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Gas Chromatographic Separation of Enantiomeric Olefins.

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be expected in the second case. The structure of the host
molecules remains virtually unchanged during the adduct
formation.
[IS] F. Diederich, K. Dick, J . Am. Chem. Sac. 106 (1984) 8024.
I191 A discussion of the individual values is not possible because of the inaccuracy of the method. Cf. M. A. Petti, T. J. Shepodd, D. A. Dougherty,
Tetrahedron Lett. 27 (1986) 807.
I201 A slightly modified version o f the apparatus originally developed for
enantiomeric separations was used: V. Prelog, M. Dumic, Helv. Chim.
Actu 69 (1986) 5 .
[21] A. Xenakis, C. Tondre, J. Phys. Chem. 87 (1983) 4737.
1221 A. J. Blacker, J. Jazwinski, J.-M. Lehn, F. X. Wilhelm, J. Chem. Sac.
Chem. Commun. 1986, 1035.
[23] MM2 program: N. L. Allinger, J. Am. Chem. Sac. 55 (1977) 8127. The
distances are referred to the atomic centers.
[24] F. Vogtle, W. M. Miiller, U. Werner, H. W. Losensky, Angew. Chem. 99
(1987) 930; Angew. Chem. I n t . Ed. Engl. 26 (1987) 901.
1251 J. F. Stoddart, N. Spencer, M. V. Reddington, D. J. Williams, A. M. Z .
Slawin, B. Odell, Angew. Chem. 100 (1988) 1605; Angew. Chem. Inr. Ed.
Engl. 27(1988) 1547; J. F. Stoddart, P. R. Ashton, M. V. Reddington, D.
1. Williams, A. M. 2. Slawin, B. Odell, &id. 100 (1988) 1608 and 27
(1988) 1550.
Gas Chromatographic Separation of Enantiomeric
Olefins**
By Jens Ehlers, Wilfried A . Konig,* Sabine Lutz,
Gerhard Wenz, and Heindirk tom Dieck*
Dedicated to Professor Hans Bock
on the occasion of his 60th birthday
Fig. 1. Top: Space-filling model (SCHAKAL program) according to the optimized geometries [23] of the host-guest molecule 2c .pyrene. Bottom:
Space-filling model (SCHAKAL program) according to the optimized geometries 1231 of the host-guest molecule Id .pyrene.
The examples given here show that arenes are bound by
cationic hosts when these are stabilized in the sandwichlike structure of the host-guest complex by strong EDA
and/or C T interactions and the otherwise usual factors. It
is then unnecessary for the host cavity to be completely
enveloped and the charge centers to lie o n the periphery.[2,31As reported in the preceding communications, J . F.
Stoddart et al. have synthesized a tetracation of type 1
with two p-xylylene bridges by the method described here
and have characterized host-guest compounds containing
dimethoxybenzene~.‘~’~
The enantiomeric excess in catalytic reactions of olefinic
substrates is often very difficult to determine, because mixtures of substances can form and the optical rotations of
many compounds are not known. Since, in addition, the
synthesis of diastereomers frequently poses problems, the
enantioselectivity in some cases cannot be determined at
all or only with great difficulty.
We were able to show that optically active 1,4-diaza-1,3dienes (dad = R’N=CR’-CR”= NR2) in catalytically active fragments “(dad)Fe” catalyze the enantioselective coupling of dienes to give cyclodimers.[” The reaction of
ethene with 1,3-dienes and norbornadiene may also be
achieved under mild conditions. For example, (Z)-3-methyI-1,4-hexadiene 1 is obtained by reaction of (E)-1,3pentadiene and ethene. Similary, norbornadiene gives
endo-3-vinylnortricyclane2, which has also been obtained
with cobalt catalysts.[’] By using chiral dad cocatalysts, op-
Received: July 15, 1988 [Z 2863 IE]
German version: Angew. Chem. 100 (1988) I61 I
[I] Review: F. P. Schmidtchen, Nachr. Chem. Tech. Lab. 36 (1988) 8.
[2] Review: F. Vogtle, H.-G. Lohr, J. Franke, D. Worsch, Angew. Chem. 57
(1985) 721; Angew. Chem. Int. Ed. Engl. 24 (1985) 127.
[3] Review: F. Diederich, Angew. Chem. 100 (1988) 372; Angew. Chem. I n t .
Ed. Engl. 27 (1988) 362.
[4] C. Tanford, Science Washington 200 (1978) 1012.
[5] J. F. Stoddart, Pure Appl. Chem. 60 (1988) 467, and earlier publications.
