Functional Conjugated Dienes from
Propargylic Carbonates and Silyl Diazo Compounds
Solenne Moulin, Hanyu Zhang, Suresh Raju, Christian Bruneau,* and Sylvie Dꢀrien*[a]
The discovery of new methods for the preparation of
stereodefined and functionalised conjugated dienes remains
an area of current investigation because numerous transfor-
mations,[1] such as the Diels–Alder reaction, are based on
1,3-diene building blocks and because of the presence of
their recurring structure in natural products[2] and molecular
materials.[3] Over the last few decades, the development of
metal-catalysed reactions has led to the proposal of new and
efficient syntheses of conjugated dienes.[4] Among these ex-
amples, ruthenium–carbene species have shown potential for
carbene unit, generated in situ from diazo compounds, to
propargylic carbonates in the presence of the [Cp*RuCl-
AHCTUNGTREG(NNUN cod)] precatalyst under mild conditions (Scheme 1).
Scheme 1. Catalytic addition of diazo compounds to propargylic carbo-
nates.
À
the formation of 1,3-dienes by ene yne, ring-closing or
cross-metathesis reactions.[5] Ruthenium precatalysts are
also known to activate diazo compounds, especially for the
preparation of alkene-metathesis catalysts.[6] During the
course of our studies on the catalytic activity of the complex
Thus, when 0.5 mmol of propargyl carbonate 1a was re-
acted with 1.2 equivalents of trimethylsilyldiazomethane (2m
in Et2O) in the presence of styrene and 5 mol% of precata-
lyst [Cp*RuClACHTNUGRTNEUNG(cod)] (I, Cp*=C5Me5) in 0.5 mL of 1,4-diox-
[Cp*RuCl
(cod)],[7] we found that this precatalyst could react
ane at 608C for 1 h, the new dienyl carbonate 2a was
formed in 90% yield (Table 1, entry 1). Great improvement
came from controlling the concentration of the substrate,
that is, low concentrations slowed the reaction and the best
result was obtained with [1a]=1 molLÀ1. Two stereoisomers
of compound 2a were obtained with a Z/E ratio of 45:55
for the silylated double bond. In contrast, high stereoselec-
tivity in favour of the Z isomer was obtained from the corre-
sponding propargylic ester under the same conditions.[9]
with diazo compounds to form ruthenium–carbene species
that were capable of activating triple bonds. Thus, functional
conjugated dienes were synthesised by the addition of two
carbene units to alkynes[8] or of one carbene unit to propar-
gylic esters.[9] Carbonate derivatives are versatile com-
pounds, owing to their utilisation as protecting groups or as
synthesis intermediates,[10] as well as their applications in
agrochemistry and pharmaceuticals.[11] In this respect, dienyl
carbonates are interesting synthons that have appeared in
various transformations, such as the Diels–Alder reaction,[12]
1,4-hydrogenation into trisubstituted allylic alcohols,[13] or
asymmetric allylation.[14] However, dienyl carbonates are
often obtained under drastic conditions, such as the treat-
ment of enones with strong acids or bases.[15] Recently, a
gold-catalysed rearrangement of propargylic carbonates al-
lowed the preparation of dienyl carbonates under mild con-
ditions.[16] Herein, we report the direct and catalytic synthe-
sis of conjugated dienyl carbonates from the addition of a
Table 1. Ruthenium-catalysed reaction of propargyl carbonate 1a with
N2CHSiMe3.[a]
Entry
Solvent
T [8C]
Yield [%][b]
Z/E ratio
1
2
3
1,4-dioxane
1,4-dioxane
1,4-dioxane
1,4-dioxane
1,4-dioxane
n-hexane
n-hexane
n-heptane
DCE
60
80
40
RT
RT
RT
60
90
93
92
90
92
98
96
90
99
98
98
45:55
45:55
48:52
55:45
58:42
49:51
33:67
35:65
66:34
70:30
60:40
4
[a] Dr. S. Moulin,+ H. Zhang,+ S. Raju, Dr. C. Bruneau, Dr. S. Dꢀrien
Organometallics: Materials and Catalysis
UMR 6226-Institut des Sciences Chimiques de Rennes
CNRS-Universitꢀ de Rennes1 Campus de Beaulieu
35042 Rennes (France)
5[c]
6
7
8
9
10
11
80
RT
RT
RT
Fax : (+33)223236939
E-mail: christian.bruneau@univ-rennes1.fr
acetone
DMC
sylvie.derien@univ-rennes1.fr
[+] These authors contributed equally to this work.
