Facile formation of chloro-η3-allyl complexes by reaction of vinyldiazoacetates and ruthenium(II) arene complexes

Article abstract of DOI:10.1021/om020160e

The reaction of vinyldiazoacetates 1 and ruthenium arene complexes 2 at room temperature resulted in the formation of a new type of chloro-substituted η³-allyl ruthenium complexes, 3, in high yield. The structure of 3a was determined by X-ray crystallographic analysis. The reaction of the ruthenium complexes 3a,d with styrene demonstrated that these complexes are capable of inducing a cyclopropanation reaction.

Full text of DOI:10.1021/om020160e

2536
Organometallics 2002, 21, 2536-2539
F a cile F or m a tion of Ch lor o-η3-Allyl Com p lexes by
Rea ction of Vin yld ia zoa ceta tes a n d Ru th en iu m (II) Ar en e
Com p lexes
Hisao Nishiyama,* Miyuki Konno, and Katsuyuki Aoki
School of Materials Science, Toyohashi University of Technology,
Tempaku-cho, Toyohashi 441-8580, J apan
Huw M. L. Davies
Department of Chemistry, University at Buffalo, The State University of New York,
Buffalo, New York 14260-3000
Received February 25, 2002
Sch em e 1
Summary: The reaction of vinyldiazoacetates 1 and
ruthenium arene complexes 2 at room temperature
resulted in the formation of a new type of chloro-
substituted η3-allyl ruthenium complexes, 3, in high
yield. The structure of 3a was determined by X-ray
crystallographic analysis. The reaction of the ruthenium
complexes 3a ,d with styrene demonstrated that these
complexes are capable of inducing a cyclopropanation
reaction.
In tr od u ction
The rhodium-catalyzed reactions of vinyldiazoacetates
with olefins has been well-developed as a general
method for the stereoselective synthesis of cyclopro-
panes and cyclopentenes, and these reactions are be-
lieved to proceed via metal carbenoids.1,2 The Nishiyama
group has investigated the carbenoid reactions and the
carbene complexes derived from the reaction of various
ruthenium species with diazoacetates and diazo-
malonates.3,4 In this paper, we disclose our studies on
the reaction of several vinyldiazoacetates 1 with ruthe-
nium arene complexes 2, which resulted in the unex-
pected formation of novel η3-allyl ruthenium complexes
3.
Resu lts a n d Discu ssion
Reaction of the vinyldiazoacetate 1a and the (η6-
benzene)ruthenium complex 2a in dichloromethane at
room temperature produced the new complex 3a (Scheme
1). The reaction was monitored by TLC, which showed
the appearance of a new yellow spot. Purification by
column chromatography gave a yellow solid, which on
the basis of NMR analysis appeared to consist of two
stereoisomers (ca. 94:6). X-ray crystallographic analysis
of the main isomer demonstrated that it was not the
anticipated ruthenium carbenoid complex. Instead, the
quite unusual 1-chloro-substituted η3-allyl ruthenium
complex 3a was formed with a Cl (syn) and CO2Me
(anti) arrangement on the C1 carbon atom (Figure 1,
Tables 1 and 2).5 Probably, the minor product is the
isomer with Cl (anti) and CO2Me (syn), but this cannot
be fully characterized because the minor isomer was not
isolated in pure form. When the (p-cymene)ruthenium
(1) Davies, H. M. L. Curr. Org. Chem. 1998, 2, 463. Davies, H. M.
L. Advances in Cycloaddition; Harmata, M., Ed.; J AI Press: New York,
1999; Vol. 5, p 119. Selected papers: Davies, H. M. L.; Bruzinski, P.
R.; Lake, D. H.; Kong, N.; Fall, M. J . J . Am. Chem. Soc. 1996, 118,
6879. Davies, H. M. L.; Hansen, T. J . Am. Chem. Soc. 1997, 119, 9075.
Davies, H. M. L.; Xiang, B.; Kong, N.; Stafford, D. G. J . Am. Chem.
