Synthesis and Atropo-diastereoselective Ring Cleavage of a [Cp*Ru]-Complexed Biaryl Lactone: Experimental and Computational Investigations

Article abstract of DOI:10.1021/om9906520

The planar-chiral biaryl lactone complex 5b is cleaved highly atropo-diastereoselectively by simple O-nucleophiles. Toward H-nucleophiles, it shows a different reactivity behavior consistent with DF calculations using the Fukui function.

Full text of DOI:10.1021/om9906520

Organometallics 1999, 18, 5017-5021
5017
Syn th esis a n d Atr op o-d ia ster eoselective Rin g Clea va ge
of a [Cp *Ru ]-Com p lexed Bia r yl La cton e: Exp er im en ta l
a n d Com p u ta tion a l In vestiga tion s†
Gerhard Bringmann,*,‡ Andreas Wuzik,‡ Ralf Stowasser,‡ Christian Rummey,‡
Lothar Go¨bel,‡ Dietmar Stalke,§ Matthias Pfeiffer,§ and Wolfdieter A. Schenk§
Institut fu¨r Organische Chemie, Universita¨t Wu¨rzburg, Am Hubland,
D-97074 Wu¨rzburg, Germany, and Institut fu¨r Anorganische Chemie, Universita¨t Wu¨rzburg,
Am Hubland, D-97074 Wu¨rzburg, Germany
Received August 13, 1999
The planar-chiral biaryl lactone complex 5b is cleaved highly atropo-diastereoselectively
by simple O-nucleophiles. Toward H-nucleophiles, it shows a different reactivity behavior
consistent with DF calculations using the Fukui function.
Sch em e 1. Ster eoselective Red u ctive Rin g
In tr od u ction
Op en in g of th e Ch r om iu m Com p lexes en d o-1c h
exo-1c To Give exo-2c a s th e On ly
Atr op o-d ia ster eom er
Axially chiral biaryls are gaining increasing signifi-
cance as chiral auxiliaries in asymmetric synthesis1 and
as bioactive natural products.2 A highly efficient ap-
proach to enantiopure biaryls is provided by the syn-
thesis and atroposelective cleavage of helically distorted,
but configurationally unstable biaryl lactones.3 An
interesting variant of this synthetic methodology is the
effective steric shielding of one of the two diastereotopic
faces by an η6-coordinated transition metal fragment
and diastereoselective ring opening of the resulting
planar-chiral benzonaphthopyranones (e.g., 1c; cf.
Scheme 1) to give configurationally stable biaryl com-
pounds. Thus reduction of the rapidly interconverting
chromium complexes endo-1c/exo-1c with NaBH4 leads
to exo-2c as the only atropo-diastereomer.4,5
The value of this remarkably stereocontrolled ring
cleavage reaction is, however, diminished by the un-
satisfactory yields obtained in the preparation of the
chromium complexes of type 1c (36%) and their low
chemical stability. In this paper, we report on the more
† Part 83 in the series Novel Concepts in Directed Biaryl Synthesis;
for part 82 see: Bringmann, G.; Wuzik, A.; Breuning, M.; Henschel,
P.; Peters, K.; Peters, E.-M. Tetrahedron: Asymmetry 1999, 10, 3025.
* Corresponding author. E-mail: bringman@chemie.uni-wuerzburg.de.
‡ Institut fu¨r Organische Chemie, Universita¨t Wu¨rzburg.
§ Institut fu¨r Anorganische Chemie, Universita¨t Wu¨rzburg.
(1) Examples of biaryl reagents: (a) Shibasaki, M.; Sasai, H.; Arai,
T. Angew. Chem., Int. Ed. Engl. 1997, 36, 1236. (b) Bringmann, G.;
Breuning, M. Tetrahedron: Asymmetry 1998, 9, 667.
efficient preparation of related, but cationic (still race-
mic) ruthenium complexes 56 and their highly diaste-
reoselective ring cleavage.
(2) (a) Asano, J .; Chiba, K.; Tada, M.; Yoshii, T. Phytochemistry
1996, 42, 713. (b) Bringmann, G.; Franc¸ois, G.; Ake´ Assi, L.; Schlauer,
J . Chimia 1998, 52, 18.
Resu lts a n d Discu ssion
(3) Bringmann, G.; Breuning, M.; Tasler, S. Synthesis 1999, 525.
