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Optically Active Tricyclo[6.4.0

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121 J . W Lauher, R. Hojjmunn, J . Am. Chem. Soc. 98, 1729 (1976).
[3] H . J . de Liefde Meijer, M . J . Janssen, G. J . M . van der Kerk, Rec.
Trav. Chim. Pays-Bas 80, 831 (1961).
[4] D. Feitler, G. M . Whitesides, Inorg. Chem. 15, 466 (1976).
151 a) F. H . Kiihler, W Priissdorf; Z . Naturforsch. 8 3 2 , 1026 (1977; b)
Chem. Ber. I 1 1,3464 ( I 978).
[6] J . H . Teuhen, H . J . de Liefde Meijer, J. Organomet. Chem. 17, 87
( I 969).
171 At 243K: cell: a=1142.9(10), b=1595.8(11), c=1585.4(12)pm,
/{= 102.21(9)", V=2826.106pm3, p,,,,=1.17g/cm3; space group P2,/c,
Z = 4 . Syntex P ~ I / X T L20<45",
.
?.=71.069pm (graphite monochromator); 2016 structure factors, F>5.4 ( F o ) , R,=0.092.
[8] a ) Cf., e.q. G. Engebrerson, R. E. Rundlr, J. Am. Chem. Soc. 85, 481
(1963): E. G. Muller, J . L. Pethrson, L. F. Dahl, J. Organomet. Chem.
111, 91 (1976), and references cited therein: b) B. F . Fieselmann, G.
D. Stucky, J. Organomet. Chem. 137, 43 (1977).
191 Cf., e.g. W A . Spoffbrd, P. D. Carfanga, E. L. Amma, Inorg. Chem.
6 , 1553 (1967); R. G. Davits, R. H . B. M a k , P. G . Orston, J. Chem.
SOC. A IY67, 1750; J . L. Atwood, M . Tsutsui, N . El!, A . G. Gebala,
J. Coord. Chem. 5, 209 (1976), and references cited therein.
[lo] The numbers refer to the protons attached to the C atoms shown
in Fig. I . A negative sign of Pa'' denotes a downfield shift; temperature
307 K : the analogous signal of (q5-C5Me4Et)2Fe[4] and of ( 4 ) served
as reference; assignment in accord with [Sb].
208 pm has j u s t been found in
[l I] Nore added in proof: A value of V-C
tetramesitylvanadium - 7: Glowiak, R . Groheln),, B. Jexw.\kaTrzebiatowsk?; G. Kreisel, W Seidel, E . Lrhlig, J. Organornet. Chem. 155,
39 ( I 978).
Optically Active Tricycl0[6.4.0.0~~~]dodecane[**l
By Hartmuth Buding and Hans Musso[*l
Dedicated to Professor Hans Brockmann on the occasion of
his 75th birthday
Chiral molecules not exhibiting measurable rotation are
very rare (for examples see Ref. [ l ,*I). According to the Brewster
rules[31the pure enantiomers of the title compound (5)-(5 a )
and (5h)-ought to be practically optically inactive. It was
therefore of interest to prepare the enantiomers and to demonstrate their chirality.
The dihydroxydiketone (1), recently shown to be readily
accessible from furanophaneL4],has the desired skeleton. The
reaction of ( I ) with (-)-(R)-2,3-b~tanedithiol[~]
affords a mixture of the diastereomeric dithioacetals ( 2 ) , which could be
separated on silica gel using carbon tetrachloride/acetone (6: 1).
The first eluted ( 2 a ) (m.p. 99-101 "C) is clearly distinguishable from the more polar ( 2 b ) (m.p. 146-147°C) by 'HNMR. In the presence of EU(DPM)~
a mutual contamination
of > O S % can be ruled out from the signals of the methyl
groups. Boiling of ( 2 a ) and ( 2 b ) with Raney nickel in methanol affords the alcohols (3) (m.p. 219-220°C) in 60%
yield, which are converted by Olah's method['] into the bromides ( 4 ) (m. p. 149-150°C) in 64 % yield. Dehalogenation
is accomplished either with LiAlH4 in dioxane or with tributyltin hydride (neat) to give the enantiomeric hydrocarbons ( 5 a )
and ( 5 b ) in 64 % yield (m. p. 47.5-49.O"C) and having easily
measurable optical rotations. A partial racemization was to
be feared only in the transition ( 3 ) - ( 4 ) ; the dibromides
( 4 ) obtained at 0°C and +25"C gave practically the same
[a]-values. Neither the 'H-NMR nor the mass spectrum
revealed any olefinic contamination of ( 5 ) , which proved
to be > 99.6 % pure on VPC. The 13C-NMR spectrum (CDC13)
[*I Dip1.-Chem. H. Buding, Prof. Dr. H. Musso
Institut fur Organische Chemie der Universitat
Richard-Willstatter-Allee 2, D-7500 Karlsruhe (Germany)
[**I We thank Prof. Dr. G. Snatzke, Bochum, for recording the CD spectra
and valuable discussions. We are also indebted t o Prof. G. Pfeiderer and
Dr. E. Pauly, Stuttgart, for measuring the O R D spectra.-This work was
supported by the Fonds der Chemischen Industrie and by BASF AG.