[a] Reaction conditions: compound 1a (0.5 mmol) was treated with
N2CHSiMe3 (1.2 equiv) in the presence of catalyst I (5 mol%) and styr-
ene (5 equiv) in solvent (0.5 mL) for 1 h. [b] Yield of isolated product ob-
tained after purification by column chromatography on silica gel. [c] Re-
action without styrene
Supporting information for this article, including full experimental
details and characterization data, is available on the WWW under
http://dx.doi.org/10.1002/chem.201203796.
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Chem. Eur. J. 2013, 19, 3292 – 3296

COMMUNICATION
Then, we investigated the influence of the solvent and tem-
perature on this reaction to improve the stereoselectivity
(Table 1). The reaction of compound 1a afforded excellent
yields (>90%) in various solvents, nonpolar solvents, such
as n-hexane, or more-polar solvents, such as 1,2-dichloro-
ethane (DCE) and acetone. Interestingly, the reaction pro-
ceeded well in a “greener” solvent; that is, compound 2a
was obtained in 98% yield after 1 h at room temperature in
dimethyl carbonate (DMC; Table 1, entry 11).[17] The stereo-
selectivity of the reaction that led to compound 2a was
strongly dependent on the nature of the solvent: Non-polar
solvents favoured E stereochemistry (Table 1, entries 7–8),
whereas more-polar solvents led to the Z isomer (Table 1,
entries 9 and 10). The reaction temperature (from RT to
808C) had no significant influence on the yield of the reac-
tion, but played an important role in determining the stereo-
selectivity: Increasing the temperature favoured the E
isomer (Table 1, entry 7 versus entry 6 and entries 1–3
versus entry 4). The reaction of carbonate 1a in the absence
of styrene gave similar results in terms of yield and stereose-
lectivity (Table 1, entry 5 versus entry 4). However, the pres-
ence of styrene was beneficial for other substrates; thus, five
equivalents of styrene were added to the solution. The coor-
dination of styrene to the ruthenium centre may temporarily
protect the intermediate species during the catalytic process.
From these experiments, we determined the optimal reac-
tion conditions to be n-hexane, 608C for the formation of
the E isomer and acetone, RT for the formation of the Z
isomer.
selectivity. A very good result was obtained with R=tBu in
acetone because compound 2c was produced in 97% yield
with a Z/E ratio of 95:5. In n-hexane at 608C, the E isomer
was only favoured for compounds 2a and d. When the sub-
stituent was bulkier (2b and c), the Z isomer remained the
major one.
Then, we studied the scope of this reaction with different
propargylic carbonates (Table 3). The reactions proceeded
smoothly with dimethylpropargyl carbonates 3a–c, thereby
Table 3. Ruthenium-catalysed reactions of propargyl carbonates 3–5 with
N2CHSiMe3.[a]
Carbonate
R1, R2, R
Diene
Acetone, RT
n-Hexane, 608C
Yield
Z/E
Yield
Z/E
[%][b]
ratio[c]
[%][b]
ratio[c]
Me, Me, Me (3a)
Me, Me, Et (3b)
Me, Me, tBu (3c)
Et, Et, Me (4a)
Et, Et, Et (4b)
Et, Et, tBu (4c)
Me, iBu, Me (5a)
Me, iBu, Et (5b)
Me, iBu, tBu (5c)
6a
6b
6c
7a
7b
7c
8a
8b
8c
82
83
91
53:47
69:31
88:12
61:39
77:23
93:7
86
98
89
25:75
51:49
76:24
34:66
28[d]
57[d]
61[d]
39[d]
79
63[d]
78[d]
71[d]
76
55:45
80:20
75:25[e]
83:17[e]
93:7[e]
36:64[e]
51:49[e]
80:20[e]
82
84
95
[a] Reaction conditions: compounds 3–5 (0.5 mmol) were treated with
N2CHSiMe3 (1.2 equiv) in the presence of catalyst I (5 mol%) and styr-
ene (5 equiv) in solvent (0.5 mL) for 1 h. [b] Yield of isolated product ob-
tained after purification by column chromatography on silica gel. [c] Z/E
ratio for the silylated double bond. [d] The conversion was not complete
after 16 h. [e] Two stereoisomers were obtained for the tetrasubstituted
double bond in a 65:35 ratio.