(4) Bringmann, G.; Go¨bel, L.; Peters, K.; Peters, E.-M.; von Schner-
ing, H. G. Inorg. Chim. Acta 1994, 222, 255.
(5) For diastereoselective biaryl syntheses by intermolecular cou-
pling reactions, assisted by planar-chiral η6-coordinated chromium
complexes, see: (a) Watanabe, T.; Uemura, M. J . Chem. Soc., Chem.
Commun. 1998, 8, 871. (b) Kamikawa, K.; Watanabe, T.; Uemura, M.
J . Org. Chem. 1996, 61, 1375.
(6) For other stereoselective reactions using chiral ruthenium or
chromium complexes, see: (a) Pearson, A. J .; Bignan, G.; Zhang, P.;
Chelliah, M. J . Org. Chem. 1996, 61, 3940. (b) Ku¨ndig, E. P.; Saudan,
C. M.; Bernardinelli, G. Angew. Chem., Int. Ed. Engl. 1999, 38, 1220.
(c) Ku¨ndig, E. P.; Leresche, J . Tetrahedron 1993, 49, 5599. (d) Blystone,
S. L. Chem. Rev. 1989, 89, 1663. (e) Schenk, W. A.; Ku¨mmel, M.;
Reuther, I.; Burzlaff, N.; Wuzik, A.; Schupp, O.; Bringmann, G. Eur.
J . Inorg. Chem. 1979, 1745.
As a η6-ruthenium fragment, the sterically demanding
Cp*Ru group was chosen, for an optimum stereodiffer-
entiation exerted by the additional element of planar
chirality of the complexes 5. Thus, reaction of the free
lactones 3 with the corresponding acetonitrile complex
47 (see Scheme 2) gave the corresponding ruthenium
complexes 5 in distinctly better yields than for the
related chromium complexes (see above). Other than in
the chromium complex 1c and independent of the size
(7) Fagan, P. J .; Ward, M. D.; Calabrese, J . C. J . Am. Chem. Soc.
1989, 111, 1698.
10.1021/om9906520 CCC: $18.00 © 1999 American Chemical Society
Publication on Web 11/02/1999

5018 Organometallics, Vol. 18, No. 24, 1999
Bringmann et al.
Sch em e 2. Syn th esis of th e Ru th en iu m Sa n d w ich
Com p lexes 5
Sch em e 3. Diver gen t Rin g-Op en in g Beh a vior of
th e [Cp *Ru ]-Com p lexed Bia r yl La cton e 5b
of R, the coordination of the Cp*Ru fragment occurs on
the distal naphthalene ring, exclusively. This is evident
1
from the H NMR signals of the protons at C9 to C12,
which, compared to the corresponding protons of the
metal-free lactone precursor 3,8 are shifted to signifi-
cantly higher field. For the chromium complexes of type
1, a complexation to that distal ring had been found only
in the case of the highly sterically hindered representa-
tives (e.g., starting from 3f), whereas in other cases, the
chromium was found to be complexed to the phenol-
derived “southern” ring as in 1c.
ment of the calculated structure of 5b with the experi-
mental one, as determined by X-ray crystallography, the
only major difference being the (not so important)
orientation of the 3-methoxy group, which may be due
to packing effects.
First experiments on the atroposelective ring cleavage
of the complexes 5 were exemplarily carried out with
the dimethoxy-substituted derivative 5b. This complex9
showed a surprising differentiation in its behavior
toward nucleophiles: The attack of NaBH4 and other
H-nucleophiles did not lead to the expected stereo-
selective lactone ring cleavage to give product 6b, which
would easily have been identified, after decomplexation,
as the well-known10 metal-free alcohol. In situ NMR
investigations rather indicated an attack on the ruthe-
nium activated distal ring, yielding an unstable product,
which upon attempted isolation by chromatography on
silica immediately decomposed back to 5b and then to
the uncomplexed benzonaphthopyranone 3b. Such ad-
dition reactions are known for cationic arene com-
plexes.11 No attack on the Cp* fragment or on the metal
was found in any case, in accordance with the Davies-
Green-Mingos rules.12 The reaction with simple O-
nucleophiles such as MeOH/Na2CO3 by contrast, pro-
ceeded smoothly, resulting in the expected ring-opening
product exo-7b as the only atropisomer13 in good yields.
