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CC-Coupling of CO2 and Butadiene on Iron(0) ComplexesЧA Novel Route to -Dicarboxylic Acids.

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CC Coupling of CO, and Butadiene on
Iron(0) Complexes-A Novel Route to
a,o-Dicarboxylic Acids
7
By Heinz Hoberg,* Klaus Jenni, Carl Kriiger, and
Eleonore Raabe
8
of the addition depends upon the pH (Scheme 4): In basic
media C-3 is attacked nucleophilically, resulting in formation of l .I6] The direction of addition can be turned around
by acid catalysis. However, the eight-membered ring thiolactone is not isolated, but the product of ring-opening,
ethyl 7-mercaptoheptanoate 9, in 40% yield. 9 reacts further in air to give the dis~1fide.I'~
Q:j*;
Carbon dioxide is attracting increasing interest as a C ,
building block in preparative chemistry, particularly in
synthetic methods involving its activation by transition metal complexes."l Stoichiometric (1 : 1) coupling reactions of
C 0 2 and systems containing multiple bonds have hitherto
only been accomplished with Ni",''.'' W" a nd Mo" complexes.12h1We have now also been able to induce such a
C C coupling with Fen complexes, whereby (q4-butadiene)tris(trimethylphosphane)iron(o) 1I3I has proven to be
a n especially suitable complex for this purpose.
'
Lj
1
ROH, H20
L=PMe,
H,C-CH,-O-CO-CH,-(CH,)~-CH,-SH
BF, ' OEt2
6('H)
9
=
1.25 2.49
6(13C) =
14.3 60.2
2.28 1.28
1 .To
173.2 34.3 29.0
28.7
28.6
27.8
4.10
24.6
2a
2b
Scheme 4. Addition 01' water to 4 .
I
The combined action of strain and polarization of the
triple bond leads to 4 readily reacting both with electrophiles as well with nucleophiles. Thus, it not only differs
significantly from other strained cycloalkynes, but also
from open-chain alkynyl sulfanes containing a less reactive
triple bond."I
Received: April 18, 1986;
supplemented: June 3, 1986 [Z 1737 IE]
German version: Angew. Chem. 98 (1986) 838
CAS Registry numbers:
1, 33131-80-5: (Q-2, 103794-89-4; ( a - 2 , 103794-90-7; 3, 103816-44-0; 4,
103794-91-8: 7,479-33-4: 8, 103794-92-9: 9, 1931-79-9.
[ I ] A. Krebs, 1. Wilke, Top. Curr. Chem. 109 (1983) 189, and references cited
therein.
[2] M. Sakurai, Y. Nakadaira, A. Hosomi, Y. Eriyama, J . Am. Chem Sor 105
(1983) 3359.
[3j E. Kloster-Jensen, G. A. Eliassen, Anqew. Chenz. 97 (1985) 587: A n g e w
Chem. l n t . Ed. Engl. 24 (1985) 565.
[4] H. Ramane, R. Borsdorf, M. Muhlstadt, J . Prakt. Chem. 312 (1971)
1058.
[ S ] Cf. H. Meier, H. Petersen, H. Kolshorn, Chem. Ber. 113 (1980) 2398.
[6] This behavior is reminiscent of that of the nonisolable 2-cyclooctyn-lone: P. E. Eaton, C. E. Stubbs, J . Am. Chem. SOC.89 (1967) 5722.
[7] If one compares the reactwily of 4 and 5 , then, aside from reactions
which are possible only with 4, and reactions which proceed analogously
to 4 and 5, also reactions with 4 can be expected that lead to quite different products than with 5 . For example, upon twofold reaction with
4-phenyl-I,2,4~triazolindone(molar ratio 1 :2), 5 undergoes a twofold ene
reaction [XI, while 4 undergoes a double cycloaddition.
[8] C C . Cheng, F. D. Greene, J F. Blount, J . Org. Chem. 49 (1984) 2917.
[9] R. M. Wilson, D. N. Buchanan, Method. Chim 7 (1976) 652, and references cited therein.
8 10
0 VCH Verlaqsgesellrchajt mhH. D-6940 Weinheim. 1986
HjO
I
@
1.
/=vCOOH
HOOCwCOOH
3
2-5
+
4
coz
1 FeCI.,
2 H,O@
+
i
2 H,O@
1
H
o
o2
C4 A
C
o
O
H
E-5
Scheme I I h r (un5)btcindtic) i i u m h ~ r i n gi n 2 and 6 serves only for assignment of the ' H - N M R signals.