Soc. 2001, 123, 7461.
(2) Doyle, M. P.; McKervey, M. A.; Ye, T. Modern Catalytic Methods
for Organic Synthesis with Diazo Compounds; Wiley: New York, 1998.
Davies, H. M. L.; Antoulinakis, E. G. Organic Reactions; Overman, L.
E., Ed.; Wiley: New York, 2001; Vol. 57, p 1.
(3) Nishiyama, H.; Itoh, Y.; Matsumoto, H.; Park, S.-B.; Itoh, K. J .
Am. Chem. Soc. 1994, 116, 2223. Nishiyama, H.; Itoh, Y.; Sugawara,
Y.; Matsumoto, H.; Park, S.-B.; Itoh, K. Bull. Chem. Soc. J pn. 1995,
68, 1247. Nishiyama, H.; Soeda, N.; Naito, T.; Motoyama, Y. Tetrahe-
dron: Asymmetry 1998, 9, 2865. Iwasa, S.; Takezawa, F.; Tuchiya, Y.;
Nishiyama, H. Chem. Commun. 2001, 59. For vinylcarbene complexes
of Ru, for example: Wu, Z.; Nguyen, S. T.; Grubbs, R. H.; Ziller, J . W.
J . Am. Chem. Soc. 1995, 117, 5503. Schwab, P.; Grubbs, R. H.; Ziller,
J . W. J . Am. Chem. Soc. 1996, 118, 100. Nishiyama, H.; Park, S.-B.;
Itoh, K. Chem. Lett. 1995, 599 and references therein.
(4) For (arene)ruthenium complex catalyzed cyclopropanations; see
for example: Ku¨cu¨kbay, H.; Cetinkaya, B.; Guesmi, S.; Dixneuf, P. H.
Organometallics 1996, 15, 2434. Simal, F.; J an, D.; Demonceau, A.;
Noels, A. F. Tetrahedron Lett. 1999, 40, 1653. Baratta, W.; Herrmann,
W. A.; Kratzer, R. M.; Rigo, R. Organometallics 2000, 19, 3664.
(5) Maxwell, J . L.; Brown, K. C.; Bartley, D. W.; Kodadek, T. Science
1992, 256, 1544. An intermediate carbene species of the rhodium-
porphyrin system was captured by iodine anion to form iodomethyl
species in the absence of styrene.
10.1021/om020160e CCC: $22.00 © 2002 American Chemical Society
Publication on Web 05/16/2002

Notes
Organometallics, Vol. 21, No. 12, 2002 2537
Sch em e 2
F igu r e 1. Molecular structure of 3a showing 30% thermal
ellipsoids.
Ta ble 1. Cr ysta l Da ta a n d Str u ctu r e Refin em en t
Deta ils of 3a
A reasonable mechanism for the formation of the η3-
allyl ruthenium complexes 3 is illustrated in Scheme 2
for the conversion of 1a + 2a to 3a . The first step is
likely to be the nucleophilic addition of the vinyldiazo-
acetate 1a to the ruthenium complex 2a to form the
monomeric betaine complex i. Coordination of the
alkene moiety, giving the complex ii (path a ), followed
by spontaneous elimination of N2 from ii would produce
the η3-vinylcarbene species iv. Alternatively, iv may be
generated via the η1-vinylcarbene complex iii (path b).
