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Enantioselective Syntheses of Cyclopentanoid Compounds from Isoprene and trans-1 3-Pentadiene.

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P. Pino. F. Piacenti, M. Bianchi in Organic Synthesis aiu Metal Curbou?l.i
fiil. I / (Eds.: I. Wender, P. Pino), Wiley, New York. 1977, pp. 43-296.
B. Cornils in New Swtheses with Carbon Monoxide (Ed.: .I. Falbe),
Springer. New York. 1980. pp. 1-225.
L. Markb. J Organornet. Chem. 1991, 404. 325; and references therein.
G. Consiglio. M. Marchetti, Cliimiu 1976, 30, 26.
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352; Angiw. Cliem. Int. Ed. Engl. 1968, 7 , 329.
I;or related considerations in another field ofinsertion polymerization, i.e.
in Ziegler-Natta catalysis, see: P. Pino, R. Miihlhaupt, Angew. Chem
1980, 92, 869; Angew. Chrm. Int. Ed. Engl. 1980, 19. 857.
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A. M. van Broekhoven, M. J. Doyle. J. Orgunomet. Chem.
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Cifrhindutigen.3rd ed.. Springer. Berlin, 1986.
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For enantiofxial selection in the carbonylation of olefins see: G. Consiglio. P. Pino, Top. Curr. Chem. 1982,105.77; G. Consiglio, P. Pino, Adv.
C ' h t w i . Scr. 1982, 77. 371.
A. Van Doorn, P. K. Wong, 0. Sudmeier. Eur. Put. Appl. 1989.376364
[Chwi. Ahvtr. 1991, 114, 247971.
P. W. N. M , van Leeuwen, C. F. Roobeek, P. K. Wong. Eur. Par. Appl.
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P. A. MacNeil, N. K. Roberts, B. Bosnich, J Am. Chem. Soc. 1981. 103,
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P. Pino. A. Stefani, G. Consiglio in Cutulvsis in Chemistry und Biochemi s c t . ~ Thm?:r
und E.qwrimenrs (Ed. : B. Pullman), Reidel, Dordrecht, 1979,
p. 347.
with precatalyst 1 b obtained from the C , symmetric (1R)menthyl-DADL3Ideliver optically active (-)-I ,7-dimethyl1,5-cyclooctadiene (-)-2 in 89 % yield with up to 61 % ee.
0.5% l b
-ll°C/ 14 d
89% (6l%@
Scheme 1. Enantioselective codimeriaation of isoprene and truns-1.3-pentadiene.
Dimethylcyclooctadiene (DMCOD) 2 isomerizes readily
under acidic conditions to derivatives of bicyclo[3.3.0]octane
(Scheme 2). The cationic intermediate may be captured
stereoselectively by a nucleophile resulting in the endo
product (3-5). Alternatively, elimination or rearrangement/
elimination may provide olefins like 7-9. This elimination is
3a,R= Ac
Jb, R = CHO
3d, R = I
Enantioselective Syntheses of Cyclopentanoid
Compounds from Isoprene and
By Kui.-U. Baldenius, Heindirk tom Dieck,*
Wilfried A . Konig, Detlef Icheln, and Torsten Runge
Dedicated to Professor Carl Heinrich Krauch
on the occasion o f his 60th birthday
Iron complexes with 1,Cdiaza-I ,3-diene (DAD) ligands catalyze the cyclodimerization of simples dienes."' A 1 : 1 mixture
of frun.v-I.3-pentadiene and isoprene, for example, can be
dimerized by 1 a activated with organomagnesium compounds121providing racemic 1,7-dimethyl-I ,5-cyclooctadiene 2 in 88 YOyield (Scheme 1). We have found that reactions
Prof. Dr. H. tom Dieck,L+' Dipl.-Chem. K.-U. Baldenius
Institut fur Anorganische nnd Angewandte Chemie der Universitiit
Martin-Luther-King-Platz 6. D-W-2000 Hamburg 13 (FRG)
Prof. Dr. W A. Konig. DipLChem. D. Icheln. Dipl.-Chem. T. Runge
lnstitut fur Organische Chemie der Universitlt Hamburg
New address:
Gesellschaft Deutscher Chemiker
Postfach 900440, D-W-6000 Frankfurt am Main 60
This research was supported by the Volkswagen-Stlftung. the Dentsche
Forschungsgemeinschaft, and the Fonds der Chemischen Industrie. We
thank Hoechst AG for their gift of chemicals.
