Trapping reactive metal-carbene complexes by a bis-pocket porphyrin: X-ray crystal structures of Ru=CHCO2et and trans-[Ru(CHR)(CO)] species and highly selective carbenoid transfer reaction

Article abstract of DOI:10.1002/chem.200901895

What's in my pockets? By employing Suslick's bis-pocket porphyrin (ttppp), a reactive M=CHCO₂Et complex and a trans-[M(CHR)(CO)] (M = Ru) complex have been structurally characterized by X-ray crystal analysis. The sterically encumbered ttppp ligand has a significant impact on both the diastereoselectivity and chemoselectivity in metalloporphyrin-catalyzed reactions of ethyl diazoacetate with conjugated aryl dienes.

Full text of DOI:10.1002/chem.200901895

COMMUNICATION
DOI: 10.1002/chem.200901895
Trapping Reactive Metal–Carbene Complexes by a Bis-Pocket Porphyrin:
X-ray Crystal Structures of Ru=CHCO2Et and trans-[RuACTHNUTRGNEUG(N CHR)(CO)]
Species and Highly Selective Carbenoid Transfer Reactions
Qing-Hai Deng,[a] Jian Chen,[a] Jie-Sheng Huang,[b] Stephen Sin-Yin Chui,[b]
Nianyong Zhu,[b] Guang-Yu Li,[a] and Chi-Ming Che*[a, b]
ꢀ
The formation of C C bonds by a metal-catalyzed reac-
tion of diazo compounds N2CR1R2 with hydrocarbons, via
putative metal–carbene intermediates, has a wide spectrum
of applications in organic synthesis.[1] Identification of the
reactive metal–carbene intermediates in these catalytic pro-
cesses is of great importance for elucidating the reaction
corresponding reactive M=CHCO2Et intermediates have
sparsely been isolated,[2,4c,d] in contrast to the report of a
good number of reactive M=CR1R2 (R1 ¼H and R2 ¼H)
complexes.[6] To the best of our knowledge, only one M=
CHCO2Et complex has been structurally characterized in
the literature, that is, Werner and co-workers’ carbene com-
mechanisms. Since the isolation of [Os
(ttp=5,10,15,20-tetrakis
(p-tolyl)porphyrinato(2ꢀ)) by Woo
and co-workers[2] and [Ru
(CHCO2R)Cl2A(pybox)] (R=aryl
groups; pybox=2,6-bis[(4’S)-isopropyloxazolin-2’-yl]pyri-
A
N
(PiPr3)2],[7] which has not
plex [OsACTHGNUTERNNU(G CHCO2Et)(Cl)(CO)(H)CAHTUNGTRENNUNG
T
been reported to undergo carbenoid transfer with hydrocar-
bons. Given the effective shielding of the carbene center by
bulky 2,6-tBu2-4-Me-C6H2 in the structure of [Ru-
A
CHTUNGTRENNUNG
AHCTUNGTRENNUNG
dine) by Nishiyama and co-workers[3] from the reaction of
diazo compounds with metal catalysts, a number of reactive
metal–carbene complexes have been isolated or directly ob-
served from such reactions.[2–4] Characterization of these re-
active complexes by X-ray crystal analysis has been realized
for the M=CR1R2 (R1 ¼H and R2 ¼H) species.[4a,b,e,h–j] Re-
cently, Simonneaux and co-workers structurally character-
(tpp)],[5] the X-ray crys-
ACHTNUGTNERU{NGN CHCO2(2,6-tBu2-4-Me-C6H2)}ACHTNURTGENG(NUN thf)ACTHUNGTRENNGUN
tal structure characterization of reactive M=CHCO2Et spe-
cies, in which the Et group is too small to shield the carbene
center, remains a challenge.