Chloride ion attacks the carbene carbon atom in iv from
the exo site to give syn-Cl and anti-CO2Me stereochem-
istry of the allylic moiety in 3a . The intermediacy of the
η3-vinylcarbene species iv would explain the stereo-
chemical outcome of the chloride addition and why the
incorporation of chloride is unique to the vinyldiazo-
acetate system. All of the intermediates described are
reasonable structures, because they have coordinatively
saturated 18-electron Ru(II) species.6 In this context,
similar nucleophilic addition of hydride (H-) to the
vinylcarbene moiety of tungsten complexes CpW(CO)2-
(vinylcarbene) was reported to be likely to form the
corresponding η3-allylic complexes.7
Preliminary studies have also been carried out on the
reactivity of the η3-allyl ruthenium complexes. Heating
of the complex 3b with styrene at 70-100 °C generated
a mixture of the corresponding cyclopropanes 4 in 54%
yield (Scheme 3; trans:cis ) 50:50). Similarly, the
cyclopropanes from 3d were also obtained, but in a lower
yield (20%, trans:cis ) 50:50). Interestingly, the dia-
stereoselectivity of these cyclopropanations is quite
different from that observed in the rhodium-catalyzed
reactions; for example, Rh2(OAc)4 (1 mol %), styrene (5
equiv with respect to vinyldiazoacetate), and CH2Cl2 (at
reflux) give the corresponding vinylcyclopropane prod-
ucts in 96% yield (trans:cis ) 89:11) from (E)-C(N2)(CO2-
Et)CHdCHCO2Et.8 These facts indicate that the reverse
route (3 f iv f iii) may be feasible at higher temper-
empirical formula
fw
C13H14O4Cl2Ru
406.22
cryst dimens
cryst syst
0.05 × 0.2 × 0.3 mm
monoclinic
space group
C2/c (No. 15)
lattice params
a
b
c
â
19.333(2) Å
7.754(2) Å
19.931(2) Å
100.689(7)°
2935.7(9) Å3
8
V
Z
density (calcd)
F000
1.838 g/cm3
1688.00
µ(Mo KR)
14.40 cm-1
55°
2θmax
no. of rflns
measd
3727
unique
3619 (Rint ) 0.02)
no. of observns (I > 3.00σ(I))
no. of variables
rfln/param ratio
residuals: R; Rw
goodness of fit indicator
2143
181
11.84
0.047; 0.050
1.21
Ta ble 2. Selected Bon d Len gth s (Å) a n d An gles
(d eg) of 3a
Bond Lengths (Å)
Ru-Cl(1)
Ru-C(1)
Ru-C(2)
Ru-C(3)
Cl(2)-C(1)
2.399(2)
2.175(7)
2.137(7)
2.207(7)
1.776(8)
C(1)-C(2)
C(2)-C(3)
C(3)-C(6)
C(1)-C(4)
1.43(1)
1.42(1)
1.50(1)
1.51(1)
Bond Angles (deg)
Cl(1)-Ru-C(1)
Cl(1)-Ru-C(2)
Cl(1)-Ru-C(3)
C(1)-Ru-C(2)
C(1)-Ru-C(3)
88.9(2)
106.2(2)
86.0(2)
38.9(3)
67.8(3)
C(2)-Ru-C(3)
38.0(3)
117.9(7)
125.8(7)
116.1(7)
114.6(6)
C(1)-C(2)-C(3)
C(2)-C(1)-C(4)
C(2)-C(3)-C(6)
C(2)-C(1)-Cl(2)
complex 2b was treated with 1a , a very fast reaction
was observed to give the corresponding η3-allyl ruthe-
nium complex 3b within 1 h. In a similar manner,
vinyldiazo compounds 1b,c were also subjected to the
reaction with 2a ,b, giving the complexes 3c-f. In the
case of vinyldiazoacetate 1c, only a single stereoisomer
was observed, probably attributed to the existence of
an ester group at the C2 position.
(6) Hofmann, P.; Ha¨mmerle, M. Angew. Chem., Int. Ed. Engl. 1989,
28, 908. References for related metallacyclobutene MC3H4 systems
derived from η3-vinylcarbene moieties were cited therein.
(7) Garrett, K. E.; Sheridan, J . B.; Pourreau, D. B.; Feng, W. C.;
Geoffroy, G. L.; Staley, D. L.; Rheingold, A. L. J . Am. Chem. Soc. 1989,
111, 8383. Mitsudo, T. Bull. Chem. Soc. J pn. 1998, 71, 1525.