With our optimised conditions in hand, we first examined
the influence of the carbonate substituent (R) on the spiro-
cyclohexylpropargyl carbonates 1a–d (Table 2). In all cases,
the reactions proceeded smoothly, thereby affording excel-
lent yields. The benzyl substituent in compound 1d led to
similar stereoselectivities to those produced with the methyl
substituent in compound 1a, but with slightly lower yield,
especially in acetone. When the methyl substituent was
changed to a bulkier substituent (Et, tBu), the ratio of the Z
isomer increased in acetone or n-hexane. In each case, the
use of the more-polar solvent (acetone) favoured Z stereo-
leading to complete conversion after 1 h into tetrasubstitut-
ed dienes 6a–c in good yields in acetone at RT or in n-
hexane at 608C. As previously observed with propargyl car-
bonates 1, the reactions in acetone at RT favoured Z stereo-
selectivity and the use of tert-butylpropargyl carbonate 3c
increased the quantity of the Z isomer. Good stereoselectiv-
ity for the E isomer was also obtained in n-hexane at 608C
for the less-hindered carbonate 6a (, Z/E 25:75). Diethyl-
propargyl carbonates 4 were less reactive, their conversions
were not complete, even after 16 h, and the yield of dienes 7
decreased, particularly in acetone. With two ethyl substitu-
ents at the propargylic position, carbonates 4 led to higher
Z ratios than those obtained from dimethylpropargyl carbo-
nates 3 under the same reaction conditions, but these ratios
were lower than those obtained from spiro-cyclohexylpro-
pargyl carbonates 1. The reactions with propargyl carbo-
nates 5 with two different substituents at the propargylic po-
sition afforded dienes 8 in good yields after 1 h as mixtures
of four stereoisomers. The Z/E ratios for the silylated
double bond were similar to those obtained from carbonates
Table 2. Ruthenium-catalysed reactions of propargyl carbonates 1 with
N2CHSiMe3.[a]
Diene 2
R
Acetone, RT
Yield [%][b]
n-Hexane, 608C
Z/E ratio
Yield [%][b]
Z/E ratio
Me (2a)
Et (2b)
tBu (2c)
CH2Ph (2d)
98
94
97
87
70:30
81:19
95:5
96
92
99
94
33:67
65:35
87:13
37:63
65:35
[a] Reaction conditions: compounds 1a–d (0.5 mmol) were treated with
N2CHSiMe3 (1.2 equiv) in the presence of catalyst I (5 mol%) and styr-
ene (5 equiv) in solvent (0.5 mL) for 1 h. [b] Yield of isolated product ob-
tained after purification by column chromatography on silica gel.
1
1 and a 65:35 ratio, as determined by H NMR spectroscopy,
was produced for the tetrasubstituted double bond in each
case.
Chem. Eur. J. 2013, 19, 3292 – 3296
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C. Bruneau, S. Dꢀrien et al.