A
strategy for kinetically stabilizing reactive M=
CHCO2Et complexes is to protect the carbene center with
sterically encumbered auxiliary ligands. In this regard, we
turned our attention to the bis-pocket porphyrin ligand
5,10,15,20-tetrakis(2,4,6-triphenylphenyl)porphyrinato(2ꢀ)
(ttppp), which was first synthesized by Suslick and co-work-
ers.[8] Metalloporphyrin-catalyzed alkene cyclopropanation
with diazo compounds, including EDA, has received a con-
siderable attention[9] since the pioneering work by Callot
and Piechocki.[10] By using simple porphyrin ligand ttp and
sterically encumbered porphyrin ligands 5,10,15,20-tetra-
ized [RuACHTUNGTRENNUNG{CHCO2(2,6-tBu2-4-Me-C6H2)}ACHTUNRTGENGN(UN thf)CATHNUGTREN(NNGU tpp)] (tpp=
5,10,15,20-tetraphenylporphyrinato(2ꢀ)),[5] an M=CHCO2R
complex kinetically stabilized by a bulky R group.
While N2CHCO2Et (EDA) has been used in numerous
studies on metal-catalyzed carbenoid transfer reactions, par-
ticularly intermolecular cyclopropanation of alkenes,[1] the
[a] Q.-H. Deng, Dr. J. Chen, G.-Y. Li, Prof. Dr. C.-M. Che
Shanghai-Hong Kong Joint Laboratory in Chemical Synthesis
Shanghai Institute of Organic Chemistry
The Chinese Academy of Sciences
ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
354 Feng Lin Road, Shanghai 200032 (China)
Fax : (+852)28571586
AHCTUNGTRENNUNG
E-mail: cmche@hku.hk
N
ACHTUNGTRENNUNG
[b] Dr. J.-S. Huang, Dr. S. S.-Y. Chui, Dr. N. Zhu, Prof. Dr. C.-M. Che
Department of Chemistry and
G
ACHTUNGTRENNUNG
these M=CHCO2Et porphyrin complexes by X-ray crystal
Open Laboratory of Chemical Biology of the
Institute of Molecular Technology for Drug Discovery and Synthesis
The University of Hong Kong, Pokfulam Road (Hong Kong)
analysis has not been realized. On the other hand, a wide
(CR1R2) (CR1R2)(L)
variety of [MACHTUNGTENRUNNG ACHUTTGNRENNUG(por)] and [MACHNUTGERTNNUNG CAHTNUGTRENN(UGN por)] (M=
Ru, Os; R1 ¼H, R2 ¼H; L=s donor, such as pyridine or 1-
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/chem.200901895.
methylimidazole) have been generated or isolated from
Chem. Eur. J. 2009, 15, 10707 – 10712
ꢁ 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
10707

treatment of [M(CO)
G
zene at 1908C to give [Ru(CO)
slow diffusion of hexane into a solution of [Ru(CO)
and THF in CH2Cl2 gave crystals of [Ru(CO)(thf)(ttppp)].
Treatment of [Ru(CO)(ttppp)] with excess N2CHR (R=
ACHTUNGTRENNUNG
shaded area),[4b,e,9b,14] consistent with the proposed involve-
ACHTUNGTRENNUNG
ment of M=CR1R2 intermediates in alkene cyclopropanation
G
ACHTUNGTRENNUNG
with N2CR1R2 catalyzed by [M(CO)
ACHTUNGTRENNUNG
CO2Et, SiMe3, Ph) in CH2Cl2 at
room temperature for 20 min,
followed by layering hexane or
isopropanol on the top of the
reaction mixtures, gave diffrac-
tion-quality crystals of 1–3. The
crystal data[17] and the X-ray
crystal structures of [Ru(CO)-
A
ACHTUNGERTN(NUNG ttppp)] and 3 are included
(Tables S1 and S2, FigACHTUNGTRENNUNGures S1
ꢀ
and S2). The Ru C(CO) length
of
[Ru(CO)
G
T
is
1.825(5) ꢂ, which is comparable
to those of other carbonyl
ruthenium porphyrin complexes
(1.77(2)–1.838(9) ꢂ).[18] The X-
ray crystal structures of 1 and 2
are depicted in Figure 1.
Complex 1 shows a Ru=C
length of 1.847(13) ꢂ and
a
ꢀ
Ru=C C angle of 137.6(10)8.
The former falls in the Ru=C
length range of 1.806(3)–
1.876(3) ꢂ, whereas the latter is
considerably larger than the
ꢀ
Ru=C C angle of ꢁ1258 found
for the Ru=CR1R2 (R1 ¼H,
R2 ¼H) porphyrin complex-
es.[14b] A water molecule trans
to the CHCO2Et carbene ligand
is weakly bound to ruthenium
Scheme 1. Formation of M=CR1R2 complexes from treatment of [M(CO)
structures of 1–3.
