Ruthenium-porphyrin-catalyzed carbenoid addition to allylic compounds: Application to [2,3]-sigmatropic rearrangements of ylides

Article abstract of DOI:10.1016/S0022-328X(00)00635-5

The catalytic effectiveness of ruthenium porphyrins for ylide generation in reactions of ethyl diazoacetate and diisopropyl diazomethylphosphonate with allylic amines, sulfides and iodides is described for the first time. These reactions result mainly in

Full text of DOI:10.1016/S0022-328X(00)00635-5

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Journal of Organometallic Chemistry 617–618 (2001) 360–363
Ruthenium–porphyrin-catalyzed carbenoid addition to allylic
compounds: application to [2,3]-sigmatropic rearrangements
of ylides
Ge´rard Simonneaux a,*, Erwan Galardon a, Christine Paul-Roth b, Mihaela Gulea c,
Serge Masson c
a Laboratoire de Chimie Organome´tallique et Biologique, UMR CNRS 6509, Uni6ersite´ de Rennes 1, 35042 Rennes Cedex, France
b Groupe de Recherche en Chimie et Me´tallurgie, I.N.S.A., 35043 Rennes Cedex, France
c Laboratoire de Chimie Mole´culaire et Thio-organique, UMR CNRS 6507, Uni6ersite´ de Caen et ISMRA, F-14050 Caen, France
Received 19 July 2000; accepted 5 September 2000
Abstract
The catalytic effectiveness of ruthenium porphyrins for ylide generation in reactions of ethyl diazoacetate and diisopropyl
diazomethylphosphonate with allylic amines, sulfides and iodides is described for the first time. These reactions result mainly in
products of the [2,3]-sigmatropic rearrangement of intermediate allylic ylides. © 2001 Elsevier Science B.V. All rights reserved.
Keywords: Ruthenium; Porphyrins; Catalysis; Sigmatropic
Ruthenium porphyrins have been used frequently for
oxidation reactions, based on the ruthenium ability to
form compounds in various oxidation states, ranging
from Ru(II) to Ru(VI) [5,6]. In contrast to these exten-
sive investigations, only a few carbene reactions cata-
lyzed by ruthenium porphyrins have been reported
using Ru(II) porphyrins as catalysts [7–11]. This is
quite unexpected since iron porphyrin complexes are
active catalysts for the cyclopropanation of alkenes by
ethyl diazoacetate [15] and osmium porphyrins catalyti-
cally convert ethyl diazoacetate to maleate and fu-
marate esters [16].
Our interest in the chemistry of ruthenium por-
phyrins prompted us to investigate the ylide generation
from diazo compounds. We previously reported cyclo-
propanation, N–H and S–H insertion reactions [12–
14]. We now want to report herein the details of the
catalytic reaction of ethyl diazoacetate and diisopropyl
diazomethylphosphonate with allylic substrates cata-
lyzed with ruthenium porphyrins. Comparison with
rhodium and copper catalyzed reactions with allylic
compounds will also be discussed.
1. Introduction
The metal-catalyzed carbene reactions have become
one of the most general and efficient methods available
to the synthetic organic chemist [1]. There is also con-
siderable interest in the development of effective cata-
lytic systems for the rearrangement of ylides generated
from reactions of diazo compounds with allylic sub-
strates [2,3]. The major advances have recently been
achieved with various rhodium derivatives. Alternatives
to Rh2(OAc)4, such as copper and to a less extent
ruthenium derivatives [4] were also evaluated for their
activity in reactions of allylic substrates with ethyl
diazoacetate (EDA). Although the accomplishments
achieved thus far are quite impressive, cyclopropana-
tion of the double bond competes with sulfonium ylide
formation [2] and exploration of new effective catalysts
is still essential to extend the scope of these reactions.
* Corresponding author. Tel.: +33-2-99286285; fax: +33-2-
99281646.
E-mail address: simonnea@univ-rennes1.fr (G. Simonneaux).
0022-328X/01/$ - see front matter © 2001 Elsevier Science B.V. All rights reserved.
PII: S0022-328X(00)00635-5