Density functional (DF) calculations are excellently
suited to describe energetic and structural properties
of transition metal activated biaryl lactones (such as 114)
precisely. This is already evident from the good agree-
This encouraged us to investigate whether the Fukui
function within the DF theory is capable of describing
the interesting reactivity differentiation detected for
complex 5b, although this is a relatively large molecule
for ab initio studies. In the case of a nucleophilic attack,
the Fukui function,15 which is defined as the variation
of the chemical potential of a system with respect to the
external potential f(r) ) (δµ/δV)N (with the number of
particles kept constant), can be approximated by (FN+1
- FN)V (F, electron density, N, electron number), after
transformation to (δF(r)/δN)V. As a result, one obtains
molecular areas of local softness.15 The Fukui function
has so far been used mainly for the calculation of small
organic molecules.16 For transition metal complexes,
there is, to the best of our knowledge, as yet only one
study in which the Fukui function has been used for
the calculation of XPtCl3 and XPt(NH3)3 model com-
plexes.17
The results of the calculation of the Fukui function
presented here are illustrated in Figure 2 as a contour
plot.18 In the upper part, green areas indicate large
values of the Fukui function as reactive areas of high
local softness; in the lower part, these areas are
indicated by arrows.
(8) Bringmann, G.; Hartung, T.; Go¨bel, L.; Schupp, O.; Ewers, C. L.
J .; Scho¨ner, B.; Zagst, R.; Peters, K.; von Schnering, H. G.; Burschka,
C. Liebigs Ann. Chem. 1992, 225.
(9) For the investigations on diastereoselective ring cleavage reac-
tions described here, it was sufficient to prepare the complex 5b in a
racemic form.
(10) Bringmann, G.; Hartung, T.; Go¨bel, L.; Schupp, O.; Peters, K.;
von Schnering, H. G. Liebigs Ann. Chem. 1992, 769.
(11) Bennett, M. A.; Kahn, K.; Wenger E. In Comprehensive Orga-
nometallic Chemistry II; Shriver, D. F., Bruce, M. I., Eds.; Pergamon:
Oxford, 1995; Vol. 7, p 473.
(12) Davies, S. G.; Green, M. L. H.; Mingos, D. M. P. Tetrahedron
1978, 34, 3047.
(13) The relative configuration at the biaryl axis was determined
by NOE/ROE experiments, showing a correlation between the hydroxy
proton and the methyl group protons of the Cp* ligand.
(14) (a) Bringmann, G.; Stowasser, R.; Vitt, D. J . Organomet. Chem.
1996, 520, 261. (b) Bringmann, G.; Stowasser, R.; Go¨bel, L. J .
Organomet. Chem. 1997, 544, 7.
(15) (a) Parr, R. G.; Yang, W. J . Am. Chem. Soc. 1984, 106, 4049.
(b) Yang, W.; Parr, R. G.; Pucci, R. J . Chem. Phys. 1984, 81, 2862. (c)
Ga´zquez, J . L.; Vela, A.; Galva´n, M. Struct. Bonding 1987, 66, 79. (d)
Lee, Ch.; Yang, W.; Parr, R. G. J . Mol. Struct. 1988, 163, 305.
(16) (a) Me´ndez, F.; Galva´n M. In Density Functional Methods in
Chemistry; Labanowski, J ., Andzelm, J ., Eds.; Springer: New York,
1991; p 387. (b) Tielemans, M.; Areschka, V.; Colomer, J .; Promel, R.;
Langenaeker, W.; Geerlings, P. Tetrahedron 1995, 48, 10575.
(17) Korchowiec, J .; Nalewajski, R. F. Int. J . Quantum Chem. 1992,
44, 1027.
(18) The use of the older Gaussian 92 program package, by contrast,
showed only large values of the Fukui function in the region of the
metal center and the Michael acceptor and phenylogous Michael
acceptor positions.

Synthesis of a [Cp*Ru]-Complexed Biaryl Lactone
Organometallics, Vol. 18, No. 24, 1999 5019
F igu r e 2. Calculated Fukui function fNu(r): (top) shown
as a contour plot (function value 0.007); green regions
indicate areas of high local softness; (bottom) additional
indication of these areas by arrows.
F igu r e 3. Selected charges of 5b calculated by the method
of Loewdin (for further values, see the table in the
Supporting Information).
