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Optically Active Cyclopentanediol Synthetic Building Blocks from Tartaric Acid.

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191 Cc; a=556.3(2), b=861.3(3), c=978.5(3) pm, b= 100.56(5)", z = 4 ;
Siemens AED2 four-circle diffractometer; MoKn; data collected at
- 70% 666 unique structure factors, 66 I with F> 3 u ( 0 ; R = 0.028,
R,,=0.025. Further details of the crystal structure investigation may be
obtained from the Fachinformationszentrum Energie, Physik, Mathematik GmbH, D-75I4 Eggenstein-Leopoldshafen 2 (FRG), on quoting
the depository number CSD-52047, the names of the authors, and the
journal citation.
[lo] T. E. Mallouk, B. Desbat, N. Bartlett, lnorg. Chem. 23 (1984) 3160.
[ I I] A. D. Walsh, J . Chem. Soc. 1953, 2266.
[I21 M. Jansen, K. M. Tobias, H. Willner, Naturwissenschuften. in press.
I
Optically Active Cyclopentanediol Synthetic Building
Blocks from Tartaric Acid
Fig. I.Stereoview of the crystal structure of C120h.CII as well as 01 and 0 2
belong to CIO ;, C12 and 0 3 - 0 6 to CIO;. Selected bond lengths [pm] and
bond angles ["I: CII-01 140.6(2), CII-02 141.0(2), C12-03 146.7(2), (212.04
143.0(2), C12-05 145.7(3), C12-06 141.7(3); 01-C11-02 I18.9(3), 0-C12-0
108.0- 110.8.
bly reduced. Since one electron is removed from an antibonding orbital in going from ClO, to ClO:, a shortening of the C l - 0 bond length would be expected, although
not by this amount (Fig. 1). On the other hand, the widening of the bond angle relative to that in ClO,--likewise expectedi1'I-is small (1.2"). The average of the bond lengths
in the C10; ion (144.2 pm) is in agreement with expectations; however, the deviation of the individual values lies
significantly above the experimental error. An association
of cations and anions is suggested by the observation that
precisely those oxygen atoms that have the smaller intermolecular distances to the chlorine atom in ClO: (250
and 251 pm) also have the (significantly) larger C1-0 distances in the C10, ion (146 and 145 pm). T h i s certainly
weak interaction cannot be viewed as a precursor for symmetrically p-0x0-bridged dimers since each cation is linked
with two anions (and vice versa) to form polymeric
chains.
Since C1,06 undergoes sublimation, a transport as the
ion pair ClO:ClO,
is unlikely, and a molecular monomeric or dimeric structure is therefore expected for gaseous CI,O,. In fact, we found that a mixed anhydride of
the chloric and perchloric acid is present in the gas
phase."']
Received: June 26, 1986 [Z 1831 IE]
German version: Angew. Chem. 98 (1986) 994
[ I ] a) M. Schmeisser, K. Brandle, Adu. Inorg. Chem. Radiochem. 5 (1963)
41; b) 0. H. Ellestad, T. Woldbaek, A. Kjekshus, P. Kleboe, K. Selte,
A d a Chem. Scand. A35 (1981) 155; K. Selte, A. Kjekshus, ibid. 22 (1968)
3309; J.-L. Pascal, A. C. Pavia, J. Potier, M. A. Potier, C. R. Acad. Sci.
279 (1974) 43; J.-L. Pascal, A. C. Pavia, J. Potier, ibid. 282 (1976) 53;
JLL. Pascal, J. Potier, J. Chem. Soc. Chem. Commun. 1973. 446; C .
Campbell, J. P. M. Jones, J . J. Turner, Chem. Commun. 1968, 888: R. C .
Loupec, J. Potier, J . Chim. Phys. Phys.-Chim. Biol. 80 (1983) 449.
[2] K. Selte, A. Kjekshus, Acta Chem. Scand. 24 (1970) 1912.
[3] C. F. Goodeve, F. A. Todd, Nature (London) 132 (1933) 514.
[4] JLL. Pascal, A. C. Pavia, J. Potier, J. M. Beny, B. Sombet, Proc. lnt.
Conf. Ramun Spectrosc. 6th. 2 (1978) 54.
[S] A. C . Pavia, J.-L. Pascal, A. Potier, C. R. Acad. Sci. 272 (1971) 1495.
[61 J:L. Pascal, J. Potier, C. S. Zhang, J . Chem SOC.Dalron Trans. 2 1985.
291; C. R . Acad. Sci. 298 (1984) 579.
I71 Caution! C1206 reacts explosively with organic substances.
[S] M. Bodenstein, P. Haneck, E. Padlet, 2. Anorg. ANg. Chem. 147 (1925)
233.
0 VCH Veriagsgesellscha~mbH, 0-6940 Weinheim. 1986
Optically active hydroxylated cyclopentanes are of general interest as building blocks for the synthesis of cyclopentanoid natural products."] We report here a route to enantiomerically pure cyclopentanediol derivatives starting
from tartaric acid (Scheme 1).
\
OCH3
0
gy+
OCHs
9
CAS Registry number:
ClzOa, 104834-96-0.
994
By Hans Jurgen Bestmann* and 7'homas Moenius
Dedicated to Professor Vfadimir Prelog
on the occasion of his 80th birthday
R
nu
P
k q -OC H3
OH
10
11
'OCH~
( R ,R ) - 1 2
( S ,S ) - 12
13
Scheme I . a) I . NaH, 2. CISiMe,, 95% yield of 2 , [a]" -53.7" (THF, c=0.5
g/ I00 mL), b.p. =65"C/O.O5 torr. h) Elimination of Me,SiOSiMe,, 56% yield
of 5, [aln -59.0" (methanol, c=O.5 g/IOO mL), m.p.=121"C. c) 56% yield
(based on 5) of 6 , [ale +50.0° (methanol, c-0.5 g/IOO mL), m.p.=91"C.
d ) He. e) NalCOI.
[*] Prof. Dr. H. J. Bestmann, Dr. T. Moenius
Institut fur Organkche Chemie der Universitat Erlangen-Niirnherg
Henkestrasse 42, D-8520 Erlangen (FRG)
0570-0833/86/1I 1 1-0994 $ 02.50/0
Angew. Chem. Inr. Ed. Engl. 25 (1986) No. I 1
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acid, synthetic, block, optically, activ, cyclopentanediyl, building, tartaric
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