2538 Organometallics, Vol. 21, No. 12, 2002
Notes
R u (p -MeC6H 4-i-P r )[η3-CCl(CO2Me)CH dCH (CO2Me)]-
Cl (3b). [Ru(p-MeC6H4-i-Pr)Cl2]2 (91.9 mg, 0.150 mmol) and
vinyldiazoacetate 1a (58.0 mg, 0.315 mmol) were reacted in
CH2Cl2 (4 mL) at room temperature for 1 h. TLC: Rf ) 0.76
(CH2Cl2:EtOAc ) 10:1) for the product and Rf ) 0.81 for 1a .
After concentration, the residue was purified by silica gel
column chromatography (SiO2, 10 g; CH2Cl2/EtOAc as eluent)
and a yellow band was collected to give yellow solids (133 mg,
0.288 mmol, 96%); mp 137-138 °C dec. IR (KBr disk): ν 1722,
Sch em e 3
1700, 1275, 1195, 1190 cm-1 1H NMR (400 MHz, CDCl3,
.
TMS): δ 1.29 (d, J ) 6.8 Hz, 3H), 1.35 (d, J ) 6.8 Hz, 3H),
2.25 (s, 3H), 2.85 (m, 1H), 3.52 (d, J ) 10.0 Hz, 1H), 3.58 (s,
3H), 3.80 (s, 3H), 5.23 (dd, J ) 6.0, 0.8 Hz, 1H), 5.27 (dd, J )
5.6, 1.2 Hz, 1H), 5.35 (dd, J ) 6.0, 0.8 Hz, 1H), 5.43 (dd, J )
5.6, 1.2 Hz, 1H), 5.56 (d, J ) 10.0 Hz, 1H) ppm; <ca. 9% of
the stereoisomer, 6.18 (d, J ) 10.1 Hz) ppm. 13C NMR (100
MHz, CDCl3, TMS): δ 16.34, 22.66, 22.97, 29.39, 51.66, 51.79,
61.10, 77.38, 84.70, 88.74, 88.92, 89.30, 90.89, 109.06, 118.77,
167.09, 173.90. Anal. Calcd for C17H22Cl2O4Ru: C, 44.16; H,
4.80. Found: C, 44.24; H, 4.84.
Ru (C6H6)[η3-CCl(CO2Me)CHdCHP h ]Cl (3c). [Ru(C6H6)-
Cl2]2 (50.0 mg, 0.10 mmol) and vinyldiazoacetate 1b (48.5 mg,
0.24 mmol) were reacted in CH2Cl2 (6 mL) at room tempera-
ture for 48 h. TLC: Rf ) 0.60 (CH2Cl2:acetone ) 5:1) for the
product and Rf ) 0.84 for 1b. After concentration, the residue
was purified by silica gel column chromatography (SiO2, 13.5
g; CH2Cl2/acetone as eluent) and a yellow band was collected
to give yellow solids (72.9 mg, 0.17 mmol, 86%); mp 153-154
°C dec. IR (KBr disk): ν 1714, 1433, 1297, 1206 cm-1. 1H NMR
(400 MHz, CDCl3, TMS): δ 3.68 (s, 3H), 4.88 (d, J ) 11.7 Hz,
1H), 5.42 (s, 6H), 5.67 (d, J ) 11.7 Hz, 1H), 7.3-7.4 (m, 5H)
ppm; <ca. 9% of the stereoisomer, 3.95 (s), 4.99 (d, J ) 11.8
Hz), 5.32 (s), 6.17 (d, J ) 11.8 Hz) ppm. 13C NMR (100 MHz,
CDCl3, TMS): δ 51.98, 79.37, 80.93, 83.04, 90.94, 126.19,
128.00, 129.08, 140.25, 167.75. Anal. Calcd for C17H16Cl2O2-
Ru: C, 48.12; H, 3.80. Found: C, 48.05; H, 3.95.
Ru (p-MeC6H4-i-P r )[η3-CCl(CO2Me)CHdCHP h ]Cl (3d ).
