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Novel Facile Synthesis of Multiply ortho-Bridged Phane-Hydrocarbons and of Dihydrocyclobutabenzenes.

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ylation to 3 this is converted by benzaldehyde dimethyl
acetal into 4, which after benzylation with benzyl bromide
affords 5 . Subsequent acid hydrolysis furnishes 6 , which
Received: July 26, 1982,
revised: October 6, 1982 [Z 109 IE]
German version: Angew. Chem. 94 (1982) 934
forms of 2.4-2.6 Hz small, which suggests different conformations in the side chains.
[ I ] A. Ya. Khorlin, J. M. Privalova, J. B. Bystrova, Curbohydr. Res. 19 (1971)
272; R. Brossmer, H. Friebolin, G . Keilich, B. Loser, M. Supp, HoppeSeyler's Z . Physiol. Chem. 359 (1978) 1064.
[2] H. Paulsen, A. Biinsch, Liebigs Ann. Chem. 1981, 2204: Carbohydr. Res.
100 (1982) 143.
[3] H. Paulsen, J.-P. Holck, Liebigs Ann. Chem. 1982, 1121; R. U. Lemieux,
S. Z. Abbas, M. H. Burzynska, R. M. Ratcliffe, Can. J. Chem. 60 (1982)
[41 400 M H z ' H - N M R in D 2 0 (relative t o acetone, 6=2.12): 8 (a-o-anomer): 6=5.11 (I-H), 4.38 (1'-H), 2.31 (3"-H,), 1.59 (3"-H,), 1.93, 1.94
I I (u-D-anomer): 6=5.01 (I-H), 4.35 (1'-H), 2.56 (3"-H,), 1.65
(N-Ac).(3"-H,,), 1.93, 1.96 (N-Ac).
I S ] U. Dabrowski, H. Friebolin, R. Brossmer, M. Supp, Tetrahedron Left.
I9 79. 463 7.
0 R1
Novel Facile Synthesis of Multiply ortho-Bridged
Phane-Hydrocarbons and of
By Brigitte Klieser and Fritz Vogtle*
10 (d-D-form)
d - D - NANA- ( 2 - 6 b p - 0 - GaI(1-4)
- D- GlcNAc 11
can be used directly for glycoside synthesis, since 6'-OH is
considerably more reactive than 4'-OH. 7 reacts with 6 in
presence of Hg(CN)z/HgBr2 (3 : 1) in dichloromethane
(20°C, 3 d) to give the glycosides 9 and 10 (molar ratio
1 : 1 ) in approximately 50% yield. Column chromatography
(chloroform/methanol) of the mixture results in isolation
of 20% a-D-form 10 ([a]: - 12.8, c = 1.0 in CHzCI,) and
20% p-D-form 9 ([a]: -4.0, c = 1.0 in CHzC12). In order to
deblock 10, the N3 group is first reduced by H2S to the
NH2 group (629/0), and both NHZ and 4'-OH groups are
subsequently acetylated (71%). The 0-acetyl groups can
then be cleaved using catalytic amounts of sodium methoxide in methanol and the methyl ester cleaved by
NaOH (99%). Finally, the benzyl ethers are cleaved by hydrogenolysis leading to the free trisaccharide 11 ([a]L6
- 0.7, c = 1.0 in H20l4I. The B-D-form 9 can be analogously
deblocked to afford the trisaccharide 8 ([a]: -3.5, c =
1.0 in Hz0)[41.
The assignment of the anomers was performed by comparison of the 'H-NMR spectra of 8 and 11. In the a - ~ form 11, the signal of 3"-H, at 6=2.56 (in D20) is characteristically[" shifted to low field (3"-H, of 8 : 6=2.31).