Treatment of a solution of 1 in tetrahydrofuran (THF) at
35°C with C 0 2 ( 3 bar) leads to formation of the carboxylate complex 2 [diamagnetic, m.p. 110°C (decomp.)] in
75% yield.I4]Like most q3-allyl-transition metal complexes 2
exhibits a dynamic behavior in solution, which manifests
itself in the ' H - N M R spectrum (2S°C, [D6]acetone) by very
broad signafs for the hydrogen atoms in the a-position to
the carboxylate group. Whether this merely indicates a reorientation of the q3-allyl moietyI5l or a dynamic equilibrium 2a + 2 + 2b, cannot be unequivocally decided from
the available data. In contrast, at - 80°C the compound is
frozen-in in the q3-allyl structure, and rotation of one of
the three PMe3 ligands is hindered. 2 also has the q3-allyl
[*] Prof. Dr. H. Hoberg, Dipl.-Chem. K Jenni, Prof. Dr. C. Kriiger,
Dr. E. Raabe ['I
Max-Planck-lnstitut fur Kohlenforschung
Kaiser-Wilhelm-Platz I . D-4330 Miilheim a. d. Ruhr I (FRG)
['I
['I
Crystal structure analysis.
0570-0833/86/0909-08)810$ 02.50/0
Angew. Chem. In!. Ed. Engl. 25 11986) No. Y
structure in the crystalline state, as has been confirmed by
a n X-ray structure analysis on a single crystal (Fig. I).'"l
intermolecular C C coupling of the allyl ligands of two molecules of 2 . Once again, only the Fe-C o-bond of 2a
reacts and not that of 2b, since the latter reaction would
have to lead to branched a-o-dicarboxylic acids.
Received: April 25, 1986 [Z 1746 IE]
German version: Angew. Chem. 98 (1986) 819
02
n
x,,
CAS Registry numbers:
1, 56315-41-4; 2, 103677-24-5; 2a, 103693-14-7; 2b, 103693-15-8; 3 (methyl
ester), 36781-66-5; 4 (methyl ester), 818-57-5; ( E ) - 5 (bis(methy1)ester).
25 126-93-6; (Z)-5 (bis(methyl)ester), 70354-00-6: 6, 80557-04-6: COZ,
124-38-9.
Fig. 1. Structure o f 2 in the crystal. Selected bond lengths 181and angles ["I:
Fe-CI 2.124(2), Fe-C2 2.050(2), Fe-C3 2.152(2); Fe-01-C5 121.3( I), 01-C5C 4 I15.5(2). CS-C4-C3 114.0(2), C4-C3-C2 123.3(2), C3-C2-C1 124.4(2).
The coordination at the Fe-atom can be described as
trigonal-pyramidal: the atoms P1 and P3 as well as the
center of the allyl group CI-C2-C3 occupy equatorial positions, while the 0 1 and P2 atoms occupy axial positions.
The Fe-C distances in the q3-bonded allyl unit are as
usually found in such units. The carboxylate group is coordinated monodentate to the Fe atom; consequently, the C0 bond lengths are markedly different: 1.274(3) (C5-01) as
compared to 1.235(3) A (C5-02). The coordination of the
chain at both ends leads to a geometrically enforced disposition, which manifests itself in the magnitude of the bond
angles. That the axial bond Fe-P2 with a length of
2.213(1) is noticeably shorter than the two equatorial
Fe-P bonds (2.249(1) and 2.236(1) A, respectively) can be
explained in terms of a trans-effect of the 0-atom of the
carboxylate group.
The reaction behavior of 2 in solution can only be explained in terms of the q'-allyl structures 2a and 2b: acid
hydrolysis in methanol ( - 30°C) affords the methyl esters
of the two carboxylic acids 3 and 4 in the molar ratio
10: I,"] from which it follows that the reactivity of 2a is
greater than that of 2b. Consistent with this finding, 2 also
reacts with C 0 2 (9OoC, 5 bar) with preferential insertion in
the Fe-C a-bond of 2a and not in that of 2b: after hydrolysis, only 1,4- and no 1,2-dicarboxylic acids were isolated.IX1The Z-isomer expected from 2a is obtained as
main product. The E-isomer is presumably formed by
isomerization of Z-5 (molar ratio Z-5/E-5 =27 : 1).
Completely unexpected was the nature of the product
obtained upon reaction of 2 and FeC13 (molar ratio 2/
FeC13= 1 :2) in THF: acid hydrolysis of the reaction mixture furnished the symmetrical, linear a-o-dicarboxylic
acid 6 containing two isolated double bonds in 93%
yield.''' The formation of 6 can be explained in terms of an
A
Atigeu,. Chrm In!. Ed. Engl. 25 (1986) No. 9
[ I ] T. Ito, A. Yamarnoto in S. Inoue, N. Yamazaki (Eds.): Organicand Bioorgonic Chemistry of Carbon Dioxide. Kodansha Ltd., Tokyo 1982.
(21 a) H. Hoberg. 8. Apotecher, J . Orgonomet. Chem. 270 (1984) C 15: H.
Hoberg, D. Schaefer, B. W. Oster, ibid. 266 (1984) 313; H. Hoberg, B. W.
Oster, ibid. 266 (1984) 321, and literature cited therein; D. Walther, E.
Dinjus, H. Gorls, J. Sieler, 0. Lindqvist, L. Andersen, ibid. 286 (1985) 103,
and literature cited therein; b) R. Alvarez. E. Carmona, D. J. Cole-Hamilton, A. Galindo, E. Gutierrez-Puebla. A. Monge, M. L. Poveda, c'. Ruiz,
J . Am. Chem. Soc. 107 (1985) 5529.