Aiigew. Chem Inr. Ed. EngI. 31 119921 No. 3
/ \
55'C I 12 h 150%
20T 120%
Scheme 2. Acid-catalyzed reactions of 2.
always a side reaction and the cause for lowered yields of the
addition product. Inspection of molecular models suggests
that the cationic intermediate has a saddle conformation, in
which the methyl group on the sp3 C atom has a stereodirecting effect due to its preference for the exo position. Diastereomeric side products and racemization do not occur. In
the reaction of 2 with acetic anhydride/BF, . Et,O, the electrophilic action of the acylium ion leads selectively to the
endo-acetyl-endo-acetoxyproduct 4.
.Q VCH Verlu~sgesrIh~huJt
mbH, W-6940 Weinhein], 1992
0570-0833192jO303-03053 3.50+ ,2510
The reaction of (-)-2 (61 % ee) with EtAICI, (20 mol%)
in the presence of bis(2-ethylhexanoato)nickel(I .5 mol YO)
hexane at 60°C furnishes ( - ) - 6 in 50% yield (Scheme 2).
Nickel plays a different role in this isomerization than that
which we had originally assumed :I1
b1 The electron-rich Ni
species present under these reaction conditions probably acts
as a nucleophile; an alkylnickel compound is formed which
undergoes a sterically favorable y elimination leading to the
tricyclic product.
(10). in analogy to 2, is
converted to 11 by treatment with acetic acid/cat. H2S04/
20°C and to 12 with acetic anhydride (Scheme 3); but in
contrast to 2 its reaction with catalytic Ni2+/EtA1C12leads
to C-C bond cleavage and product 13. A Wagner-Meerwein
ready pointed out the importance 1,5-DMCOD 14 and its
derivatives could have in the synthesis of several naturally
occurring triquinanes. Closer examination of the substructures of some of these synthetic targets as well as biologically
interesting compounds with intact eight-membered rings
make 1,7-DMCOD 2 appear to be an attractive starting
material with an already respectable enantiomeric excess.[81
Other COD derivatives, some demonstrating fascinating isonierizations, are accessible by iron cataly~is.~',
In addition our results emphasize the value of derivatized
cyclodextrins (CDs) as stationary G C phases for the analytical control of asymmetric syntheses.['
All the chiral
reaction products in this report could be separated completely into their enantiomers on selectively 0-alkylated p- and
y-CD derivative^"^] in glass or fused silica capillaries.
Experimental Procedure
(-)-2: Isoprene and trans-1.3-pentadiene (dried over LiAIH, and distilled underN,; 11.2 g, 165mmolofedch)werecooledto -4O'CunderN,. Butadienemagnesium-bis(tetrahydr0furan)(260 mg. 1.2 rnmol) was then added followed
by 1 b (380 mg, 0.8 mmol). The reaction mixture was stirred at least 2 h at
- 20 " C .The deep red-brown solution was held at - 17 "C for 14 d. The product
mixture was distilled off at room temperature (RT) under vacuum ( 5
0.05Torr): 22.1 g condensate contained (GC): 90% 1.7-DMCOD 2, 1 2 %
1,4-DMCOD. < 1 % 14 and 16. Product 2 was purified by spinningband distillation to > 9 5 % . [a], - 4 ( c = 4.5, CHCI,), ee = 61 %. Higherreaction temperatures accelerate the reaction but with resulting loss in ee.