However, this rule does not apply to blocked N-acetylneuraminic acid oligosaccharides. Here we can state a new assignment rule for the case when the N-acetylneuraminic
acid moiety is completely acetylated. In 10 and 9, and in
all intermediates the signal of 4"-H in the a-form at
6 = 4.89-4.93 lies at higher field than in the p-form (4"-H,
6 = 5.68-5.8 I). Furthermore, the J7,8coupling of 6.2-8.2
Hz in all the a-forms is large, and in contrast that in the p928
0 Verlag Chemie GmbH. 6940 Weinheim. 1982
We have now found that the cesium-catalyzed sulfidecyclization recently developed by us enabled the one-step
synthesis of multiply ortho-bridged benzene rings"], e. g.
of 1 ; following on from that we have now succeeded by sulfone pyrolysis in synthesizing multiply 12-bracketed
phane-hydrocarbons in a few simple steps, and-surprisingly-also of bridged dihydrocyclobutabenzenes. Multiply orrho-bridged phanes, unlike their meta-bridged analog~'~
~ , hitherto not accessible from sulfones[21.
Pyrolysis (600 "C/0.005 torr) of the mixture of sulfones
2a, b (sublimation temp. 550 "C) obtainable from the mixture of the tetrasulfides l a , b"], does not yield the desired
fourfold bracketed phane 4[41,but the doubly bridged 1,2dihydrocyclobutabenzene 3. The 'H-NMR data of 3['] and
4[41are in complete accord with those quoted in the literature.
On pyrolysis of 2 at higher temperature (75O0C/O.15
torr; sublimation temperature 700 "C), however, we were
able to isolate a 1 :2 mixture of 3 and 4 in ca. 40% yield
(unequivocal identification from 'H-NMR signals and
mass spectra).
[*I Prof. Dr. F. Vogtle, B. Klieser
lnstitut fur Organische Chemie und Biochemie der Universit3.t
Gerhard-Domagk-Strasse I, D-5300 Bonn I (Germany)
0570-0833/82/1212-0928 $ 02.50/0
Angew. Chem. I n t . Ed. Engl. 21 (1982) No. 12
Our experimental findings that 1,2,4,5,7,8,10,1 l-octahydrobiscyclobuta[4,5]benzo[1,2-a : 1’,2’-e]cyclooctene 3 is
formed initially, and not the []cyclophane 4, is very
interesting, because 3 occurs as intermediate in the multistep synthesis of 4I5l, and 4 has already been obtained by
thermolysis of 3.
The novel synthetic route uia an “ortho-sulfone pyrolysis” not only offers the advantage of a small number of
rapid and simple steps, but also enables synthesis of dihydrocyclobutabenzene intermediates such as 3, which are
thus also conveniently accessible for other reactions. Furthermore, numerous unsymmetric phane-hydrocarbons
such as the pyrazinobenzophane 5 should now be accessible in an analogous way from the corresponding unsym-
metrical sulfones, whereas previous methods were restricted to symmetrical compounds of type 3 and 4. Fivefold and sixfold bracketed arenes-e.g. superphanes-including the corresponding dihydrocyclobutabenzene intermediates, should also be obtainable by this novel combination of cesium-catalyzed sulfide cyclization“] and orthosulfone pyrolysis.
Received: July 28, 1982 [Z110 IE]
German version: Angew. Chem. 94 (1982)922
The complete manuscript of this communication appears in:
Angew. Chem. Suppl 1982, 1956-1961
F. Vogtle, B. Klieser, Angew. Chem. 94 (1982)632;Angew. Chem. Int. Ed.
Engl. 21 (1982)618.
F. Vogtle, G. Hohner, Top. Curr. Chem. 74 (1978) 1.
F. Vogtle, L. Rossa, Angew. Chem. 91 (1979)534;Angew. Chem. Int. Ed.
Engl. 18 (1979)515;V. Boekelheide, R. A. Hollins, J. Am. Chem. Soc. 95
V. Boekelheide, R. Gray, Angew. Chem. 87 (1975)138;Angew. Chem. Int.
Ed. Enyl. 14 (1975) 107: J. Kleinschroth, H. Hopf, ibid. 91 (1979)336 and
18 (1979)329.
V. Boekelheide, G. Ewing, Tetrahedron Lett. 1978. 4245.
Bis[bis(trimethylsilyl)acetylenejdicarbonylchromium* *
By Karl Heinz Do&* and Jochen Muhlemeier
Pentacarbonyl[aryl(methoxy)carbene]chron~ium complexes 1 react with equimolar amounts of bis(trimethy1si1yl)acetylene 2 to give the metal-coordinated vinylketenes
3, which can be formally described as products of a headto-tail addition of the carbene and a carbonyl ligand to the
alkyne[41.In contrast, if the reaction is carried out with an
excess of alkyne (e. g. in the ratio 1 : 2 = 1 :2.2) in tert-butyl methyl ether, then, on heating, the uncoordinated vinylketene 4 and the title compound 5 are also obtained.