Table 5. Ruthenium-catalysed reactions of propargyl carbonates 1, 3–5
Non-silylated dienyl carbonates could also be synthesised
by using this catalytic process. Indeed, the in situ formation
of the desilylated double bond from N2CHSiMe3 in MeOH
has already been obtained from alkynes in the presence of
catalyst I to produce desilylated dienes.[8] Thus, when the re-
action of carbonate 1a was performed in MeOH, the forma-
tion of desilylated dienyl carbonate 9a was observed
(Table 4). However, under the preceding conditions, the re-
action was not complete. To improve the efficiency of the
with N2CHSiMe3 in MeOH, providing desilylated dienes.[a]
Entry
Carbonate R1, R2, R
(CH2)5, Me (1a)
(CH2)5, Et (1b)
(CH2)5, tBu (1c)
(CH2)5, CH2Ph (1d)
Diene
Yield [%][b]
1
2
C
9a
9b
90
95
3
G
9c
87
4
G
9d
86
5
6
7
8
Me, Me, Me (3a)
Me, Me, Et (3b)
Me, Me, tBu (3c)
Et, Et, Me (4a)
Et, Et, Et (4b)
Et, Et, tBu (4c)
Me, iBu, Me (5a)
Me, iBu, Et (5b)
Me, iBu, tBu (5c)
10a
10b
10c
11a
11b
11c
12a
12b
12c
82
95
80
Table 4. Ruthenium-catalysed reaction of propargyl carbonate 1a with
N2CHSiMe3 in MeOH providing desilylated dienes.[a]
77[c]
80[c]
65[c]
71[d]
76[d]
90[d]
9
10
11
12
13
Entry
A
Cat. I
[mol%]
T
Conversion
[%]
Yield
[%][b]
A
]
A
[8C]
[a] Reaction conditions: compounds 1 and 3–5 (0.5 mmol) were treated
with N2CHSiMe3 (1.2 equiv) in the presence of catalyst I (8 mol%) and
styrene (5 equiv) in MeOH (1 mL) for 2 h. [b] Yield of isolated product
obtained after purification by column chromatography on silica gel.
[c] The conversion was not complete after 16 h. [d] Two stereoisomers
were obtained for the tetrasubstituted double bond in a 65:35 ratio.
1
2
3
4
5
6
7
1.0
0.67
0.5
1.0
0.67
0.5
5
5
5
8
8
8
8
60
60
60
60
60
70
85
90
100
100
100
100
55
79
81
58[c]
82[c]
90
60
RT
0.5
90
with trimethylsilyldiazomethane and its stabilization with
styrene, leading to ruthenium–carbene species II. After the
displacement of styrene by the coordination of propargylic
carbonates, carbene II can undergo a regioselective [2+2]
cycloaddition[18] with the triple bond of propargylic carbo-
nates, as in enyne metathesis,[19] thus producing ruthenacy-
clobutene intermediate III (or III’ in MeOH), followed by
the formation of the vinylcarbene–ruthenium intermediate
[a] Reaction conditions: compound 1a (0.5 mmol) was treated with
N2CHSiMe3 (1.2 equiv) in the presence of catalyst I and styrene (5 equiv)
in MeOH (0.5–1 mL) for 2 h. [b] Yield of isolated product obtained after
purification by column chromatography on silica gel. [c] 10% of silylated
derivative 2a was also obtained.
formation of the desilylated dienyl carbonates, we screened
the concentration of the substrate and the amount of cata-
lyst. With 5 mol% of complex I, complete conversion of car-
bonate 1a was never obtained at different concentrations of
substrate, temperatures or reaction times (Table 4, entries 1–
3). On the other hand, complete conversion was obtained
after 2 h by using 8 mol% of the catalyst (Table 4, entries 4–
7). Silylated derivatives could be obtained, along with the
expected desilylated compounds, if the concentration of
compound 1a was too high (Table 4, entries 4 and 5) and
the best result was observed with [1a]=0.5 molLÀ1. Finally,
90% yield in desilylated dienyl carbonate 9a was obtained
at 608C or at room temperature (Table 4, entries 6 and 7).