[6] A. Ledwith, H. J. Woods, J. Chem. SOC.Chem. Commun. 1970, 1422.
[7] B. G. White, Trans. Faraduy Soc. 65 (1969) 2000.
[8] W. Geuder, S . Hiinig, A. Suchy, Tetrahedron 42 (1986) 1665; Angew.
Chem. 55 (1983) 501; Angew. Chem. In!. Ed. Engl. 22 (1983) 489.
191 W. Geuder, Dissertation, Universitat Wiirzburg 1985.
[lo] W.-K. Gries, Dissertation. Universitat Wiirzburg 1987.
[ I l l Whether the increase in yield described by K. Saigo, R.-J. Lin, M. Kubo,
A. Youda, M. Hasegawa ( J . Am. Chem. Sac. 108 (1988) 1996) is to be
considered as a template effect must remain open, since the macrocycle
formed only binds benzene in the lattice in the crystalline state.
[12] IR, UV, ‘H- and ”C-NMR spectra as well as elemental analyses are
consistent with the given structures.
[I31 H:J. Schneider, W. Miiller, D. Giittes, Angew. Chem. 56 (1984) 909; Angew. Chem. Int. Ed. Engl. 23 (1984) 910.
[I41 P. Job, Ann. Chim. Paris 9 (1928) 113; E. Asmus, 2. Anal. Chem. I83
(1961) 321, 401.
[IS] A. J. Blacker, J. Jazwinski, J.-M. Lehn, Helu. Chim. Actu 70 (1987) I .
1161 H. A. Benesi, J. H. Hildebrand, J . Am. Chem. SOC.7 1 (1949) 2703.
[I71 G. Scatchard, Ann. N . Y. Acad. Sci. 51 (1949) 660.
1556
0 VCH Verlagsgesellschaft mbH. 0-6940 Weinheim. I988
c,
1
3
2. X = CH2
4,x=o
5 , X = N-
?
I
[‘I Prof. Dr. H. tom Dieck, DipLChem. J. Ehlers
Institut fur Anorganische und Angewandte Chemie der Universitat
Martin-Luther-King-Platz 6, D-2000 Hamburg 13 (FRG)
Prof. Dr. W. A. Konig, DipLChem. S. Lutz
lnstitut fur Organische Chemie der Universitat
Martin-Luther-King-Platz 6, D-2000 Hamburg 13 (FRG)
Dr. G. Wenz
Max-Planck-Institut fur Polymerforschung
Jakoh-Welder-Weg 11, D-6500 Mainz {FRG)
[**I Diazadienes as Controlling Ligands in Homogeneous Catalysis, Part 16.
Part 15: H. tom Dieck, M. Mallien, R. Diercks, J . Mol. Cat.. in press.
Part 14: M. Mallien, E. T. K. Haupt, H. tom Dieck, Angew. Chem. 100
(1988) 1091; Angew. Chem. In!. Ed. Engl 27 (1988) 1062.
0570-0833/88/1111-1556 $ 02.50/0
Angew. Chem. Inr. Ed. Engl. 27(1588) No. I1
tically active products are obtained. The enantiomeric excess and the configuration of the major isomer were determined for 1 by hydrogenation and comparison of the optical rotation with that of independently synthesized, optically pure 3-methylhexane 3-a relatively involved proced ~ r e . ' ~In- ~the
' case of 2, the vinyl group was transformed
into an aldehyde function (4) by oxidation with rn-chloroperbenzoic acid and cleavage with periodic acid, and the
aldehyde was then converted into the aldehyde-SAMP hydrazone 5.15]The ee value of 5 could be determined from
the OCH, signal in the 'H NMR spectrum.
Konig et al. recently introduced new a-and p-cyclodextrin phases as chiral stationary phases for capillary gas
chromatography16' to separate a variety of enantiomers at
temperatures up to at least 210°C. The enantiomeric separation of the aldehyde 4 was achieved on heptakis(2,3,6tri-0-n-penty1)-13-cyclodextrinas a stationary phase.
Surprisingly, it was also possible to separate easily the
olefins 1 (Fig. 1) and 2 into their enantiomers. The results
(Table 1) are in good agreement with the enantiomeric excesses determined by chemical methods. There have only
been scattered reports on the chromatographic separation
of chiral ole fin^.^']
Table I . Enantiomeric yields and absolute configuration of the major isomer
of catalysis products separated by gas chromatography.
Product
[aslbo [a]
(c [g mL-'I)
ee [Yo]
(configuration)
Controlling ligand [b]
Ph
- 34.8
(0.1)
N-R
- 12.6
HXH
(neat)
R-N'
'N-R
la1 1 in CH2C12, 6 in Et2O. [bl 0-py = 2-pyridyl; R = (lR,ZS,5R)-menthyl.