The deep-violet complex 5 , which is moderately sensitive to light and extremely sensitive to oxidation, was char[*] Priv.-Doz. Dr. K. H.Dotz, J. Muhlemeier
Anorganisch-chemisches lnstitut der Technischen Universitat Miinchen
Lichtenhergstrasse 4, D-8046 Garching (Germany)
[**I Vinylketenes, Part 4. This work was supported by the Deutsche Forschungsgemeinschaft and the Fonds der Chemischen Industrk-Part 3:
Angew. Chem. Int. Ed. Engl. 21 (1982) No. 12
c = c’
Aryl‘ Cr(C013
p-C6Hq-R (R
= H. Me. OMe.CF3)
acterized by total analysis and by spectroscopic methods[’]
[IR: v(C=O) 1965, 1904 cm-’ (n-hexane), v(C=C) 1705
c m - ’ (Nujol); ‘H-NMR: 6=0.28; MS: m/z=448 ( M + ) ,
392 ( M + - 2 CO), 222 ( M +- 2 C0-Me3Si--C=CSiMe,). In solution, bis(trimethylsilyl)acetylene is slowly
cleaved from the complex if not kept in the dark, thus ruling out coupling of the alkyne ligands in the complex. Information about the coordination of the alkyne ligands is
provided, in particular, by the I3C-NMR spectrum: The
signal of the C-atoms of the two CO-ligands appears at
6=258.9, that of the alkyne C-atoms at 6 = 197.8; such
downfield shifts (free alkyne: 6= 115.4) are regarded as a
criterion for the alkynes functioning as four-electron ligandsI6l, thus leading to the noble gas configuration of the
chromium in 5 . In contrast, the 29Si chemical shift
(6= - 7.4) is unsuited for investigation of the electron-donor capability of the alkyne, as is revealed on comparison
(6= - 8.5)[91.
The bis(a1kyne)dicarbonyl complex 5 constitutes the
first satisfactorily characterized ternary alkyne-carbonyl
compound of chromium, after the synthesis of the tris(a1kyne)carbonyl complexes of molybdenum and tungsten
could so far not be extended to the lightest homologue.
Received: August 2, 1982 [ZI16 IE]
supplemented: October I I , 1982
German version: Angew. Chem. 94 (1982)936
The complete manuscript of this communication appears in:
Angeng. Chem. Suppl. 1982. 2023-2029
[I] K. H. Dotz, B. Trenkle, U. Schuhert, Angew. Chem. 93 (1981)296;Angew.
Chem. Int. Ed. Engl. 20 (1981)287.
[4] K. H. Dotz, B. Fugen-Koster, Chem. Ber. 113 (1980) 1449.
151 We thank Priv.-Doz. Dr. H. G. All and Priv.-Doz. Dr. F. R. Kreissl for recording the NMR spectra ([D,]-toluene, rel. int. TMS) and the mass spectrum.
161 J. L. Templeton, B. C. Ward, J. Am. Chem Soc. 102 (1980)3288.
191 K. H. Pannell, A. R. Bassindale, J. W. Filch, J. Organomet. Chem. 209
Coordinatively Unsaturated Trinuclear
Molybdenum-Sulfur Cluster Chelates
with Dithiophosphinato Bridge
By Helmut Keck. Wilhelm Kuchen*, Jurgen Mathow,
and Hartmut Wunderlich
We have found that by allowing Mo,S,-cluster dithiophosphinates l 1 I 1 to react with triphenylphosphane partial
[*]Prof. Dr. W. Kuchen, Dr. H. Keck, J. Mathow, Dr. H. Wunderlich
Institut fur Anorganische Chemie und Strukturchemie der Universitat
Universitatsstrasse 1 , D-4000 Dusseldorf (Germany)
0 Verlag Chemie GmbH, 6940 Wemheim, 1982
0570-0833/82/1212-0929 $ 02.50/0
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synthesis, hydrocarbonic, bridge, novem, faciles, multiple, phan, dihydrocyclobutabenzenes, ortho
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