G. Simonneaux et al. / Journal of Organometallic Chemistry 617–618 (2001) 360–363
361
2. Results and discussion
with copper and rhodium catalysts [18], the ruthenium–
porphyrin catalytic system is remarkably specific with
alkyl allyl sulfides and provides the formal C–S inser-
tion product in nearly quantitative yield. However,
reaction with allyl phenyl sulfide provided mainly the
coupling products, diethyl maleate and fumarate, and
only small amounts of product 2 resulting from ylide
rearrangement. Masson et al., using rhodium and cop-
per complexes as catalyst [19] have previously reported
such a decrease of reactivity with aromatic sulfide to-
wards diazo derivatives. Due to the conjugation of the
sulfur doublet with the aromatic system, the rate of the
electrophilic addition of the metal carbene to the sulfide
group is probably too low and consequently, the com-
petitive formation of the coupling products, diethyl
maleate and fumarate, becomes the major process
(Scheme 1). In contrast, the reaction is less influenced
by steric effect. Thus, formation of 3 which derives
from [2,3]-sigmatropic rearrangement of the isopropylic
sulfur ylide is obtained in a fairly good yield (73%).
To complete these data, we also studied the reaction
of ethyl diazoacetate with 2-propene-1-thiol. For this
substrate, a potential competition between cyclopropa-
nation, ylide rearrangement and the insertion of the
diazo compound into a sulfur–hydrogen bond is possi-
ble. As previously reported with alkyl and aromatic
thiols, we observed complete insertion of the diazo
compound into the S–H bond [14] and product 4 was
exclusively obtained (Table 1, Scheme 2). It should be
noted that a preference for heteroatom–hydrogen in-
sertion has already been observed in the rhodium-cata-
lyzed reaction of diazoesters with unsaturated alcohols
[20].
2.1. Reaction of EDA with different allyl sulfides
(1, 2, 3, 4)
Treatment of allyl methyl sulfide with ethyl diazoac-
etate at 25°C in the presence of 1 mol% of meso-te-
traphenylporphyrin carbonyl ruthenium (TPPRuCO)
[17] results in the formation of ethyl 2-
(methylthio)pent-4-enoate 1 with 96% yield. Table 1
summarizes results obtained from reactions of ethyl
diazoacetate with various alkyl allyl sulfides, allylic
secondary and tertiary amines and allyl halides. The
formation of 1 derives from [2,3]-sigmatropic rear-
rangement of the sulfur ylide. As previously observed
Table 1
Ratio of insertion product (P)/(diethyl fumarate) (E)/(diethyl
maleate) (Z) from (TPP)Ru(CO) catalyzed reactions of ethyl diazoac-
etate with allyl sulfides, amines and halides
Allyl
Insertion product (P)
Ratio of
P/E/Z
CH2ꢀCHCH2SMe
CH2ꢀCHCH2SPh
CH2ꢀCHCH2SCHMe2
CH2ꢀCHCH2SH
CH2ꢀCHCH2CH(CO2Et)-
SMe (1)
CH2ꢀCHCH2CH(CO2Et)-
SPh (2)
CH2ꢀCHCH2CH(CO2Et)-
SCHMe2 (3)
CH2ꢀCHCH2SCH2CO2Et
(4)
100/0/0
8/0/92
73/0/27
100/0/0
CH2ꢀCHCH2NMe2
CH2ꢀCHCH2NHMe
CH2ꢀCHCH2CH(CO2Et)-
NMe2 (5)
CH2ꢀCHCH2NMe(CH2-
CO2Et) (6)
100/0/0
95/0/5
CH2ꢀCHCH2Cl
CH2ꢀCHCH2Br
CH2vCHCH2I
CH2ꢀCHCH2CH(CO2Et)-
6/4/90
2.2. Reaction of EDA with different allyl amines (5, 6)
Cl (7)
CH2ꢀCHCH2CH(CO2Et)-
Br (8)
CH2ꢀCHCH2CH(CO2Et)I
(9)
7/36/57
88/0/12
To explore the reactivity profile between secondary
and tertiary amines, the reaction between ethyl diazoac-
etate and alkyl allyl amines was examined. As expected,
a tertiary amine such as N,N-dimethylallylamine,
yielded exclusively the product of sigmatropic rear-
rangement as previously reported with rhodium(II) ace-
tate [18]. Since N–H insertion of metallocarbenoids are
widely used in amino acid synthesis [21], secondary allyl
amines were also tested as substrates. As expected, the
reaction was regioselective yielding mainly N–H inser-
tion with formation of 6 with 95% yield (Table 1).
Scheme 1. Dimerization of ethyl diazoacetate.
2.3. Reaction of EDA with different allyl halides
(7, 8, 9)
Using rhodium-catalyzed reactions with Rh6(CO)16
or Rh(OAc)4, Doyle et al. have shown that competition
between ylide generation and cyclopropanation of the
olefin can be manipulated by varying the nucleophilic-
ity of the halogen in the reactant allyl halide [18]. We
Scheme 2. Reaction of ethyl diazoacetate with allyl sulfides and
thiols.