(por)] with N2CR1R2 and schematic
ACHTUNGTRENNUNG
in 1, with a Ru···OACHTUNRGTNEUNG(H2O) length
Os).[2,4e,f,9b,c,14a,15] Recently, we reported a highly selective
of 2.753(13) ꢂ.
ꢀ
carbenoid insertion into primary C H bonds of alkanes cat-
In contrast, the Ru=C length of 2.027(4) ꢂ found in 2 is
much longer than that found in 1, although the latter has a
alyzed by [Rh(Me)(MeOH)
G
N
ꢀ
ꢀ
G
(ttppp)] intermediate was proposed based on
Ru=C Si angle of 140.0(3)8 similar to the Ru=C C angle in
ꢀ
the result of DFT calculations.
the former. The Ru C(CO) bond of 2 is also substantially
lengthened to 2.125(7) ꢂ, about 0.3 ꢂ longer than that in
of [Ru
(CHCO2Et)
E
G
[Ru(CO)ACHTNGUTRENNU(G thf)ACHTUNGTREN(NUNG ttppp)]. This indicates that both the CO and
tivity toward alkene cyclopropanation, and also the follow-
ing findings originating from the sterically encumbered
ttppp ligand: 1) A dramatic change in the chemoselectivity
CHSiMe3 ligands have a large trans effect.
Complex 3 is disordered between two spatial orientations
(one is depicted in Figure S2 in the Supporting Information)
because the Ru atom lies on the inversion center of the
space group C2/c. In the structure refinement, the best R
value was obtained for a structure in which the Ru-bound C
atoms of CHPh and CO occupy the same position, with a
of [Ru(CO)
and X-ray crystal structure determination of [Ru-
(CHR)(CO)(ttppp)] (2: R=SiMe3, 3: R=Ph; Scheme 1).
ACHTUNGTRENNUNG(por)]-catalyzed reactions of EDA, 2) isolation
A
ACHTUNGTRENNUNG
There are no precedents in the literature for the crystal
structures of carbene complexes of metalloporphyrins with a
trans CO ligand; their formation provides useful information
on the mechanisms of the carbenoid transfer reactions cata-
lyzed by carbonyl metalloporphyrins.
ꢀ
Ru C length of 1.953(1) ꢂ (see the Supporting Informa-
tion). The CO ligand in 3 can be readily replaced by a coor-
dinating solvent, such as H2O, MeOH, or THF.
To the best of our knowledge, structurally characterized
metal complexes that contain a CHR carbene ligand trans
to a CO ligand have not been reported previously. Two re-
The insertion of ruthenium into ttppp was accomplished
by treating [Ru3(CO)12] with H2ACTHNUTRGENUGN(ttppp) in 1,2,4-trichloroben-
10708
www.chemeurj.org
ꢁ 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2009, 15, 10707 – 10712

Trapping Reactive Metal–Carbene Complexes
COMMUNICATION
IR spectroscopy. As the reac-
tions proceeded, a new band at
n˜ =2016 cmꢀ1 that is markedly
different from the n(CO) band
of
[Ru(CO)
G
(n˜ =
1952 cmꢀ1) appeared in the IR
spectra of the reaction mixtures.
We tentatively attribute this
new band to the weakly bound
CO trans to the CHR ligand.
Interestingly, the reaction of
[Ru(CO)ACHTUNTRGNEU(GN ttppp)] with EDA
(3 equiv) also generated a simi-
lar new band at n˜ =2016 cmꢀ1,
which
eventually
vanished
within 1 h, accompanied by for-
mation of diethyl maleate. This
reveals the possible formation
of [Ru
in the reaction.
The 1H NMR spectrum of 1
in CDCl3 shows Ru=CH
signal at d=13.07 ppm, similar
to those of [Ru(CHCO2Et)-
(ttp)] (d=13.43 ppm)[12a] and
[Ru(CHCO2Et)(tmp)] (d=
ACHUTGTNRNE(UNG CHCO2Et)(CO)ACHTUNGTRENNUNG(ttppp)]
a
AHCTUNGTRENNUNG
AHCTUNGTRENNUNG
A
ACHTUNGTRENNUNG
13.79 ppm).[12b] For complex 2,
the 1H NMR spectrum in
CDCl3 shows a Ru=CH signal
at d=18.55 ppm, which is com-
parable to that of [Ru-
Figure 1. Structures of a) 1 and b) 2. Hydrogen atoms have been omitted for clarity, with the exception of
those bonded to the carbene carbon atoms.