F igu r e 1. (top) Formula structure; (middle) crystal struc-
ture; (bottom) match plot of crystal structure (dark) and
calculated structure (light). Selected bond lengths [Å] of
the crystal structure: RuC(Cp*, average), 2.18(6); RuC-
(η6-C, average), 2.23(6); C(1)O(1), 1.36(6); C(3)O(2), 1.36-
(7); C(6)O(3), 1.37(7); C(6)O(4), 1.22(7); C(1)O(2), 1.38(7);
C(4a)O(3), 1.40(6); C(6)C(6a), 1.47(9); C(7)C(8), 1.34(9);
C(8a)C(12a), 1.43(8); C(9)C(10), 1.40(9); C(12b)C(12c), 1.45-
(7). The hydrogen atoms and the triflate counterion are
omitted for clarity.
by the bulky Cp* and arene ligands. Hydrides may, in
principle, also attack the Cp* ring system, which,
however, was not observed, as mentioned before (see
above). Since no reaction can take place at the carbonyl
oxygen due to its high electronegativity, C9 in the
benzonaphthopyranone system remains the position
most likely to be attacked, which supports our discus-
sions described before. Hard nucleophiles, by contrast,
should react charge controlled at hard positions of the
molecule, i.e., at places of high positive partial charges.
According to the calculations, complex 5b has the
largest calculated positive charge on the lactone carbo-
nyl C atom (cf. Figure 3). Thus the reaction of MeOH/
Na2CO3sin contrast to that of the soft hydridessled to
the desired stereoselective ring opening. As a conse-
quence, hard nucleophiles can be recommended for ring
cleavage reactions on this type of molecules, resulting
in good chemo- (and stereo-) selectivities.
These results make the above-described experimental
findings understandable: Hydrides, which may be clas-
sified as soft according to the HSAB concept,19 should
react mainly at the metal center as the position of the
highest Fukui value in the complex 5b. For a coordi-
natively saturated 18-electron complex such a hydride
addition would, however, be thermodynamically disfa-
vored and, in the present case, also sterically inhibited
(19) (a) Pearson, R. G. Hard and Soft Acids and Bases; Dowden,
Hutchinson & Ross: Stroudsville, PA, 1973. (b) Klopman, G. Chemical
Reactivity and Reaction Paths; Wiley: New York, 1974.
As exemplarily shown here for 5b, such ruthenium

5020 Organometallics, Vol. 18, No. 24, 1999
Bringmann et al.
274 (100) [M+ - C19H14O2+]. Anal. Calcd for C30H29F3O5SRu:
C, 54.62; H, 4.43; S, 4.86 Found: C, 53.57; H, 4.54; S, 4.84.
P r ep a r a tion of 5d . According to the general procedure, 500
mg (1.65 mmol) of lactone 3d and 841 mg (1.65 mmol) of
[Cp*Ru(NCMe)3]OTf (4) gave 682 mg (60%) of 5d . Mp: 247
complexes are most rewarding substrates for highly
atroposelective cleavage reactions and, simultaneously,
interesting objects of useful reactivity studies by means
of DF calculations involving the Fukui function, leading
to good agreements with the experimental results.
1
°C. H NMR (CD2Cl2): δ ) 8.26 (d, J ) 8.6 Hz, 1 H), 8.03 (d,
J ) 8.6 Hz, 1 H), 7.29-7.59 (m, 2 H), 6.93 (m, 1 H), 6.81 (m,
1 H), 6.49-6.62 (m, 2 H), 2.83-2.90 (m, 1 H), 2.77 (m, J ) 7.5
Hz, 2 H), 2.52-2.61 (m, 1 H), 1.53 (s, 15 H), 1.29 (t, J ) 7.4
Hz, 3 H), 0.91 (t, J ) 7.4 Hz, 3 H). 13C NMR (CD2Cl2): δ )
163.4 (-COO-), 156.8 (CH), 135.2 (CH), 132.5 (CH), 131.4
(CH), 130.4 (CH), 129.3 (CH), 127.3 (CH), 126.8 (CH), 125.9
(CH), 120.5 (CH), 116.8 (CF), 111.5 (CH), 96.55 (CH), 93.74
((CMe)5), 89.11 (CH), 85.82 (CH), 84.90 (CH), 84.23 (CH), 28.90
(CH), 28.27 (CH), 15.73 (CH), 14.62 (CH), 9.31 ((CMe)5). IR
(KBr): ν (cm-1) ) 1700 (s), 1590 (m), 1030 (s). MS (DCI, 70
eV): m/z (%) ) 538 (1) [M+], 302 (100) [M+ - Ru(CMe)5], 287
(49) [M+ - Me], 259 (8) [287 - CO]. Anal. Calcd for C32H33F3O5-
SRu: C, 55.87; H, 4.84; S, 4.66. Found: C, 55.39; H, 4.60; S,
4.39.