[Ru(p-MeC6H4-i-Pr)Cl2]2 (91.9 mg, 0.150 mmol) and vinyldiazo-
acetate 1b (72.8 mg, 0.36 mmol) were reacted in CH2Cl2 (2
mL) at room temperature for 2 h. TLC: Rf ) 0.61 (CH2Cl2:
acetone ) 10:1) for the product and Rf ) 0.88 for 1b. After
concentration, the residue was purified by silica gel column
chromatography (SiO2, 35 g; CH2Cl2/acetone as eluent) and a
yellow band was collected to give yellow solids (138 mg, 0.29
mmol, 96%); mp 127-128 °C dec. IR (KBr disk): ν 1718, 1435,
1297, 1202 cm-1. 1H NMR (300 MHz, CDCl3, TMS): δ 1.18 (d,
J ) 6.9 Hz, 3H), 1.33 (d, J ) 6.9 Hz, 3H), 1.56 (s, 3H), 2.50
(m, 1H), 3.65 (s, 3H), 4.64 (dd, J ) 6.0, 0.9 Hz, 1H), 4.73 (d, J
) 11.7 Hz, 1H), 4.93 (dd, J ) 6.9 Hz, 0.9 Hz, 1H), 5.29 (dd, J
) 6.9 Hz, 0.9 Hz, 1H), 5.32 (dd, J ) 6.9 Hz, 0.9 Hz, 1H), 5.36
(d, J ) 11.7 Hz, 1H), 7.27-7.40 (m, 5H) ppm; <ca. 6% of the
stereoisomer, 6.02 (d, J ) 10.0 Hz) ppm. 13C NMR (75 MHz,
CDCl3, TMS): δ 15.41, 22.04, 23.45, 29.01, 52.85, 77.46, 78.29,
83.98, 86.46, 89.12, 92.21, 108.30, 117.79, 126.49, 127.37,
129.19, 129.22, 138.98, 168.16. Anal. Calcd for C21H24Cl2O2-
Ru: C, 52.50; H, 5.04. Found: C, 52.34; H, 5.07.
Ru (C6H6)[η3-CCl(CO2Me)C(CO2Me)dCH(CO2Me)]Cl (3e).
[Ru(C6H6)Cl2]2 (35.0 mg, 0.07 mmol) and vinyldiazoacetate 1c
(36.3 mg, 0.15 mmol) were reacted in CH2Cl2 (4 mL) at room
temperature for 48 h. TLC: Rf ) 0.64 (CH2Cl2:acetone ) 5:1)
for the product and Rf ) 0.88 for 1c. After concentration, the
residue was purified by silica gel column chromatography
(SiO2, 8 g; CH2Cl2/acetone as eluent) and a yellow band was
collected to give yellow solids (49.2 mg, 0.11 mmol, 76%); mp
atures, as the carbene complex iii would be an active
species expected to undergo a cyclopropanation reaction
with styrene.
In summary, we have discovered a facile method for
the preparation of chloro-substituted η3-allyl ruthenium
complexes by using vinyldiazoacetates. These η3-allyl
ruthenium complexes are capable of undergoing cyclo-
propanations, presumably via vinylcarbene ruthenium
intermediates. These findings give useful information
for the further development of metal carbenoid chem-
istry and catalysis.
Exp er im en ta l Section
Gen er a l Con sid er a tion s. The vinyldiazoacetates 1 were
synthesized from commercially available trans-glutaconic acid
(Aldrich), trans-styrylacetic acid (Aldrich), and trans-aconitic
acid (Tokyo Kasei) in two steps: methyl esterification with
orthoformate in methanol catalyzed by a few drops of concen-
trated H2SO4 followed by transformation to the corresponding
diazoacetates with 4-acetamidobenzenesulfonyl azide9 (ABSA)
(Aldrich) and 1,8-diazabicyclo[5.4.0]-7-undecene (DBU) in CH3-
CN. See the Supporting Information for the procedure and
spectroscopic data. 1H and 13C NMR spectra were measured
on Varian Inova-400 and Mercury-300 spectrometers. IR
spectra were measured on a J asco FT/IR-230 spectrometer.