[c] Not determined.
In further experiments, we were able to show that 3 3 dimethyl- 1,4-hexadiene 6,14] obtained from ethene and 2methyl- 1,3-pentadiene on an optically active catalyst,
could be resolved into enantiomers on this phase (Fig. 1).
Finally, two products of the iron-catalyzed addition of isoprene to norbornadiene (7 and 8) were investigated. The
ex0 adduct 7 is separated (Table I), the 1,6 endo adduct is
(51-1
5
4
3
-t
2
1
0
Lminl
Fig. I. Gas-chromatographic separation of the chiral olefins 1 and 6 (42-m
perpentyl-B-CD column, 25"C, 1 bar HI, head-space injection).
tion of enantioselective homogeneously catalyzed reactions.
Experimental Procedure
1 was obtained from (E)-1,3-pentadiene and ethene in excess (carried out in
a glass ampoule, 50 bar counter pressure in an autoclave) in the presence of I
mol% of "(dad)Fe" [I] at room temperature. 'H NMR (360 MHz, CDCI,):
6=5.75 (dddd), 5.43 (dq), 5.22 (ddq), 4.97 (ddd), 4.89 (ddd), 3.45 (ddq), 1.61
(dd), 1.05 (d). Hydrogenation of 1 on Pd/C gave 3-methylhexane 3. Optically pure (R)-(-)-3-methylhexane was obtained from (S)-(-)-citronello1 by
a similar procedure to that in 131: it was transformed into the olefin by tosylation and LiAIH4 reduction. (S)-4-Methylhexanal, obtained by oxidation of
this olefin with m-chloroperbenzoic acid and cleavage with periodic acid,
was reduced to ( R ) - ( - ) - 3 by Wolff-Kishner reduction: [a]b=-6.8 (c=O.I
in Et20) [4]. From the gas-chromatographic separation and the ee value of 1,
we calculated a value of +6.5 for ( S ) - ( + ) - 3 (c=O.I in CHzCI,).
2 : Synthesized from norbornadiene and ethene in analogy to 1. "C NMR
(90.5MHz,CDCI,):6=139.33, 114.46,48.28,34.29,34.17,29.13, 14.19, 11.28,
9.54. MS (70 ev): m / z 120 (23%, M"), 105 (SO), 92 (100). 91 (96), 79 (89). 77
(49), 66 (68).
4 : IR: V = 1760 c m - ' (C=O); 'H NMR (360 MHz, CDCI,): 6=9.64 ('J=2.3
93 (57), 91 (97), 79 (25), 78 (74),
Hz, CHO). MS (70 ev): m / z 122 (25%, Ma),
77 (loo), 66 (38). Isothermal gas-chromatographic separation at 50°C (in
CH2C12).
5 : Synthesis from 4 following the procedure in IS]. ' H NMR (360 MHz,
CDCI3): 6=3.394, 3.390 (OCH,). MS (70 eV): m / z 234 (3%. M"), 189 (loo),
118 (21). 93 (161, 91 (32), 77 (20), 70 (30). ee from the NMR spectrum 20°/0.
6 : Synthesis from 2-methyl-1,3-pentadienein analogy to 1. "C NMR (90.5
MHz, CDC1,): 6 = 149.4, 130.9, 128.6, 1 1 1.7, 36.5, 25.7, 20.6, 17.8. 'H NMR
(360 MHz, CDCI;): 6=5.76 (ddd), 4.96 (dqq), 4.95 (dd), 4.88 (dd), 3.04 (ddq),
1.69 (d), 1.62 (d), 1.03 (d). MS (70 ev): m / z I10 (36%, M"),95 (IOO), 67 (64),
55 (37), 53 (l4), 41 (37), 39 (29). Synthesis of 7 and 8 from norbornadiene
and isoprene; purification by preparative G C and separation of isodimers.
7: I3C NMR (90.5 MHz, CDC13): 6 = 148.8, 135.8, 135.0, 107.4, 44.4, 44.1,
42.3, 40.6, 40.4, 33.3, 24.9, 20.5. MS (70 ev): m/z 160 (5%, M"), 94 (58), 93
(46), 92 (52), 91 (83), 79 (IOO), 66 (65), 39 (30). Temperature-programmed
gas-chromatographic separation: TO= 50°C. T increase 2"/min, in CH,Cl2,
retention times ca. 26 and 26.2 min.