A
E
(d=
lated examples are the N-heterocyclic carbene (NHC) com-
signal of 3 is located at d=12.38 ppm. Lowering the temper-
ature from 27 to ꢀ608C did not result in either significant
ꢀ
plexes
2.128(4) ꢂ,
(NHC)(CO)(Cl)(H)
[Ru
G
E
G
(Ru C
and
E
1.849 ꢂ)[19a]
broadening or splitting of the H NMR signals for 2 and 3.
1
(NHC) 2.1282(18) ꢂ,
both of which have rather short
M C(CO) lengths compared with 2. A nonporphyrin diphe-
In the 13C NMR spectrum of 3, signals at d=298.19 and
199.51 ppm were discernible and could be assigned to Ru=C
ꢀ
Ru C(CO) 1.884(2) ꢂ),
ꢀ
ꢀ
and Ru CO, respectively. Upon prolonged standing at room
nylcarbene complex [Ru
G
N
temperature, the solution of 2 in CDCl3 showed no Ru=CH
dihydro-6,8,15,17-tetramethyldibenzo-[b,i]-[1,4,8,11]tetraaza-
cyclotetradecinato(2ꢀ)) was reported,[20] but its structure
has not been determined by X-ray crystal analysis.
proton resonance, and [Ru(CO)
54% yield from the solution.
Complex 1 is reactive toward the stoichiometric cyclopro-
panation of styrene (4). Treatment of 1 with 4 (10 equiv) in
CH2Cl2 at room temperature gave 5 in 88% yield with a
trans/cis ratio of 20:1 (Scheme 2). Both the yield and trans/
ACHTUNGERTN(NUNG ttppp)] was isolated in
The structure determination of 2 provides a measure of
ꢀ
the trans influence of a non-NHC carbene ligand on the M
CO bonding, and vice versa. For this purpose, a more com-
plicated case is the crystal structure of [WACTHNUTRGNEUNG
(CPh2)(CO)5].[21]
ꢀ
This tungsten complex not only has a long W CACTHUNRGTNEUNG(CPh2)
ꢀ
length of 2.14(2) ꢂ and a W C(CO trans to CPh2) length of
2.04(2) ꢂ, but also contains four CO ligands cis to the CPh2
ꢀ
ligand with W C(CO) lengths of 1.98(2), 2.02(2), 2.02(2),
and 2.03(3) ꢂ.
Scheme 2. Stoichiometric cyclopropanation of styrene (4) by 1.
IR measurements revealed that the crystals of 2 and 3
readily lose their CO ligands during sample preparation. To
observe the n(CO) bands in these complexes, we monitored
cis ratio are similar to those obtained for the same product
the treatment of [Ru(CO)
G
in the cyclopropanation of styrene (2 mmol) with EDA
Ph; 2 equiv) in CH2Cl2 at room temperature by using in situ
(0.20 mmol) catalyzed by 1 mol% [Ru(CO)ACTHNUTRGNE(NUG ttppp)] in
Chem. Eur. J. 2009, 15, 10707 – 10712
ꢁ 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
10709

C.-M. Che et al.
Table 2. Decomposition of EDA catalyzed by [Ru(CO)
ttppp, tmp).
ACHTUNGTRENUN(NG por)] (por=
CH2Cl2 for 4 h (85% yield, trans/cis 19:1). These results,
along with the facile formation of 1 by treating [Ru(CO)-
A
ACHUTGTNRNE(UNG CHCO2Et)(L)ACHTUNGTRNE(NUGN ttppp)]
AHCTUNGTRENNUNG
cyclopropanation with EDA. At this point, we do not exact-
ly know the ligand trans to Ru=CHCO2Et in [Ru-
N
ACHTUNGTRENNUNG(ttppp)]. As 64% of [Ru(CO)ACHTUNGTNER(NUGN ttppp)] was
Catalyst
[Ru(CO)
[Ru(CO)(ttppp)]
t [h]
Yield[a] [%]
8:9[b]
N
4
42
93 (8)[c]
11 (cis-8)[d]
79 (9)
–
AHCTUNGTRENNUNG
E
4.2:1
N
ACHTUNGTRENNUNG
[a] Isolated yield. [b] Determined by 1H NMR spectroscopy. [c] Ratio of
cis-8/trans-8=55:1; no 9 was detected. [d] No trans-8 was detected.
ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
A
Also, there is an enormous difference in reactivity be-
(6a–f) with EDA (see Table 1). Both catalysts resulted in
the formation of cyclopropanation products 7a–f in excel-
tween [Ru(CO)ACTHNGURTENNU(G ttppp)] and [Ru(CO)ACTHUNGTREN(NUNG tmp)] in catalyzing
the reaction of allyl bromides 10a–c with EDA to afford
11a–c (Table 3). Such reactions
of allyl halides with EDA cata-
Table 1. Comparison of the catalytic properties of [Ru(CO)ACTHNUTRGENN(GU ttppp)] and [Ru(CO)ACHTUNGTRNE(NUGN tmp)] in the cyclopropana-
tion of 6 with EDA.[a]
lyzed by metal complexes are
sparse.[24] A proposed mecha-
nism involves attack of metal–
carbene intermediates by allyl
halides to generate halonium
ylides; the latter undergo [2,3]-
sigmatropic rearrangement to
give the observed products.[24]
[Ru(CO)
(ttppp)]
[Ru(CO)ACTHNGUETRNNU(G tmp)]
Entry
X
Yield of 7[b] [%]
trans/cis[c]
Yield of 7[b] [%]
trans/cis[c]
1
2
3
4
5
6
H (6a)
p-OMe (6b)
p-Br (6c)
p-NO2 (6d)
m-NO2 (6e)
p-OBn (6 f)
97 (7a)
96 (7b)
93 (7c)
94 (7d)
94 (7e)
95 (7 f)
7.1:1
7.0:1
7.7:1
6.2:1
7.1:1
9.0:1
96 (7a)
96 (7b)
94 (7c)
94 (7d)
95 (7e)
95 (7 f)
1.9:1
1.7:1
1.8:1
1.2:1
1.3:1
2.0:1
With catalyst [Ru(CO)ACHTUNGTRENNUNG(tmp)]
(0.1 mol%), the reaction of
10a–c with EDA gave 8 as the
major product, with a low 11:8
yield ratio of (0.15–0.43):1. A
lower 11:8 yield ratio of 0.075:1
was previously reported for the
[a] Reaction conditions: 6 (0.2 mmol), EDA (0.24 mmol), catalyst (0.001 mmol), CH2Cl2 (3 mL), RT. [b] Isolat-
1
ed yield. [c] Determined by H NMR spectroscopy.
[Ru(CO)
tion of 10a with EDA.[24c] Re-
markably, the reactions of 10a–c with EDA catalyzed by
[Ru(CO)(ttppp)] (0.1 mol%) gave 11a–c in 81–88% yields,
higher than the 75 and 57% yields obtained for 11a and
11b, respectively, by using silver(I) catalyst
(2.5 mol%).[24d] In the [Ru(CO)
(ttppp)]-catalyzed reactions,
ACHTUNGERTN(NUNG tpp)]-catalyzed reac-
lent yields (ꢁ95%, total yield of trans- and cis-7) with trans
selectivity. The trans/cis ratios obtained by using catalyst
AHCTUNGTRENNUNG
[Ru(CO)
ACHTUNGTRENNUNG
those of (1.2–2.0):1 obtained using catalyst [Ru(CO)
A
a
Note that previous reports on the metal-catalyzed cyclopro-
panation of 6 with EDA to form 7 are rare. Doyle and co-
workers reported a trans/cis ratio of 1.6:1 for 7a in the [Rh2-
ACHTUNGTRENNUNG
the yield ratios of 11:8 reach up to 25:1.
In conclusion, we have determined the crystal structures
A
of
a reactive M=CHCO2Et species and a trans-[M-
a recent report by Katsuki and co-workers,[23b] the IrIII–
salen-catalyzed cyclopropanation of 6a with EDA gave 7a
in 99% yield with a cis-selectivity (cis/trans up to ꢁ3.8:1).