Melting points were measured on a Yanaco MP-J 3. Elemental
analyses were measured on a Yanaco CHN Corder, Model MT-
6. Column chromatography was performed with silica gel
(Merck, Art. No. 7734). Analytical thin-layer chromatography
(TLC) was performed on glass plates with silica gel (Merck,
Art. No. 5715).
Ru (C6H6)[η3-CCl(CO2Me)CHdCH(CO2Me)]Cl (3a ). In a
20 mL flask were placed [Ru(C6H6)Cl2]2 (79.5 mg, 0.159 mmol)
and the vinyldiazoacetate 1a (58.0 mg, 0.315 mmol) under an
argon atmosphere. CH2Cl2 (6 mL) was then added. The
mixture was stirred at room temperature for 48 h; TLC: Rf )
0.53 (CH2Cl2:MeOH ) 10:1) for the product and Rf ) 0.83 for
1a . After concentration, the residue was purified by silica gel
column chromatography (SiO2, 10 g; CH2Cl2/MeOH as eluent)
and a yellow band was collected to give yellow solids (105 mg,
0.26 mmol, 81%); mp 179-180 °C dec. IR (KBr disk): ν 1720,
1703, 1275 cm-1. 1H NMR (400 MHz, CDCl3, TMS): δ 3.55 (d,
J ) 10.0 Hz, 1H), 3.62 (s, 3H), 3.82 (s, 3H), 5.75 (s, 6H), 5.77
(d, J ) 10.0 Hz, 1H); ca. 6% of the stereoisomer was obtained,
3.57 (d, J ) 10.3 Hz, 1H), 3.84 (s, 3H), 3.93 (s, 3H), 5.71 (s,
6H), 6.26 (d, J ) 10.3 Hz, 1H) ppm. 13C NMR (100 MHz, CDCl3,
TMS): δ 52.31, 52.94, 61.02, 78.96, 86.03, 92.15, 166.62,
174.34. Anal. Calcd for C13H14Cl2O4Ru: C, 38.44; H, 3.47.
Found: C, 38.17; H, 3.37.
179-181 °C dec. IR (KBr disk): ν 1748, 1715, 1445, 1238 cm-1
.
1H NMR (400 MHz, CDCl3, TMS): δ 3.46 (s, 1H), 3.63 (s, 3H),
3.79 (s, 3H), 3.86 (s, 3H), 6.00 (s, 6H) ppm; no stereoisomer
was observed. 13C NMR (100 MHz, CDCl3, TMS): δ 52.13,
52.31, 52.44, 54.19, 75.23, 95.79, 97.42, 166.28, 166.92, 174.02.
Anal. Calcd for C15H16Cl2O6Ru: C, 38.81; H, 3.47. Found: C,
38.80; H, 3.46.
(8) Davies, H. M. L.; Clark, T. J .; Church, L. A. Tetrahedron Lett.
1989, 30, 5057. For asymmetric versions, see: Davies, H. M. L.; Huby,
N. J . S.; Cantrell, W. R., J r.; Olive, J . L. J . Am. Chem. Soc. 1993, 115,
9468. Davies, H. M. L.; Panaro, S. A. Tetrahedron Lett. 1999, 40, 5287
and related references cited in ref 1.
(9) Davies, H. M. L.; Cantrell, W. R., J r.; Romines, K. R.; Baum, J .
S. Org. Synth. 1991, 70, 93.

Notes
R u (p -Me C 6H 4-i -P r )[η3-C C l(C O 2Me )C (C O 2Me )dC H -
Organometallics, Vol. 21, No. 12, 2002 2539
Crystallographic data have been deposited with the Cambridge
Crystallographic Data Centre (No. CCDC-179396). Copies of
the data can be obtained free of charge on application to the
CCDC, 12 Union Road, Cambridge CD21EZ, U.K. (e-mail,
deposit@ccdc.cam.ac.uk; web, http://www.ccdc.cam.ac.uk/).