8 : "C NMR (90.5 MHz, CDCI,): 6 = 134.9, 121.4, 41.2, 40.9, 40.6, 35.4, 29.7,
27.5, 13.7, 10.6. MS (70 ev): m / z 160 (16%, Ma),94 (30), 91 ( 5 2 ) , 81 (23). 80
(loo), 79 (71), 77 (29), 39 (29).
Received: July 1, 1988 [Z 2840 IE]
German version: Angew. Chem. 100 (1988) 1614
CAS Registry numbers:
( k ) - l , 117310-08-4; (S)-1, 117406-02-7; (k)-Z, 117310-11-9; ( + - ) - 6 ,11731009-5; (9-6, 117406-03-8; (+)-7, 117310-10-8; (k)-S, 117310-12-0; heptakis(2,3,6-tri-o-n-pentyl)-B-cyclodextrin,
1 17340-78-0.
f
6
7
8
not. The latter finding might be due to the spherical shape
of the molecule or the absence of a sterically easily accessible double bond.
The possibility of separating many chiral olefins by gas
chromatography will undoubtedly encourage the optimizaAngew. Chem. I n t . Ed. Engl. 27 (1988) No. I I
[I] H. tom Dieck, J. Dietrich, Angew. Chem. 97 (1985) 795; Angew. Chem.
Inl. Ed. Engl. 24 (1985) 781; Chem. Ber. 117 (1984) 694.
[2] J. E. Lyons, H. K. Myers, A. Schneider, J . Chem. SOC. Chem. Commun.
1978. 638.
[31 K . Mori, T. Suguro, M. Uchida, Tetrahedron 34 (1978) 31 19.
[4] In P. A. Levene, R. E. Marker, J. Biol. Chem. 91 (1931) 761, a value of
[a]b2=3.67 was given for (S)-(+)-3 and adjusted to 9.9 by a presumably
false comparison. For (9-(
+)-2,4-dimethylhexane, the hydrogenation
0 VCH Verlagsgesellschaft mbH, 0-6940 Weinheim. 1988
0570-0833/88/1111-1557 $ 02.50/0
I557
product of 6, a value of [a]&'=21.3 (homogeneous) was given. By means
of a chiral catalysis, gas-chromatographic ee determination, and hydrogenation, the R / S sequence shown in Figure I can be assigned to 6. [a]::
of the hydrogenation product was determined to be + I 9 3 (c=O.15 in
CH2C12).
[51 D. Enders, H. Kipphardt, Nachr. Chem. Tech. Lab. 33 (1985) 882.
[6] W. A. Konig, S. Lutz, G . Wenz, Angew. Chem. 100 (1988) 989; Angew.
Chem. Int. Ed. Engl 27 (1988) 979; W. A. Konig, S. Lutz. G. Wenz, E.
van der Bey, J. High Resolut. Chromatogr. Chromatogr. Commun. I 1
(1988) 506; W. A. Konig, S . Lutz, C. Colberg, N. Schmidt, G. Wenz, E.
von der Bey, A. Mosandl, C. Gunther, A. Kustermann, ibid. I1 (1988), in
press.
[7] Gas-chromatographic separation on a chiral Rh complex: V. Schurig, Angew. Chem. 89 (1977) 113; Angew. Chem. I n t . Ed. Engl. 16 (1977) 110;
gas-chromatographic separation of e.g. a-pinene on methylated cyclodextrin phases: T. Koscielski, D. Sybilska, S. Belniak, J. Jurczak, Chromatographia 21 (1986) 413; V. Schurig, H:P. Novotny, J. Chromatogr. 441
(1988) 155; liquid chromatographic separation on Pt complexes: M.
Goldmann, Z. Kustanovich, A. Tishbee, E. Gil-Av, Vth Int. Symp. Column
Liquid Chromatogr. (Avignon, May 1981); J. Kohler, G. Schomburg,
Chromafographia 14 (1981) 559; J . Chromatogr. 25s (1983) 311.
-
One of the results (B, E) of the IGOR 2 analysis of R, the
reaction 1 2 3, corresponds to the unique basic reactionf3]4 5 + 6 .
+
+
COOMe
1
2
3
4
5
6
The homopyrrole 1 was already found to be a suitable
homodiene component in cycl~additions.[*.~~
Tropone 2
was chosen as triene component. On attempting to obtain
3 by reaction of 1 with 2, however, 7 was formed (as racemate), as follows from the NMR data (Table 1) and the
X-ray structure
All C atoms of the cage molecule 7 are constitutionally non-equivalent.["]
Reaction of Tropone with a Homopyrrole. The
Result of a Computer-Assisted Search for Unique
Chemical Reactions**
By Dietmar Forstmeyer, Johannes Bauer, Eric Fontain.