A significant change in chemoselectivity was found for
ACHTUNGTRENNUNG
by Suslickꢀs bis-pocket porphyrin ttppp. This sterically en-
cumbered porphyrin ligand also has a significant impact on
the chemoselectivity in [Ru(CO)
of EDA. The isolation of 2 and 3 implies that trans-[M-
(CHCO2Et)(CO)(por)] could be an intermediate in
[M(CO)(por)]-catalyzed carbenoid transfer reactions. Such
intermediates have not been structurally characterized pre-
ACHTUNGTNER(NUNG por)]-catalyzed reactions
the [Ru(CO)ACHTUNGTRENNUNG(por)]-catalyzed decomposition of EDA upon
changing the porphyrin ligand from tmp to ttppp (Table 2).
At a catalyst loading of 0.04 mol%, the decomposition of
A
ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
EDA catalyzed by [Ru(CO)ACTHNUTRGENUGN(tmp)] at 08C for 4 h gave 8 in
93% yield (cis/trans 55:1). However, under the same condi-
viously; a related model complex, trans-[RuACTHGNUTERNNU(G NSO2R)(CO)-
ꢀ
tions, a much slower decomposition of EDA was observed
N
N
when using [Ru(CO)
N
after 42 h. The major product is 9, which was isolated in
intermolecular nitrene transfer reactions.[25] The present
ꢀ
79% yield.
work provides useful information on the mechanism of C C
10710
www.chemeurj.org
ꢁ 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2009, 15, 10707 – 10712

Trapping Reactive Metal–Carbene Complexes
COMMUNICATION
Table 3. Comparison of the catalytic properties of [Ru(CO)
(ttppp)] and [Ru(CO)
N
[5] P. Le Maux, T. Roisnel, I. Nicolas,
G. Simonneaux, Organometallics
2008, 27, 3037–3042.
allyl halides (10) with EDA.[a]
[6] For reviews, see: a) M. Broo-
khart, W. B. Studabaker, Chem.
Rev. 1987, 87, 411–432; b) H.-W.
Frꢃhauf, Chem. Rev. 1997, 97,
523–596;
c) J. W.
Herndon,
[Ru(CO)
(ttppp)]
[Ru(CO)ACTHNGUETRNNU(G tmp)]
Coord. Chem. Rev. 2000, 206–207,
237–262; d) J. Barluenga, J. San-
tamarꢄa, M. Tomꢅs, Chem. Rev.
2004, 104, 2259–2283.
Entry Allyl halide
Product
Yield of 11:8[c] cis/trans (8)[c] Yield of 11:8[c] cis/trans (8)[c]
11[b] [%]
11[b] [%]
1
2
88
25:1
12:1
cis only
13
0.43:1 1:0.5
0.15:1 1:0.32
[7] H. Werner, W. Stꢃer, J. Wolf, M.
Laubender, B. Weberndçrfer, R.
Herbst-Irmer, C. Lehmann, Eur.
J. Inorg. Chem. 1999, 1889–1897.
[8] K. S. Suslick, M. M. Fox, J. Am.
Chem. Soc. 1983, 105, 3507–3510.
[9] a) J. L. Maxwell, K. C. Brown,
D. W. Bartley, T. Kodadek, Sci-
ence 1992, 256, 1544–1547; b) C.-
M. Che, J.-S. Huang, Coord.
Chem. Rev. 2002, 231, 151–164;
c) G. Simonneaux, P. Le Maux, Y.
81
1:0.07
6
6
3
84 (1:1)
16:1
1:0.05
0.18:1 1:0.38
[a] Reaction conditions: 10 (1 mL), EDA (1.0 mmol), catalyst (0.001 mmol), RT. [b] Isolated yield. [c] Deter-
mined by H NMR spectroscopy.
1
Ferrand,
J.
Rault-Berthelot,
Coord. Chem. Rev. 2006, 250,
2212–2221.
bond formation reactions with diazo compounds catalyzed
by carbonyl metalloporphyrins.[4f]
[10] H. J. Callot, C. Piechocki, Tetrahedron Lett. 1980, 21, 3489–3492.
[11] R. L. Halterman, S.-T. Jan, J. Org. Chem. 1991, 56, 5253–5254.