Angew. Chem. l n t . Ed. Engl. 17 (1978) No. 11
(31, R = OH
(4), R = Br
(5). R = H
(1)
(2)
(3)
(4)
(5)
-.
-69.9"
-49.6"
-38.8"
-30.0"
. ~.
-103.W+5.0 (c=O.12, dioxane)
+ 84.4Of0.4 (c=0.52, CHCI3)
49.Wf0.4 (c=2.02, CH3OH)
38.Wk0.4 (c=2.04, CHC13)
+ 27.0" k2.0 (c=0.23, cyclohexane)
+
+
~~
~
~
is consistent with the structure (5) [6=21.1 (t), 27.8 (t), 32.3
(t), 34.2 (d; C-I, C-4), 36.3 (t), 36.7 (d; C-8, C-9)]F7].
The dithioacetal ( 2 b ) afforded some optically active diketone (1 b ) (decomp. pt. 237°C). The interaction of the carbonyl
chromophores raises doubts concerning the validity of the
octant rule in this special case. An X-ray structure analysis
on (I)["] has shown that all three cyclohexane rings exist
in slightly twisted chair conformations. This has also been
demonstrated by EFF calculations[s1for the minimum energy
conformation of the hydrocarbon ( 5 ) , and this might be the
reason for the unexpectedly high optical rotation.-The determination of the absolute configuration is being attempted.
Received: September 8, 1978 [Z 76 IE]
German version: Angew. Chem. YO. 899 (1978)
CAS Registry numbers:
( I ) , 68122-42-9: ( 2 a ) , 68122-43-0; ( 2 b ) , 68170-32-1; ( 3 a ) , 68122-44.1;
( 3 b ) , 68122-45-2; ( 4 a ) , 68122-46-3; ( 4 b ) , 68122-47-4; ( S a ) , 68122-48-5;
( 5 b ) , 68122-49-6; (-)-(R)-2,3-butanedithiol, 68 170-33-2
H . Wynberg, G. L. Hekkert, J . P. M . Houbiers, H . W Bosch, J . Am.
Chem. SOC.87, 2635 (1965).
M . Bloch, N . Luu, H . Musso, U . 1. Zdhorszky, Chem. Ber. 105, 1790
(1972).
J . H . Brewster, Tetrahedron 13, 106 (1961); J. Am. Chem. SOC. 81,
5475, 5483, 5493 (1959).
H:G. Fritz, H . H m k e , H . Musso, Chem. Ber. 107, 3164 (1974).
(+)-(S)-2,3-Butanediol, which is available from (+)-(R)-tartaric acid ( J .
J . Plattner, H . Rapoport, J . Am. Chem. Soc. 93,1758 (1971)) was converted
into (-)-(R)-2,3-butanedithiol analogously t o the method described by
E. J . Carey, R. B. Mitra, J. Am. Chem. Soc. 84, 2938 (1962).
G. Olah, J . Welch, Synthesis 1974, 653.
Correct elemental analyses and spectra were obtained for all the new
compounds.
Empirical force field or molecule-mechanistics calculations by E. Osawa,
K . Aiqanii, E Inamoto, J . Chem. SOC. Perkin Trans. 2 (1978), in press.
Template Reactions on Chromium(0): Synthesis of a
Functionalized Indene from Pentacarbonyl[methoxy(phenyl)carbene]chromium and Bis(diethy1amino)acetylene['1
By Karl-Heinz Dotz and Dietmar Neugebauer"]
Dedicated to Professor E. 0. Fischer on the occasion
qf his 60th birthday
Carbene complexes of the type (CO)5MCR1R2react with
nucleophilic alkynes such as ynamines and ynediamines at
[*] Dr. K. H. Dotz, D. Neugebaner
Anorganisch-chemisches lnstitut der Technischen Universitat Miinchen
Lichtenbergstrasse 4, D-8046 Garching (Germany)
851
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