131 a) T. V. Harris, J. W. Rathke, E. L. Muetterties, J . Am. Chem. Soc. 100
(1978) 6966; b) S. S . Wreford, J. F. Whitney, Inorg. Chem. 20 (1981)
3918.
141 Procedure for 2 : A solution of 1 (6.75 g, 20 mmol) in T H F (100 mL) was
transferred to a 200-mL steel autoclave and treated with 1350mL
(60 mmol) of C 0 2 at 78°C: the stirred mixture was heated to 35°C and
kept at this temperature for 72 h. After cooling and removal of the sediment by filtration (0.45 g, discarded), two-thirds of the solvent was removed from the filtrate by distillation. An orange-red, rnicrocryrtalline
solid precipitated from the concentrate. This was recovered by suction on
a frit and dried. Yield 5.73 g (15 mmol, 75%); m.p. I 10°C (decornp.); IR
(KBr): v= 1610 c m - ' (C=O): correct elemental analysis; ' H - N M R
[(D,C)ZCO, 6=2.04, -80°C. 400 MHz]: 6=4.37 (4, I H: H-4). 3.72 (q,
1 H ; H-3). 3.05 (t, I H ; H-5), 2.41 (dd, I H; H-I). 1.65 (d. I H ; H-2). 0.66
(d, I H ; H-6), 1.48 (d, 9 H ; (CH,),-7), 1.43 (d, 9 H , (CH3),-8), 0.8R, 0.75.
0.74 (each d, 3 H; 3CH1-9).
151 A. N. Nesmeyanow, Yu. A. Ustynyuk, I I. Kritskaya, G. A. Shchernbelov,
J . Organornet. Chem. 14 (1968) 395.
[6] Crystal structure analysis of 2 : space group P2,/n, Z = 4 , P'.~,,=1.28~g
cm-'; p(MoK,,)=9.94 c m - ' ; a=8.661(2), b= 15.248(3), c = 15.223(1) A:
p=98.069(7)". Solution of structure by the Patterson method. 4349 independent reflections with I > 2u(f), R=0.033, R, =0.043. Further details
of the crystal structure investigation are available on request from the
Fachinformationszentrum Energie, Physik, Mathematik GmbH, D-75 14
Eggenstein-Leopoldshafen 2, o n quoting the depository number CSD51930, the names of the authors, and the full citation of the journal
171 Procedure for 3 and 4 : 2 (1.48 g, 3.88 rnmol) was treated at -30°C with
5 mL of 6N methanolic HCI and the resulting solution, after 24 hours'
stirring, was neutralized with NaHCO, The volatile components were
then distilled off in a vacuum (2 x lo-" bar). According to a GC analysis
the distillate contained 314.0 mg (2.75 rnmol: 70.X0/o) of the methyl ester
of the acid 3 and 31.5 mg (0.28 mmol, 7.2%) of the methyl ester of the
acid 4 . The products were unequivocally identified by combined GC-MS
and comparison of the NMR spectral data with data given in the literature.
[8] Procedure for 5 : A solution of 2 (1.93 g, 5.05 mmol) in T H F (80 mL) was
treated at -78OC with 3 7 0 m L (15.2 mmol) of C 0 2 . The solution was
transferred to a steel autoclave and stirred for 4 d at 90°C and 5 bar. The
insoluble product was recovered by suction on a frit, dried, and workedup as described for 3, 4 in Ref. 171. The quantitative G C analysis afforded
the bis(methy1) esters of the acids 2 - 5 (156.2 m g = 1.37 mmol: 27%) and
E-5 (1.37 mg=0.05 mmol; I'Yo), which were identified as described in ref.
[7] for 3, 4.
[9] Procedure for 6 : A solution of 2 (1.91 g, 5 mmol) in T H F (ISOmL) was
treated at -78OC with 1.63 g (IOmmol) of FeCI.? and the resulting mixture heated, with continuous stirring, to room temperature. After 24 h. the
solvent was removed by distillation and the brown residue (3.36 g) remaining behind was hydrolyzed with ca. 5 m L of 2~ H2S04 in the presence of diethyl ether. The organic phase was dried over MgSO, and then
purified by chromatography o n silica gel 60 (toluene/diethyl ether I : 1).
Yield of 6 : 461.3 mg (2.33 mmol; 93%). M.p. 52°C; correct elemental
analysis; IR (KBr): v=1710 (C=O), 965 c m - ' (E-CH=CH); MS (Cl,
reactant gas NHI): m / z 216 [ ( M t N H ? ) , loo%]; ' H ~ N M R(CDCI,, 25"f,
6=7.24, 200 MHz): 6=8.62 (broad, 2 H ; H-I], 5.55 (m, 4 H ; H-3,4), 3.09
(dd, 4 H , H-2), 2.12 (s, 4 H ; H-5).
~
0 VCH Verlagrge.sellschaji mbH, 0-6940 Weinherm. 1986
OS7O-0833/86/O909-O81I $ O2.50/0
811
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acid, couplings, iron, co2, novem, complexes, dicarboxylic, route, butadiene
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