(CO2Me)]Cl (3f). [Ru(p-MeC6H4-i-Pr)Cl2]2 (15.3 mg, 0.025
mmol) and vinyldiazoacetate 1c (13.3 mg, 0.055 mmol) were
reacted in CH2Cl2 (0.5 mL) at room temperature for 1 h. TLC:
Rf ) 0.55 (CH2Cl2:EtOAc ) 10:1) for the product and Rf ) 0.74
for 1c. After concentration, the residue was purified by silica
gel column chromatography (SiO2, 6 g; CH2Cl2/EtOAc as
eluent) and a yellow band was collected to give yellow solids
(24.5 mg, 0.047 mmol, 94%): mp 129-130 °C dec. IR (KBr
Rea ction of 3b w ith Styr en e. A mixture of 3b (69.3 mg,
0.15 mmol) and styrene (0.17 mL, 1.5 mmol) in toluene (0.7
mL) and ClCH2CH2Cl (0.7 mL) was heated to 70-100 °C for
13 h. After concentration, the residue was purified by column
chromatography with ether-hexane as eluent to give the oily
product 4 (21.2 mg, 0.081 mmol) in 54% yield. The trans:cis
disk): ν 1750, 1713, 1448, 1229 cm-1 1H NMR (400 MHz,
.
CDCl3, TMS): δ 1.29 (d, J ) 6.8 Hz, 3H), 1.37 (d, J ) 6.8 Hz,
3H), 2.29 (s, 3H), 2.85 (m, 1H), 3.47 (s, 1H), 3.60 (s, 3H), 3.79
(s, 3H), 3.85 (s, 3H), 5.46 (d, J ) 5.6 Hz, 1H), 5.58 (d, J ) 5.58
Hz, 1H), 5.59 (d, J ) 5.58 Hz, 1H), 5.69 (d, J ) 5.6 Hz, 1H)
ppm; no stereoisomer was observed. 13C NMR (100 MHz,
CDCl3, TMS): δ 16.44, 22.54, 22.79, 29.41, 51.77, 51.80, 53.96,
56.79, 73.55, 91.27, 91.71, 91.91, 94.17, 95.21, 114.02, 122.47,
166.63, 167.40, 173.22. Anal. Calcd for C19H24Cl2O6Ru: C,
43.85; H, 4.65. Found: C, 43.83; H, 4.61.
Cr ysta llogr a p h ic Str u ctu r e Deter m in a tion of 3a . A
single orange prismatic crystal (0.05 × 0.2 × 0.3 mm) was
obtained by recrystallization from CH2Cl2/n-hexane. The in-
tensity data (2θ < 55.0°, ω-2θ scan technique) were collected
on a Rigaku AFC-7R diffractometer with graphite-monochro-
mated Mo KR radiation (λ ) 0.710 69 Å), and the structure
was solved by direct methods (SAPI91). The final cycle of
refinement was based on 2143 observed reflections (I >
3.00σ(I)) and 181 variable parameters and converged with
R ) 4.7% and Rw ) 5.0%. Relevant data are listed in Table 1.
1
ratio was determined by H NMR: olefinic part, trans δ 6.63
(d, J ) 15.9 Hz, 0.50H), cis δ 5.82 (d, J ) 15.9 Hz, 0.50H)
ppm.
Ack n ow led gm en t. This work was supported by a
Grant-in-Aid for Scientific Research from the Ministry
of Education, Science and Culture of J apan (Tokutei A,
412).
Su p p or tin g In for m a tion Ava ila ble: Tables of atomic
coordinates and anisotropic displacement parameters, bond
lengths, and torsion angles for 3a , figures and tables giving
molecular structures and atomic coordinates for 3b,f, and text
detailing the preparation of vinyldiazoacetates. This material
is available free of charge via the Internet at http://pubs.acs.org.
OM020160E