Exp er im en ta l Section
The experiments were performed under an argon atmo-
sphere with dried and distilled solvents using Schlenk tech-
niques. [Cp*Ru(NCMe)3]OTf (4)7 and the lactones 38 were
synthesized according to literature procedures. NMR spectra
were recorded with a Bruker AM 250 and a Bruker DMX 600
spectrometer at the Institut fu¨r Organische Chemie, Univer-
sita¨t Wu¨rzburg. Elemental analyses were carried out by the
microanalytical laboratory of the Institut fu¨r Anorganische
Chemie, Universita¨t Wu¨rzburg.
Gen er a l P r oced u r e for th e Syn th esis of th e Ru th e-
n iu m Com p lexes 5. To a solution of 1 equiv of lactone 3 in
CH2Cl2 (20 mL/mmol) was added 1 equiv of [Cp*Ru(CH3CN)3]-
OTf. After 24 h stirring at room temperature and separation
of the precipitate, the reaction solution was diluted with 30
mL of Et2O to give complex 5. Recrystallization of the crude
product from CH2Cl2/Et2O (1:1) yielded the product in an
analytically pure form.
P r ep a r a tion of 5a . According to the general procedure
described above, 500 mg (2.03 mmol) lactone 3a and 1.03 g
(2.03 mmol) of [Cp*Ru(NCMe)3]OTf (4) gave 850 mg (66%) of
5a . Mp: 232 °C. 1H NMR (CD2Cl2): δ ) 8.43 (m, 1 H), 8.30 (d,
J ) 8.6 Hz, 1 H), 8.12 (d, J ) 8.6 Hz, 1 H), 7.33-7.55 (m, 3
H), 6.97 (m, 1 H), 6.79 (m, 1 H), 6.59-6.70 (m, 2 H), 1.50 (s,
15 H). 13C NMR (CD2Cl2): δ ) 161.0 (-COO-), 154.3 (CH),
136.5 (CH), 134.8 (CH), 131.5 (CH), 131.4 (CH), 128.9 (CH),
128.3 (CH), 127.8 (CH), 126.5 (CH), 123.3 (CH), 118.2 (CF),
112.7 (CH), 97.27 (CH), 95.33 ((CMe)5), 93.72 (CH), 91.23 (CH),
87.12 (CH), 83.56 (CH), 9.52 ((CMe)5). IR (KBr): ν (cm-1) )
1700 (s), 1590 (m), 1040 (s). MS (DCI, 70 eV): m/z (%) ) 482
(1) [M+], 246 (100) [M+ - Ru(CMe)5], 218 (67) [M+ - CO], 126
(14) [C10H6+], 94 (19) [C6H6O+]. Anal. Calcd for C28H25F3O7-
SRu: C, 53.24; H, 3.99; S, 5.08. Found: C, 52.87; H, 3.71; S,
4.88.
P r ep a r a tion of 5e. Following the general procedure, 500
mg (1.51 mmol) of lactone 3e and 770 mg (1.51 mmol) of
[Cp*Ru(NCMe)3]OTf (4) gave 628 mg (58%) of 5e. Mp: 249
1
°C. H NMR (CD2Cl2): δ ) 8.30 (d, J ) 8.7 Hz, 1 H), 8.08 (d,
J ) 8.7 Hz, 1 H), 7.33-7.61 (m, 2 H), 6.99 (m, 1 H), 6.87 (m,
1 H), 6.51-6.63 (m, 2 H), 3.11 (sept, J ) 6.8 Hz, 1 H), 2.99 (m,
J ) 6.8 Hz, 1 H), 1.59 (d, J ) 6.8 Hz, 3 H), 1.48 (s, 15 H), 1.38
(d, J ) 6.6 Hz, 3 H), 1.36 (d, J ) 6.8 Hz, 3 H), 0.71 (d, J ) 6.6
Hz, 3 H). 13C NMR (CD2Cl2): δ ) 162.9 (-COO-), 155.3 (CH),
135.2 (CH), 132.8 (CH), 131.2 (CH), 129.6 (CH), 128.5 (CH),
125.8 (CH), 124.8 (CH), 121.8 (CH), 120.8 (CH), 115.8 (CF),
112.3 (CH), 99.34 (CH), 94.55 ((CMe)5), 91.33 (CH), 88.56 (CH),
85.43 (CH), 83.93 (CH), 33.26 (CH), 30.93 (CH), 26.86 (CH),
22.91 (CH), 22.34 (CH), 19.52 (CH), 9.44 ((CMe)5). IR (KBr):
ν (cm-1) ) 1700 (s), 1580 (m), 1020 (s). MS (DCI, 70 eV): m/z
(%) ) 566 (1) [M+], 330 (100) [M+ - Ru(CMe)5], 315 (36) [M+
- Me], 273 (58) [M+ - C4H9]. Anal. Calcd for C34H37F3O5SRu:
C, 57.05; H, 5.21; S, 4.48. Found: C, 56.72; H, 5.02; S, 4.21.