With these optimised conditions in hand, we examined
the scope of the reaction with various propargylic carbo-
nates in MeOH (Table 5). Excellent yields of the dienyl car-
bonates were obtained under mild conditions from proparg-
yl carbonates 1 and 3 (Table 5, entries 1–7). Diethylproparg-
yl carbonates 4 were still less reactive and the conversion
was stopped at 90%, even after 16 h or with a larger
amount of catalyst (Table 5, entries 8–10). The reactions of
carbonates 5 led to dienes 12 in good yields as a mixture of
two stereoisomers for the tetrasubstituted double bond in a
65:35 ratio (Table 5, entries 11–13); this ratio was similar to
that obtained for this double bond in silylated compounds 8.
A plausible mechanism is proposed in Scheme 2. This
mechanism involves the initial interaction of the catalyst
Scheme 2. Proposed catalytic cycle.
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Ruthenium-Catalysed Synthesis of Functional Conjugated Dienes
COMMUNICATION
IV . As previously reported with carboxylate groups, the 1,2-
shift of the carbonate group onto the carbene carbon could
release dienyl carbonates.[20] However, attack of the carbo-
nate group onto the ruthenium centre in intermediate IV
and subsequent reductive elimination, leading to the same
dienes, cannot be ruled out. A catalytic test reaction with a
mixture of two different substrates (2b and 3a) showed that
the migration of the carbonate group was an intramolecular
process. The favoured Z stereochemistry of the silylated
double bond may arise from the interactions of the silyl
group with the chloride during the ring-opening of inter-
mediate III.[8,9] A possible coordination of the carbonate
group on the ruthenium centre, if the R substituent is not
Scheme 4. Formation of silylated a,b-unsaturated ketone 13a.
0.5 mmol of propargyl carbonate 1a with 1.2 equivalents of
N2CHSiMe3 in the presence of 8 mol% of precatalyst I in
MeOH (1 mL), followed by the in situ addition of two
equivalents of BnMe3NOH after 2 h. After 3 h at room tem-
perature, compound 14a was isolated in 75% yield
(Scheme 5). The same compound was obtained from the re-
action of propargyl ethyl carbonate 1b under the same con-
ditions, thus showing that compound 14a resulted from the
Michael addition of MeOH onto an a,b-unsaturated desily-
lated ketone intermediate.
À
too bulky, could disturb the Cl Si interactions and partially
lead to the E isomer. Similar effects with coordinated
double bonds have already been proposed.[21] A more polar
À
solvent could strengthen the Cl Si interactions, which would
À
then favour Z stereochemistry. In the same way, the Cl Si
interactions could become weaker at high temperatures and
the opening of intermediate III, owing to steric hindrance,
would increase the ratio of the E stereoisomer.[8b] In MeOH,
desilylated dienyl carbonates were obtained. The solvent
could interact with the trimethylsilyl group, because of the
À
more-reactive Si C bond in MeOH, to produce desilylated
ruthenacyclobutene intermediate III’.[8b]
Alternatively, another mechanism (Scheme 3) would in-
volve the initial interactions of the catalyst with the propar-
gylic carbonate and the rearrangement of an h2-alkyne–
Scheme 5. Formation of saturated ketone 14a.
In summary, we have successfully developed a direct and
catalytic route to new dienyl carbonates. This one-pot
[Cp*RuClACTHNUTRGENUG(N cod)]-catalysed method proceeded in excellent
yields from readily accessible propargylic carbonates under
mild conditions. This transformation represents a rare exam-
ple in catalysis of the 1,2-shift of a carbonate group from a
propargylic carbonate under mild neutral conditions. The
stereoselectivity of these reactions was found to be strongly
dependent on the reaction conditions and polar solvents se-
lectively led to the Z isomers of the silylated derivatives. In-
terestingly, the reaction could be performed smoothly in
DMC as a “greener” solvent. This method provides a new
approach to the synthesis of functional conjugated dienes
and has potential application in further transformations.