Rainer Herges, Rudolf Herrmann, and Iuar Ugi*
Dedicated to Professor Heinrich Noth
on the occasion of his 60th birthday
COOMe
The computer-assisted discovery of novel molecules and
reactions is especially challenging with regard to the use of
computers in chemistry. The computer program IGOR (Interactive Generation of Organic Reactions) first described
by Bauer and Ugi in 1982"l is based o n the theory of B/E
and R matrices (the matrices B and E describe the chemical constitution of starting materials and products, respectively; the matrix R corresponds to the electron shift
scheme of the reaction)['] and can generate any desired
molecules and chemical reactions with a reaction generaFrom the theory of the B/E and R matrices a hierarchical classification of chemical reactions can also be derivedJsl which enables the degree of novelty of a unique
reaction to be d e t e r ~ n i n e d . ~ ~In. ' ~the search for reactions
with a high degree of novelty the irreducible matrix R&
of the resonance of lO.n,-arenes was incorporated into
IGOR2, a modified PC-adaptable FORTRAN 77 version
of IGOR.
' 0 - 1
0
0
0
0
0
0
0
1
-1
0
1
0
0
0
0
0
0
0
0
I
0 - 1
0
0
0
0
0
0
0
0 - 1
0
1
0
0
0
0
0
0
0
1 0 - 1
0
0
0
0
0
0 - 1
0
1
0
0
0
0
0
0
0
0
0
0
0
1
0 - 1
0
0
0
0
0
0
0
0 - 1
0
1
0
0
0
0
0
1 0 - 1
0
0
0
, I
0
0
0
0
0
0
0 - 1
0
Table I. NMR spectroscopic and mass spectrometric data of 7.
'H NMR [a] (CDCI,, 360 MHz, TMS): 6= 1.92 (s, 2H; H'"), 2.18 (m, 1 H:
HI'), 2.95 (m. 1 H ; HI), 3.05 (m,1 H; H'), 3.15 (m. 1 H; H5), 3.23 (m, 1 H ; H'),
3.45 (m, 1 H; H4), 3.65 (s, 3 H; OCH,), 4.77 (m. 1 H; H'), 4.88 (m, 1 H; H9),
6.15 (t, 1 H, J13.12=7.9 Hz; H13), 6.31 (I, I H , J12,13=7.9 Hz; H12)
''C NMR (CDCI,, 90.56 MHz, TMS): 6=29.56 ( I C), 36.29 (1 C), 38.48 (2C),
45.47 (1 C), 48.18 ( I C), 52.48 (1 C), 56.44 (1 C), 57.17 (1 C), 59.51 (1 C), 130.86
(IC), 132.91 (IC), 153.39 (IC), 207.40 ( I C )
MS (70 eV): m/z 246 (lOO%, Me),214 (9, 154 (3), 138 (3), 107 (I), 80 ( I )
[a] Assignment of signals by means of NOE difference measurements
When 1 and 2 as starting compounds and 7 as product
are fed into the recently implemented program
a reaction network is obtained which contains two further
reaction pathways besides that of 1 + 2 + 3 + 7 , namely:
1 + 2 + 8 - 7 and 1 2-9-7. The first step in the forma-
+
COOMe
[*] Prof. Dr. I. Ugi, DipLChem. D. Forstmeyer, Dr. J. Bauer, Dr. E. Fon-
[**I
tain, Dr. R. Herrrnann
Institut fur Organische Chemie der
Technischen Universitat Munchen
Lichtenbergstrasse 4, D-8046 Garching (FRG)
Dr. R. Herges
lnstitut fur Organische Chemie der Universitat
Erlangen-Nurnberg
Henkestrasse 4, D-8520 Erlangen (FRG)
This work was supported by the Deutsche Forschungsgemeinschaft and
the Fonds der Chemischen Industrie.
1558
0 VCH Verlagsgesellschaft mbH, 0.6940 Weinheim. 1988
COOMe
&
9
8
+
tion of 7,however, is probably a n endo-[4 61-addition of
the homodiene 1 to the triene 2 to give 3, since the reactions via 8 and 9 include steps that are forbidden under
thermal conditions.['31
The reason for the relatively high reactivity of 1 as homodiene (compared to other vinylcyclopropane systems)
can be deduced from an analysis of the frontier orbitals
0S70-0833/88/1fll-1558 $. 02.50/0
Angew. Chem. Int. Ed. Engl. 27 (1988) No. I 1
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