P r ep a r a tion of 5f. According to the general procedure, 120
mg (240 µmol) of lactone 3f and 86.0 mg (240 µmol) of [Cp*Ru-
1
(NCMe)3]OTf (4) yielded 111 mg (63%) of 5d . Mp: 256 °C. H
NMR (CDCl3): δ ) 8.19 (d, J ) 9.0 Hz, 1 H), 7.71 (d, J ) 2.0
Hz, 1 H), 7.68 (d, J ) 9.0 Hz, 1 H), 7.27 (d, J ) 2.0 Hz, 1 H),
6.82 (d, J ) 6.0 Hz, 1 H), 6.64 (m, 1 H), 6.35-6.47 (m, 2 H),
1.43 (s, 15 H), 1.42 (s, 9 H), 1.15 (s, 9 H). 13C NMR (CDCl3):
δ ) 160.0 (-COO-), 156.0 (CH), 151.9 (CH), 139.8 (CH), 127.5
(CH), 126.4 (CH), 125.8 (CH), 125.2 (CH), 124.7 (CH), 123.2
(CH), 122.9 (CH), 122.7 (CH), 121.6 (CH), 120.1 (CH), 115.1
(CF), 111.0 (CH), 110.7 (CH), 98.23 (CH), 95.39 ((CMe)5), 94.45
(CH), 93.69 (CH), 89.51 (CH), 87.84 (CH), 40.12 (CH), 35.62
P r ep a r a tion of 5b. According to the general procedure, 301
mg (0.98 mmol) of lactone 3b and 500 mg (0.98 mmol) of
[Cp*Ru(NCMe)3]OTf (4) gave 420 mg (62%) of 5b. Mp: 218
1
°C. H NMR (CDCl3): δ ) 8.16 (d, J ) 8.9 Hz, 1 H), 7.54 (d, J
) 8.9 Hz, 1 H), 6.66 (m, 1 H), 6.62 (m, 1 H), 6.60 (d, J ) 2.2
Hz, 1 H), 6.55 (d, J ) 2.2 Hz, 1 H), 6.49 (t, J ) 5.8 Hz, 1 H),
6.32 (t, J ) 5.8 Hz, 1 H), 3.94 (s, 3 H), 3.92 (s, 3 H), 1.52 (s, 15
H). 13C NMR (CDCl3): δ ) 164.10 (-COO-), 160.3 (CH), 157.6
(C-OMe), 154.4 (C-OMe), 138.1 (CH), 127.4 (CH), 126.1 (CH),
120.7 (CH), 118.7 (CH), 101.2 (CH), 97.80 (CH), 96.73 (CH),
96.14 (CH), 94.93 ((CMe)5), 94.43 (CH), 91.03 (CH), 88.06 (CH),
85.89 (CH), 85.16 (CH), 56.28 (OMe), 56.12 (OMe), 9.51
((CMe)5). IR (KBr): ν (cm-1) ) 1720 (s), 1600 (m), 1030 (m).
(CH), 33.66 (CH), 31.25 (CH), 9.35 ((CMe)5). IR (KBr): ν (cm-1
)
) 1720 (s), 1580 (m), 1020 (s). MS (DCI, 70 eV): m/z (%) )
595 (1) [M+], 358 (100) [M+ - Ru(CMe)5], 343 (77) [M+ - Me],
329 (53) [343 - Me]. Anal. Calcd for C36H41F3O5SRu: C, 58.13;
H, 5.56; S, 4.31. Found: C, 57.86; H, 5.29; S, 4.29.