ZO"C11 h/52%
Ni2'/ EtAICI, I n-C,H,,
68°C I 2 h 175%
Scheme 3. Isomerizations of 1.2.4-trimethyl-15cyclooctadiene (10).
rearrangement could precede the addition of the Ni nucleophile present in relatively low concentration here, as well in
the reaction to 6. A similar mechanism dependent on the
presence of a nucleophile was formulated by Whitesell et
al.L4I and Haufe et al.[5a1for the acid-catalyzed isomerization
of 1,5-DMCOD 14. The product of the rearrangement/elimination described by Whitesell et al. (15, Scheme 4) is also
accessible from 1,6-DMCOD 16 and in better yields. Diene
16, in turn, may be obtained with high selectivity from the
dimerization of isoprene with DAD-iron
BF3 Et,O I PhH
Received: August 19, 1991 [Z4877IE]
German version: Angew. Chem. 1992, 104, 338
CAS Registry numbers:
Ib, 87226-78-6; 2.138541-38-5; 3a, 138541-39-6; 3b, 138541-40-9;3c, 13854141-0; 3d, 138541-42-1; 4, 138541-43-2; 5, 138541-44-3; 6. 138661-25-3; 7,
35408-34-5; 8, 35408-33-4; 9, 138541-45-4; 10, 115679-01-1; 11, 138541-46-5;
12, 138541-47-6; 13,115679-05-5; 14,3760-14-3; 15,60329-18-2;16,3760-13-2;
1.+DMCOD, 19435-33-7; isoprene, 78-79-5; trans-l,3-pentadiene, 2004-70-8.
80°C I 68%
Scheme 4. Acid-catalyzed isomerizations of 14 and 16.
The very simple approach to differently functionalized
optically active bicyclo[3.3.0]octanes described here should
provide new impetus for the synthesis of cyclopentanoid
compounds. Mehta et a1.16] and Pattenden et al.['] have al306
(-)-3a: Acetic acid (8 mL) was allowed to react with conc. sulfuric acid
(0.1 mL) and (-)-2 (1.55 g, 95% purity, 11 mmol, 56% re). The reaction mixture was stirred 15 h a t RT, then taken up in 2 M NaOH, extracted with hexane,
and dried over sodium sulfate. After the solvent was removed, the product was
distilled (ca. 0.08 Torr. 42 T),Yield: 1.3 g colorless liquid (6.6 mmol, 61 %,
54% ee. [z],, - 82 ( c = 1.6, CDCI,)). According to GC, fourisomenc side products were also present (each less than 2%). The preparations of 3bd and 11
proceeded analogously. Treatment with formic acid did not require additional
catalysis. Reactions with alcohols require higher temperatures (55 "C) and yield
products of lower purity.
(-)-4: A solution of ( - ) - 2 (0.87 g. 90% purity, 5.7 mmol. 56% ee) in acetic
anhydride (7 mL) at - 50 "C was stirred vigorously and BF, . Et,O (7.7 mmol)
was added. The reaction mixture was allowed to stand 10 h at -20°C before
workup with hexaneiNaHC0,. Chromatography (silica gel, hexaneiethyl acetate) provided 0.55 g colorless oil (40 %, [& - 30 (c = 1.7. CDCI,)). The preparation of 12 proceeded analogously.
Q V C f l VerIagsgeseNsch+fimbfl, W-6940 Weinheim. 1992
(11 a) H. tom Dieck, J. Dietrich, Angew. Chem. 1985, 97, 795; Angeiv. Chem.
Znt. Ed. Engl. 1985,24,781;b) M. Mallien, E. T. K. Haupt, H. tom Dieck,
&id. 1988, 100, 1091 and 1988.27, 1062.
[2] Butadienemagnesium has proven to be an effective activator: U. M.
Dzhemilev, A. G. Ibragimov. G. A. Tolstikov, J. Organornet. Chem. 1991,
406, 1 . Preparation see K. Fujita, Y Ohnuma. H. Yasuda, H. Tani, ibid.
1976, 113, 201.
[3] Preparation from (1R)-menthylamine (see 0. Wallach, M. Kuthe, Ann.
Chem. Pharm. 1893, 276, 296) and glyoxal in CH,CI,/NaSO,/cat.
HCOOH at 2 0 T (see H. tom Dieck, J. Dietrich, Chem. Ber. 1984, 117.
694). Recrystallization from cold methanol gives colorless crystals,
m.p. =78"C, [aID-163 (c = 1 , CDCI,).