362
G. Simonneaux et al. / Journal of Organometallic Chemistry 617–618 (2001) 360–363
Table 2
vestigated the reaction of diisopropyl diazomethyl
phosphonate with alkyl allyl sulfides, allyl amines and
allyl thiols. The results are summarized in Table 2. All
the data show that the major reaction with alkyl allyl
sulfides is the [2,3]-sigmatropic Wittig rearrangement of
the intermediate sulfonium ylide to give the formal C–S
insertion as the final compound (compounds 10 and
11). In contrast, only the S–H insertion is observed
with allyl thiol to give the (allylthio)methylphosphonate
12 (Scheme 3).
Ratio of (insertion product, P)/(E, tetraisopropylethene-1,2-diyl-bis-
(phosphonate)) from (TPP)Ru(CO) catalyzed reactions of diisopropyl
diazomethylphosphonate with allyl sulfides and amines
Allyl
Insertion product (P)
Ratio of
P/E
CH2ꢀCHCH2SMe
CH2ꢀCHCH2CH[PO(OiPr)2]-
SMe (10)
100/0
100/0
CH2ꢀCHCH2SCHMe2 CH2ꢀCHCH2CH[PO(OiPr)2]-
SCHMe2 (11)
CH2ꢀCHCH2SH
CH2ꢀCHCH2SCH2[PO(OiPr)2] 100/0
(12)
2.5. Reaction of diisopropyl diazomethyl phosphonate
with different allyl amines (13, 14)
CH2ꢀCHCH2NMe2
CH2ꢀCHCH2NHMe
CH2ꢀCHCH2CH[PO(OiPr)2]-
NMe2 (13)
0/100
CH2ꢀCHCH2NCH2[PO(OiPr)2]- 39/61
Me (14)
Since N–H insertion reactions of carbenoids from
diazophosphonates are still rare [24], we next investi-
gated the reaction of the diazophosphonate with a
secondary allyl amine as a route to aminophosphonate.
Addition of diisopropyl diazomethyl phosphonate to
N-methyl allyl amine, in the presence of a catalytic
amount of TPPRuCO, gave the corresponding phos-
phonic ester 14 in reasonable yield, but in this case the
coupling product was more abondant (Table 2). On the
other hand, reaction with N,N-dimethylallylamine did
not lead to the ylide formation (in contrast with the
result observed with EDA) but only the carbene dimer
tetraisopropyl (E)-ethene-1,2-diyl-bis-phosphonate was
isolated (Scheme 4) [19].
Scheme 3. Reaction of diisopropyl diazomethylphosphonate with
allyl sulfides.
3. Conclusion
In summary, we have demonstrated that simple
ruthenium porphyrins are highly effective catalysts for
carbenoid reactions with alkyl allyl sulfides and alkyl
allyl amines providing the formal C–S or C–N inser-
tion rather than the more classical cyclopropanation.
To fully characterize the catalytic properties of the
porphyrin compound, we have also shown that in the
competition process between ylide generation and the
insertion of the diazo compound into heteroatom–hy-
drogen bond, only the Z–H insertion compound is
observed. Future studies will focus on developing
stereoselective versions of these [2,3]-sigmatropic rear-
rangements using chiral ruthenium porphyrins.
Scheme 4. Dimerization of diisopropyl diazomethylphosphonate.
observed similar results with reactions catalyzed by the
ruthenium catalyst. The product expected from the
[2,3]-sigmatropic rearrangement of an intermediate
ylide was actually observed with allyl iodide (Table 1).
In contrast, reaction of ethyl diazoacetate with allyl
chloride or allyl bromide yielded only diethyl maleate
and fumarate. The relative proportions of these by-
products are variable, but as usually observed, the
product of dimerization (maleate) is the main product.
This result was not unexpected since the ruthenium
catalyst is known to be ineffective for cyclopropanation
of electron deficient olefins. It should be underlined that
iodides and sulfides are very similar in their ability to
intercept carbenoid intermediates [18].
4. Experimental
4.1. General data
NMR spectra were recorded in CDCl3 on a Brukner
200 DPX and chemical shifts are referenced to internal
TMS. GC/MS analyses were performed on a CE
GC8000 coupled with a Finnigan Mat AutomassII.
Ethyl diazoacetate and allyl derivatives were purchased
from Fluka and Lancaster.
2.4. Reaction of diisopropyl diazomethyl phosphonate
with different allyl sulfides (10, 11, 12)
Since a-phosphoryl sulfides have recently found large
application in organic synthesis [19,22,23], we also in-

G. Simonneaux et al. / Journal of Organometallic Chemistry 617–618 (2001) 360–363
363
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We gratefully acknowledge the financial support of the
MESR for a grant to E.G.
.