Scheme 3. Alternative mechanistic pathway.
ruthenium species into a vinylcarbene–ruthenium intermedi-
ate, which results from 1,2-carbonate migration in a Rauten-
strauch-type process.[16,20c,22] Because the ability of the
Cp*RuCl moiety to accommodate two cis-carbene ligands is
known,[8,23] the addition of the diazo compound could lead
to a bis-carbene–ruthenium species, thereby affording the
formation of the same dienyl carbonates.
These dienyl carbonates might be good precursors of a,b-
unsaturated ketones. To test their reactivity, 0.5 mmol of
dienyl carbonate 2a was reacted with two equivalents of
Experimental Section
Typical procedure for the catalytic reactions: In a Schlenk tube under an
inert atmosphere, styrene (2.5 mmol) and (trimethylsilyl)diazomethane
(0.6 mmol, 2.0m in Et2O) were added to a solution of the propargyl car-
bonate (0.5 mmol) in degassed solvent (0.5–1.0 mL). Then, the
benzyltrimethylammonium hydroxide (as
a solution in
MeOH) in MeOH (1 mL) at room temperature. After 3 h,
the (E)-a,b-unsaturated silylated ketone 13a was isolated in
80% yield (Scheme 4).
Because the formation of desilylated dienyl carbonates
from propargylic carbonates took place in MeOH (Table 4
and Table 5), we examined the one-pot reactivity of
[(C5Me5)RuClACTHNUGRTNEUNG(cod)] precatalyst (5 mol%) was introduced and the mix-
ture was stirred at RT for 1–2 h. The reaction was monitored by GC or
TLC. After the reaction had been completed, the solvent was removed
under vacuum and the dienes were separated as pure compounds by
column chromatography on silica gel (Et2O/pentane).
Chem. Eur. J. 2013, 19, 3292 – 3296
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C. Bruneau, S. Dꢀrien et al.
[8] a) J. Le Paih, S. Dꢀrien, I. ꢃzdemir, P. H. Dixneuf, J. Am. Chem.
Soc. 2000, 122, 7400–7401; b) J. Le Paih, C. Vovard-Le Bray, S.
Dꢀrien, P. H. Dixneuf, J. Am. Chem. Soc. 2010, 132, 7391–7397.
[9] C. Vovard-Le Bray, S. Dꢀrien, P. H. Dixneuf, Angew. Chem. 2009,
121, 1467–1470; Angew. Chem. Int. Ed. 2009, 48, 1439–1442.
[10] a) P. G. M. Wuts, T. W. Greens, Greenꢀs Protective Groups in Organ-
ic Synthesis, 4th ed., Wiley, Hoboken, 2007; b) A. A. G. Shaikh, S. Si-
varam, Chem. Rev. 1996, 96, 951–976.
Acknowledgement
The authors are grateful to the CNRS, the Ministꢂre de la Recherche,
and the Region Bretagne for financial support, the latter through a PhD
grant to S.M. as part of the ARED program. We also thank Dr. Mathieu
Achard for his helpful discussions.
[11] a) P. Vlieghe, T. Clerc, C. Pannecouque, M. Witvrouw, E. De Clercq,
J. P. Salles, J. L. Kraus, J. Med. Chem. 2001, 44, 3014–3021; b) N.
Murakami, M. Sugimoto, M. Kawanishi, S. Tamura, H. Kim, K.
Begum, Y. Wataya, M. Kobayashi, J. Med. Chem. 2003, 46, 638–641.
[12] P. F. De Cusati, R. A. Olofson, Tetrahedron Lett. 1990, 31, 1409–
1412.
Keywords: azo compounds · carbenes · carbonates · dienes ·
ruthenium
[13] C. Fehr, I. Magpantay, M. Vuagnoux, P. Dupau, Chem. Eur. J. 2011,
17, 1257–1260.
[14] a) D. C. Behenna, B. M. Stoltz, J. Am. Chem. Soc. 2004, 126, 15044–
15045; b) B. M. Trost, J. Xu, J. Am. Chem. Soc. 2005, 127, 17180–
17181.