[4] J. K. Whitesell, R. S. Matthews, P. A. Solomon, Tetrahedron Lett. 1976,
1.51 a) G. Haufe, A. Wolf, K. Schulze, Telrahedron 1986, 42, 1549. b) The
acid-catalyzed cyclization with addition of solvent is known: A. C. Cope,
M. M. Martin, M. A. Kervey, Q . Rev. Chem. Sac. 1966, 20, 119.
[6] G. Mehta. S. K. Rao, J: Am. Chem. Sac. 1986,42,1549,and literature cited
[7] G. Pattenden. S. J. Teague. Tetrahedron Leu. 1984, 25, 3021.
0570-0833/92j0303-0306 $ 3.50+.25/0
Angew. Chem. Int. Ed. Engl. 31 (1992) N o . 3
L. A. Paquette. H.-J. Kang, J. Am. Chem. Soc. 1991, 113.2610, and literature cited therein; L. A. Paquette. Top. Curr. Chem. 1984. 119, l ; ihid.
1979. 79.41; M. Vaudewalle, P. DeClercq, Terrahedron, 1985.41, 1767;M.
Braun. Nadir. Chem. Tech. Lab. 1985, 33, 803.
H. tom Dieck, C . Munz, J. Ehlers in Orgunometallics in Organic Syn/hesis,
Vol. 2 (Eds : H. Werner, G. Erker), Springer, Heidelberg, 1989. pp. 21-43.
[lo] The iron catalysts employed are as sensitive as they are selective and
usually do not tolerate dienes with heteroatom substituents. Other products than the desired ones with eight-membered rings are often produced
due to steric reasons. For example, the reaction of I-vinylcyclopentene
with an excess of isoprene and I c does not lead to the anticipated bicyclo[6.3.0]undecadiene but rather to 4-(l-cyclopentenyl)-2-methylcyclohexene.
1111 a) W. A. Konig. Nuchr. Chem. ETrh. Lab. 1989. 37, 411: b) V. Schurig,
H.-P. Nowotny. Angew. Chem. 1990, 102. 969; Angew. Chem. I n t . Ed.
E@. 1990, 29,939.
[12] J. Ehlers. W. A. Konig, S. Lutz, G. Wenz, H. tom Dieck, Angew. Chem.
1988, 100. 1614: Anger. Chem. I n / . Ed. Engl. 1988, 27, 1556.
[13] W. A. Konig, D. Icheln. T. Runge, I. Pforr, A. Krebs, J. High Rex Chrornuroxr. 1990. 13. 702.
Also [3.3.3]cyclophanetrione 4, synthesized here for
the first time, could be transformed selectively into the hitherto unknown ketones 5 (25 % yield) and 6 (20% yield from
4)1'01 and then finally into the hydrocarbon 7 (31 Yoyield in
relation to 4).['']
Selective Ketone Pyrolysis: New Synthetic Method
for Mono- and Polycyclic Hydrocarbons**
By Jorg Breitenbach, Frank Ott, and Fritz Vogtle*
The interest in polycyclic almost spherical molecular
frameworks has increased, not least, through the results
from the dodecahedrane['I and fullerene area.['] Our goals
are large-cavity cage compounds, which could be isomerized
and dehydrogenated to fullerene-like polycycles and those
which retain guest molecules indefir1ite1y.I~~
In this context,
we searched for synthetic methods for the preparation of
macropolycyclic hydrocarbons. These can be obtained from
the corresponding cyclic sulfones via the loss of sulfur dioxide.r4I However, sparing solubility, high melting points, and
the insufficient volatility of sulfones as well as the sensitivity
of some thiols and sulfides provide difficulties. Also the elimination of heteroatoms from aza-L5I and selenocyclophanesC61does not occur readily. We have now found that
cyclic ketones, via CO loss and C-C bond formation, can be
preparatively ring contracted. As substrates for the development of the synthetic method, we chose cyclophanes which
permit comparisons with the sulfone pyrolysis. The simple
experimental design used there (horizontal, evacuated quartz
tube, two tubular furnaces) also proved to be suitable here.