[12] a) J. P. Collman, P. J. Brothers, L. McElwee-White, E. Rose, L. J.
Wright, J. Am. Chem. Soc. 1985, 107, 4570–4571; b) J. P. Collman,
E. Rose, G. D. Venburg, J. Chem. Soc. Chem. Commun. 1993, 934–
935.
Acknowledgements
[13] W.-C. Lo, C.-M. Che, K.-F. Cheng, T. C. W. Mak, Chem. Commun.
1997, 1205–1206.
We gratefully acknowledge the financial support by The University of
Hong Kong (University Development Fund), Hong Kong Research
Grants Council (HKU 1/CRF/08), and the University Grants Council of
HKSAR (Area of Excellence Scheme: AoE 10/01P). Q.H. Deng thanks
the Croucher Foundation of Hong Kong for a postgraduate studentship.
[14] a) C.-M. Che, J.-S. Huang, F.-W. Lee, Y. Li, T.-S. Lai, H.-L. Kwong,
P.-F. Teng, W.-S. Lee, W.-C. Lo, S.-M. Peng, Z.-Y. Zhou, J. Am.
Chem. Soc. 2001, 123, 4119–4129; b) Y. Li, J.-S. Huang, G.-B. Xu, N.
Zhu, Z.-Y. Zhou, C.-M. Che, K.-Y. Wong, Chem. Eur. J. 2004, 10,
3486–3502.
[15] a) E. Galardon, P. Le Maux, G. Simonneaux, Chem. Commun. 1997,
927–928; b) M. Frauenkron, A. Berkessel, Tetrahedron Lett. 1997,
38, 7175–7176; c) Z. Gross, N. Galili, L. Simkhovich, Tetrahedron
Lett. 1999, 40, 1571–1574; d) E. Galardon, P. Le Maux, G. Simon-
neaux, Tetrahedron 2000, 56, 615–621; e) A. Berkessel, P. Kaiser, J.
Lex, Chem. Eur. J. 2003, 9, 4746–4756.
Keywords: carbenoids
intermediates · ruthenium · structure elucidation
·
porphyrinoids
·
reactive
[16] H.-Y. Thu, G. S.-M. Tong, J.-S. Huang, S. L.-F. Chan, Q.-H. Deng,
C.-M. Che, Angew. Chem. 2008, 120, 9718–9722; Angew. Chem. Int.
Ed. 2008, 47, 9747–9751.
[1] For selected reviews, see: a) M. P. Doyle, M. A. McKervey, T. Ye,
Modern Catalytic Methods for Organic Synthesis with Diazo Com-
pounds, Wiley, New York, 1998; b) M. P. Doyle, D. C. Forbes, Chem.
Rev. 1998, 98, 911–935; c) H. M. L. Davies, R. E. J. Beckwith,
Chem. Rev. 2003, 103, 2861–2903; d) W. Kirmse, Angew. Chem.
2003, 115, 1120–1125; Angew. Chem. Int. Ed. 2003, 42, 1088–1093.
[2] D. A. Smith, D. N. Reynolds, L. K. Woo, J. Am. Chem. Soc. 1993,
115, 2511–2513.
[17] CCDC-627545 ([Ru(CO)ACTHUNTGRNENUG(thf)AHCUTNGTREN(NUNG ttppp)]), -627546 (1), -627547 (2), and
-632137 (3) contain the supplementary crystallographic data for this
paper. These data can be obtained free of charge from The Cam-
bridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_
request/cif.
[18] a) J. J. Bonnet, S. S. Eaton, G. R. Eaton, R. H. Holm, J. A. Ibers, J.
Am. Chem. Soc. 1973, 95, 2141–2149; b) R. G. Little, J. A. Ibers, J.
Am. Chem. Soc. 1973, 95, 8583–8590; c) J. T. Groves, Y. Han, D. Va-
n Engen, J. Chem. Soc. Chem. Commun. 1990, 436–437; d) C. Sle-
bodnick, K. Kim, J. A. Ibers, Inorg. Chem. 1993, 32, 5338–5342;
e) P. Le Maux, H. Bahri, G. Simonneaux, L. Toupet, Inorg. Chem.
1995, 34, 4691–4697; f) R. Salzmann, C. J. Ziegler, N. Godbout,
M. T. McMahon, K. S. Suslick, E. Oldfield, J. Am. Chem. Soc. 1998,
120, 11323–11334.