[15] a) M. Kawanisi, Y. Itoh, T. Hieda, S. Kozima, T. Hitomi, K. Kobaya-
shi, Chem. Lett. 1985, 647–650; b) P. F. De Cusati, R. A. Olofson,
Tetrahedron Lett. 1990, 31, 1405–1408; c) L. M. Harwood, Y. Hou-
miner, A. Manage, J. L. Seeman, Tetrahedron Lett. 1994, 35, 8027–
8030.
[16] S. Wang, L. Zhang, Org. Lett. 2006, 8, 4585–4587.
[17] B. Schꢄffner, F. Schꢄffner, S. P. Verevkin, A. Bçrner, Chem. Rev.
2010, 110, 4554–4581.
[1] a) F. Fringuelli, A. Taticchi, Dienes in the Diels–Alder Reaction,
Wiley, New York, 1990; b) W. Oppolzer, Comprehensive Organic
Synthesis, Vol. 5 (Ed.: B. M. Trost), Pergamon, Oxford, 1991, p. 315;
c) T. Y. Luh, K. T. Wong, Synthesis 1993, 349–370; d) J. D. Winkler,
Chem. Rev. 1996, 96, 167–176; e) M. E. Welker, Tetrahedron 2008,
64, 11529–11539.
[2] a) Z. Rappoport, The Chemistry of Dienes and Polyenes, Vol. 1,
Wiley, Chichester, 1997 and Z. Rappoport, The Chemistry of Dienes
and Polyenes, Vol. 2, Wiley, Chichester, 2001; b) K. C. Nicolaou,
S. A. Snyder, T. Montagnon, G. Vassilikogiannakis, Angew. Chem.
2002, 114, 1742–1773; Angew. Chem. Int. Ed. 2002, 41, 1668–1698;
c) M. Mori, Adv. Synth. Catal. 2007, 349, 121–135.
[3] a) M. Hissler, P. H. Dyer, R. Rꢀau, Coord. Chem. Rev. 2003, 244, 1–
44; b) E.-i. Negishi, Z. Huang, G. Wang, S. Mohan, C. Wang, H.
Hattori, Acc. Chem. Res. 2008, 41, 1474–1485; c) Q. Luo, C. Wang,
L. Gu, W. X. Zhang, Z. Xi, Chem. Asian J. 2010, 5, 1120–1128.
[4] a) R. F. Heck, Org. React. 1982, 27, 345–390; b) N. Miyaura, A.
Suzuki, Chem. Rev. 1995, 95, 2457–2483; c) R. C. Larock, Compre-
hensive Organic Transformations, Wiley, New York, 1999, pp. 463–
522; d) Z. Xi, Eur. J. Org. Chem. 2004, 2773–2781; e) Z. Xi, W.-X.
Zhang, Synlett 2008, 2557–2570.
[5] a) R. M. Garbaccio, S. J. Stachel, D. K. Baeschlin, S. J. Danishefsky,
J. Am. Chem. Soc. 2001, 123, 10903–10908; b) C. A. Dvorak, W. D.
Schmitz, D. J. Poon, D. C. Pryde, J. P. Lawson, R. A. Amos, A. I.
Meyers, Angew. Chem. 2000, 112, 1730–1732; Angew. Chem. Int.
Ed. 2000, 39, 1664–1666; c) J. Wagner, L. M. M. Cabrejas, C. E.
Grossmith, C. Papageorgiou, F. Senia, D. Wagner, J. France, S. P.
Nolan, J. Org. Chem. 2000, 65, 9255–9260; d) S. T. Diver, A. J. Gies-
sert, Chem. Rev. 2004, 104, 1317–1382; e) T. W. Funk, J. Efskind,
R. H. Grubbs, Org. Lett. 2005, 7, 187–190; f) S. T. Diver, J. Mol.
Catal. A Chem. 2006, 254, 29–42; g) S. T. Diver, Coord. Chem. Rev.