Optimization of the pyrolysis of the 12-membered ring
showed that the conditions (heat and pyrolysis
temperature, vacuum) can be set to obtain the desired product
(monoketone 2,23 % yield; hydrocarbon 3, 22 YOyield from
2 +
+ 3
[*] Prof. Dr. F. Vogtle, Dipl.-Chem. J. Breitenbach, F. Ott
Institut fur Organische Chemie und Biochemie der Universitat
Gerhard-Domagk-Strasse 1, D-W-5300 Bonn 1 (FRG)
[**I This work was supported by the Deutsche Forschungsgemeinschaft (SFB
Angew. Chem. I n t . Ed. Engl. 31 (1992) N o . 3
In the paracyclophane series this pyrolysis, which only
requires a few minutes, was achieved as before without problems : the [2.2]paracyclophane was obtained from [3.3]para~yclophane-2,12-dione~~~~
at 625 "C in 30% yield; the intermediate monoketone ([3.2]paracyclophane-2-one) could be
obtained in 32% yield at 614"C.['31
Table 1. Physical and spectroscopic data as well as yields of the new compounds 2 - 6 and 8. NMR spectra at 250 MHz ('H) and 50.3 MHz (I3C)measured in CDCI,.
2:Yield23% [8]:m.p. =115-116"C; ' H N M R : 6=1.32(s. 18H:CH3).2.20
(AA, 2H; C H A 3.04 (XX', 2H; CH,), 3.39-3.55 [(AB),, 4H; CH,], 4.98 ( s ,
2H; CH,,,,), 7.10 (s, 4H; CHd,om);MS (70eV): m/z 348.2447 [M'], Cdk.
3: Yield 22% [8]; m.p. =176-178"C; ' H N M R : S = 1.35 (s. 18H; CH,), 2.09
(AA'; 4H; CH,), 3.05 (XX, 4H; CH,), 4.08 (s, 2H: CH,,,,), 7.05 (s, 4H;
CHsra,); MS (70 eV): M / Z 320.2510 [ M + ] calc.
4:Yield7%:FP = 289-291"C:'HNMR:S = 3.77(~,12H;CH,),6.87(~,6H;
MS (70eV): m / z 318.1256 [M+],calc. 318.1386.
5: Yield 25% [lo]; m.p. = 261 "C; 'H N M R : 6 = 3.11 (s, 4H; CH,). 3.68 (s.
8H; CH,), 6.39 (s, br, 4H: CH,,,,), 7.00 (s, br, 2H; CHa,J; MS (70 eV): nijr
290.1308 [Mi], Cdk. 290.1310.
6 : Yield 20% [lo]; m.p. = 210"C, 'H N M R : 6 = 2.88-3.08 (AA'BB. 8H;
CH,), 3.54 (s, 4H; CH,), 5.61 (s, br. 2H: CH,,,,), 6.51 (s, br, 4H; CHa,om);MS
(70eV): mi; 262.1351 [M+], calc. 262.1357.
8 : Yield 10%; m.p. = > 250°C (decomp.); ' H N M R : 6 = 3.82 (s, 12H: CH,),
6.90 (AA, 12H; CHaro,,,),7.08 ( B B , 12H: CH,,,,), 7.29 (s, 6H; CH,,J; MS
(FABI): m/z 775.3 [ M + + HI.
Thus, the ketone pyrolysis offers, besides a method for the
production of the hydrocarbons, the possibility to obtain
hitherto unknown, not easily accessible macrocyclic ketones.
From the available examples, we conclude that the bond
formation, as with the sulfone pyrolysis, occurs to a large
extent intramolecularly. Even though the pyrolysis is a consecutive reaction, in which the intermediate products do not
arise separately, the preferred formation of one of the products can nevertheless be achieved by the selection of the
For the preparation of the ketones, the TosMIC cyclization proved
apart from the good accessibility of the building blocks, the simple procedure, and the
good yields, the ketones obtained can be isolated without
problems and are readily soluble. Starting from the tris(bromomethyl) compounds 9["] and
and toluene-4-sul-
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cyclopentanone, compounds, synthese, enantioselectivity, pentadiene, transp, isoprene
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