MS (DCI, 70 eV): m/z (%) ) 542 (11) [M+], 306 (100) [M+
Ru(CMe)5], 291 (11) [306 - Me], 262 (11) [306 - CO2]. Anal.
Calcd for C30H29F3O7SRu: C, 52.09; H, 4.23; S, 4.64. Found:
C, 51.63; H, 4.20; S, 4.74.
P r ep a r a tion of 5c. According to the general procedure, 280
mg (1.02 mmol) of lactone 3c and 520 mg (1.02 mmol) of
[Cp*Ru(NCMe)3]OTf (4) gave 417 mg (62%) of 5c. Mp: 216
-
Rin g Clea va ge of Com p lex 5b w ith MeOH/Na 2CO3. To
a solution of 100 mg (0.14 mmol) of 5b in 15.0 mL of CH2Cl2
was added a suspension of 30.7 mg (0.28 mmol) of Na2CO3 in
11.7 mL of methanol. The solution was stirred for 3 h at room
temperature, filtered, and diluted with 20 mL of Et2O to give
complex 7b. Recrystallization from CH2Cl2/Et2O (1:1) yielded
70.1 mg (67%) of 5 as a yellow to orange-colored solid. Mp:
168 °C. 1H NMR (CDCl3): δ ) 8.62 (br s, 1 H), 7.93 (d, J ) 9.0
Hz, 1 H), 7.46 (d, J ) 9.0 Hz, 1 H), 6.59 (d, J ) 2.0 Hz, 1 H),
6.44 (d, J ) 6.0 Hz, 1 H), 6.13 (m, 2 H), 5.96 (t, J ) 6.0 Hz, 2
H), 5.76 (t, J ) 6.0 Hz, 2 H), 3.84 (s, 3 H), 3.73 (s, 3 H), 3.51
(s, 3 H), 1.68 (s, 15 H). 13C NMR (CDCl3): δ ) 167.52 (-COO-
), 162.35 (CH), 157.92 (C-OMe), 156.34 (C-OMe), 136.31
(CH), 133.98 (CH), 130.69 (CH), 125.49 (CH), 103.50 (CH),
99.41 (CH), 96.36 (CH), 94.98 ((CMe)5), 94.20 (CH), 91.29 (CH),
88.20 (CH), 84.91 (CH), 84.06 (CH), 77.22 (OCOMe), 55.52
1
°C. H NMR (CDCl3): δ ) 8.27 (d, J ) 9.0 Hz, 1 H), 7.71 (d, J
) 9.0 Hz, 1 H), 7.19 (s, 1 H), 7.14 (s, 1 H), 6.81 (d, J ) 6.0 Hz,
1 H), 6.54 (m, 3 H), 2.50 (s, 3 H), 2.40 (s, 3 H), 1.51 (s, 15 H).
13C NMR (CDCl3): δ ) 170.9 (-COO-), 159.9 (CH), 151.9
(CH), 143.0 (CH), 138.1 (CH), 137.3 (CH), 136.2 (CH), 130.3
(CH), 128.6 (CH), 114.7 (CH), 97.41 (CH), 96.00 (CH), 95.13
((CMe)5), 91.44 (CH), 88.31 (CH), 85.43 (CH), 83.89 (CH), 23.72
(CH), 21.4 (CH), 9.04 ((CMe)5). IR (KBr): ν (cm-1) ) 1720 (s),
1600 (m), 1025 (s). MS (DCI, 70 eV): m/z (%) ) 510 (1) [M+],

Synthesis of a [Cp*Ru]-Complexed Biaryl Lactone
Organometallics, Vol. 18, No. 24, 1999 5021
(OMe), 52.78 (OMe), 9.69 ((CMe)5). IR (KBr): ν (cm-1) ) 3400
(m, br), 1680 (s), 1590 (m), 1010 (m). MS (CI, 70 eV): m/z (%)
) 574 (1) [M+], 515 (100) [M+ - C2H3O2], 338 (1) [M+ - Ru-
(CMe)5]. Anal. Calcd for C31H33F3O8SRu: C, 51.59; H, 4.60; S,
4.43. Found: C, 51.29; H, 4.73; S, 4.51.
Crystallographic Data Centre as supplementary publication
no. CCDC-101332. Copies of the data can be obtained free of
charge on application to CCDC, 12 Union Road, Cambridge
CB2 1EZ, U.K. [fax (internat.) +44(1223)336-033; e-mail
deposit@ccdc.com.ac.uk].