2007, 251, 671–701; h) S. Kotha, M. Milind, T. Arti, Chem. Rev.
2009, 38, 2065–2092; i) C. Fischmeister, C. Bruneau, Beilstein J. Org.
Chem. 2011, 7, 156–166.
[6] a) P. Schwab, M. B. France, J. W. Ziller, R. H. Grubbs, Angew.
Chem. 1995, 107, 2179–2181; Angew. Chem. Int. Ed. Engl. 1995, 34,
2039–2041; b) P. Schwab, R. H. Grubbs, J. W. Ziller, J. Am. Chem.
Soc. 1996, 118, 100–110; c) T. M. Trnka, R. H. Grubbs, Acc. Chem.
Res. 2001, 34, 18–29.
[7] a) P. H. Dixneuf, C. Bruneau, S. Dꢀrien, Pure Appl. Chem. 1998, 70,
1065–1070; b) S. Dꢀrien, P. H. Dixneuf, J. Organomet. Chem. 2004,
689, 1382–1392; c) C. Vovard-Le Bray, S. Dꢀrien, P. H. Dixneuf, C.
R. Chim. 2010, 13, 292–303.
[18] a) P. S. Kumar, K. Wurst, M. R. Buchmeiser, J. Am. Chem. Soc.
2009, 131, 387–395; b) S. Naumov, M. R. Buchmeiser, Organometal-
lics 2012, 31, 847–856.
[19] a) A. Kinoshita, M. Mori, Synlett 1994, 1020–1022; b) S. H. Kim,
N. B. Bowden, R. H. Grubbs, J. Am. Chem. Soc. 1994, 116, 10801–
10802; c) S. H. Kim, W. J. Zuercher, N. B. Bowden, R. H. Grubbs, J.
Org. Chem. 1996, 61, 1073–1081.
[20] a) K. Ohe, M. Fujita, H. Matsumoto, Y. Tai, K. Miki, J. Am. Chem.
Soc. 2006, 128, 9270–9271; b) E. J. Cho, M. Kim, D. Lee, Eur. J.
Org. Chem. 2006, 3074–3078. With carbonate groups : c) A. K.
Buzas, F. M. Istrate, F. Gagosz, Tetrahedron 2009, 65, 1889–1901.
[21] a) F. Monnier, D. Castillo, S. Dꢀrien, L. Toupet, P. H. Dixneuf,
Angew. Chem. 2003, 115, 5632–5635Angew. Chem. Int. Ed. 2003,
42, 5474–5477; b) F. Monnier, C. Vovard-Le Bray, D. Castillo, V.
Aubert, S. Dꢀrien, P. H. Dixneuf, L. Toupet, A. Ienko, C. Mealli, J.
Am. Chem. Soc. 2007, 129, 6037–6049.
[22] a) V. Rautenstrauch, J. Org. Chem. 1984, 49, 950–952; for the initial
report of
a Rautenstrauch rearrangement with ruthenium com-
plexes, see: b) K. Miki, K. Ohe, S. Uemura, J. Org. Chem. 2003, 68,
8505–8513; for reports of the Rautenstrauch rearrangement of
propargylic carbonates with gold or platinum complexes, see: c) A.
Buzas, F. Gagosz, Org. Lett. 2006, 8, 515–518; d) J. Zhao, D. A.
Clark, Org. Lett. 2012, 14, 1668–1671.
[23] a) C. Gemel, A. LaPensꢀe, K. Mauthner, K. Mereiter, R. Schmid, K.
Kirchner, Monatsh. Chem. 1997, 128, 1189–1199; b) J. Le Paih, F.
Monnier, S. Dꢀrien, P. H. Dixneuf, E. Clot, O. Eisenstein, J. Am.
Chem. Soc. 2003, 125, 11964–11975; c) H. Klein, T. Roisnel, C. Bru-
neau, S. Dꢀrien, Chem. Commun. 2012, 48, 11032–11034.
Received: October 24, 2012
Published online: February 5, 2013
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