[19] a) R. J. Sundberg, R. F. Bryan, I. F. Taylor Jr. , H. Taube, J. Am.
Chem. Soc. 1974, 96, 381–392; b) S. Burling, M. F. Mahon, R. E.
Powell, M. K. Whittlesey, J. M. J. Williams, J. Am. Chem. Soc. 2006,
128, 13702–13703.
[3] S.-B. Park, N. Sakata, H. Nishiyama, Chem. Eur. J. 1996, 2, 303–306.
[4] For selected examples, see: a) H. Nishiyama, K. Aoki, H. Itoh, T.
Iwamura, N. Sakata, O. Kurihara, Y. Motoyama, Chem. Lett. 1996,
1071–1072; b) E. Galardon, P. Le Maux, L. Toupet, G. Simonneaux,
Organometallics 1998, 17, 565–569; c) H. M. Lee, C. Bianchini, G.
Jia, P. Barbaro, Organometallics 1999, 18, 1961–1966; d) C. Bianchi-
ni, H. M. Lee, Organometallics 2000, 19, 1833–1840; e) Y. Li, J.-S.
Huang, Z.-Y. Zhou, C.-M. Che, J. Am. Chem. Soc. 2001, 123, 4843–
4844; f) C. G. Hamaker, J.-P. Djukic, D. A. Smith, L. K. Woo, Orga-
nometallics 2001, 20, 5189–5199; g) B. F. Straub, P. Hofmann,
Angew. Chem. 2001, 113, 1328–1330; Angew. Chem. Int. Ed. 2001,
40, 1288–1290; h) Y. Li, J.-S. Huang, Z.-Y. Zhou, C.-M. Che, X.-Z.
You, J. Am. Chem. Soc. 2002, 124, 13185–13193; i) X. Dai, T. H.
Warren, J. Am. Chem. Soc. 2004, 126, 10085–10094; j) P. Hofmann,
I. V. Shishkov, F. Rominger, Inorg. Chem. 2008, 47, 11755–11762.
[20] a) A. Klose, E. Solari, C. Floriani, S. Geremia, L. Randaccio,
Angew. Chem. 1998, 110, 155–158; Angew. Chem. Int. Ed. 1998, 37,
Chem. Eur. J. 2009, 15, 10707 – 10712
ꢁ 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
10711

C.-M. Che et al.
148–150; b) A. Klose, E. Solari, J. Hesschenbrouck, C. Floriani, N.
Re, S. Geremia, L. Randaccio, Organometallics 1999, 18, 360–372.
[21] C. P. Casey, T. J. Burkhardt, C. A. Bunnell, J. C. Calabrese, J. Am.
Chem. Soc. 1977, 99, 2127–2134.
[22] J. P. Collman, P. J. Brothers, L. McElwee-White, E. Rose, J. Am.
Chem. Soc. 1985, 107, 6110–6111.
[23] a) M. P. Doyle, R. L. Dorow, W. E. Buhro, J. H. Griffin, W. H. Tamb-
lyn, M. L. Trudell, Organometallics 1984, 3, 44–52; b) H. Suematsu,
S. Kanchiku, T. Uchida, T. Katsuki, J. Am. Chem. Soc. 2008, 130,
10327–10337.
[24] a) M. P. Doyle, W. H. Tamblyn, V. Bagheri, J. Org. Chem. 1981, 46,
5094–5102; b) M. P. Doyle, D. C. Forbes, M. M. Vasbinder, C. S. Pe-
terson, J. Am. Chem. Soc. 1998, 120, 7653–7654; c) G. Simonneaux,
E. Galardon, C. Paul-Roth, M. Gulea, S. Masson, J. Organomet.
Chem. 2001, 617–618, 360–363; d) P. Krishnamoorthy, R. G. Brown-
ing, S. Singh, R. Sivappa, C. J. Lovely, H. V. Rasika Dias, Chem.
Commun. 2007, 731–733.
[25] X. Lin, C.-M. Che, D. L. Phillips, J. Org. Chem. 2008, 73, 529–537.
Received: June 20, 2009
Published online: September 16, 2009
10712
www.chemeurj.org
ꢁ 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2009, 15, 10707 – 10712