Cr ysta l Str u ctu r e of 5b. C30H29F3O7RuS, M ) 691.66,
crystal size: 0.4 × 0.3 × 0.1 mm3, triclinic, P1h, unit cell
dimensions a ) 7.375(4) Å, b ) 11.802(5) Å, c ) 16.827(8) Å,
R ) 80.54(3)°, â ) 82.50(3)°, γ ) 75.60(4)°, V ) 1393(2) Å3, Z
) 2, Dc ) 1.649 Mg m-3, F(000) ) 704, λ ) 0.71073 Å, T )
133(2) K, µ ) 0.706 mm-1; total number of reflections mea-
sured 4301, unique 3634 (Rint ) 0.047). Final R indices: R1(F
> 2σ(F)) ) 0.044, wR2 ) 0.103 on all data, largest difference
peak and hole 925 and -588 e nm-3. Data were collected from
a shock-cooled crystal on an Enraf Nonius CAD4 four-circle
diffractometer (graphite-monochromated Mo KR radiation, λ
) 71.073 pm) equipped with a low-temperature device.20 The
structure was solved by direct methods using SHELXS-9721
and refined against F2 on all data by full-matrix least-squares
with SHELXL-97.22 Crystallographic data for the structure
reported in this paper have been deposited with the Cambridge
Th eor etica l Ca lcu la tion s. The structure of 5b was mini-
mized on a CRAY computer YMP/8-128 by means of the
standard optimization algorithm, as implemented in the
program DGAUSS 3.0.23 As the functional/basis set combina-
tion, BLYP/DZVP was applied. The electron density was fitted
by a triple-· A1 set. Electron densities FN+1 and FN at fixed
nucleus positions were calculated on an SGI INDIGO R4400
workstation by means of the program package Gaussian 94
(UHF/LANL1DZ).24 The subtraction of the electron densities
was performed by the tool CUBMAN, as implemented in
Gaussian 94. For the visualization of the Fukui function, the
SYBYL molecular modeling package was used.25 Charges were
calculated by the method of Loewdin by means of the program
DGAUSS 3.0.23
Ack n ow led gm en t. This work was supported by the
Deutsche Forschungsgemeinschaft (SFB 347 “Selektive
Reaktionen Metall-aktivierter Moleku¨le”) and by the
Fonds der Chemischen Industrie (graduate research
fellowship to R.S. and financial support). We thank Prof.
Dr. B. Engels for helpful discussions.
(20) Stalke, D. Chem. Soc. Rev. 1998, 27, 171.
(21) Sheldrick, G. M. Acta Crystallogr. Sect. A 1990, 46, 467.
(22) Sheldrick, G. M. SHELXL-97 program for crystal structure
refinement; Universita¨t Go¨ttingen, 1997.
(23) Andzelm, J . In Density Functional Methods in Chemistry;
Labanowski, J ., Andzelm, J ., Eds.; Springer: New York, 1991; p 155.
DGAUSS is part of the UniChem-Programs of Cray Research, Inc.,
Eagan, MN.
(24) J ohnson, B. G.; Robb, M. A.; Cheeseman, J . R.; Keith, T. A.;
Petersson, G. A.; Montgomery, J . A.; Raghavachari, K.; Al-Laham, M.
A.; Zakrzewski, V. G.; Ortiz, J . V.; Foresman, J . B.; Cioslowski, J .;
Stefanov, B. B.; Nanayakkara, A.; Challacombe, M.; Peng, C. Y.; Ayala,
P. Y.; Chen, W.; Wong, M. W.; Andres, J . L.; Replogle, E. S.; Gomperts,
R.; Martin, R. L.; Fox, D. J .; Binkley, J . S.; Defrees, D. J .; Baker, J .;
Stewart, J . P.; Head-Gordon, M.; Gonzalez, C.; Pople, J . A. Gaussian
94; Gaussian, Inc.: Pittsburgh, PA, 1995.
Su p p or tin g In for m a tion Ava ila ble: Table with the
calculated charges of 5b. Text giving details of the X-ray
crystal structure studies and tables of crystal structure de-
termination data, atomic coordinates, anisotropic thermal
parameters, and bond length and angles for compound 5b. This
material is available free of charge via the Internet at
http://pubs.acs.org.
(25) SYBYL 6.2; Tripos Associates: 1699 St. Hanley Road, Suite
303, St. Louis, MO, 63114.
OM9906520