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New Bicyclic Ketones and the Stereochemistry of Their Reaction with Carbanions.

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donor and is thus analogous to the previously reported
(dppe = Ph2P(CHJ2PPh2).I21
Experimental procedure
5 : A solution of 2 (1.30 g, 5.0 mmol) in acetonitrile (40 mL) was allowed to
react at 20°C with Ph3P (1.30g. 5.0 mmol). After 16 h, the volume was reduced to 10 mL and diethyl ether (30 mL) was added to give a yellow precipitate. This was collected by filtration, washed with ether, and suspended in
ethanol (50 mL). Upon addition of 1 (0.50 mL, 5.0 mmol), the mixture turned
deep red. After 1 h, the volume was reduced to 25 mL and water ( 5 mL) was
added to precipitate the orange product 5 . Yield 1.65 g (65%). decomp. p.
6 , 7: 6 (SO%, m.p.=90"C (decomp.)) and 7 (70%. m.p.=103-105"C (decamp.)) were obtained analogously.
8 : A solution of W(CO)6 (0.46 g, 1.30 mmol) in T H F (100 mL) was irradiated
until 1 equiv. of CO was liberated. After addition of 7 (0.64 g, 1.20 mmol),
the volume was reduced to 5 mL and hexane (15 mL) was added to precipitate 8 as a yellow-orange powder. Yield 0.68 g (66%), m.p.= 107-1 10°C (de-
sient associative interaction of the organometallic compound with the ethylene or benzene rc-system can result in
a diastereoselective addition. We have directed our attendid
tion to the ketones 2 and 3 since the results for
not provide a clear picture. We describe here a remarkably
simple preparation of the new ketones 2b and 3 (Table 1)
and report on the stereochemistry of their reaction with organometallic compounds.
[I] W. A. Schenk, T. Schwietzke, H. Muller, J. Organomet. Chem. 232 (1982)
121 W. A. Schenk, T. Schwietzke, Organometallics 2 (1983) 1905.
[3] R. G. W. Gingerich, R. J. Angelici, J. Organomet. Chem. 132 (1977) 377;
W. E. Buhro, A. T. Patton, C. E. Strouse, J. A. Gladysz, F. B. McCormick,
M. C. Etter, J. Am. Chem. Sac. 105 (1983) 1056; M. Herberhold, W. Ehrenreich, W. Biihlmeier, Angew. Chem. 95 (1983) 332; Angew. Chem. Int.
Ed. Engl. 22 (1983) 315; H. Werner, W. Paul, ibid. 96 (1984) 68 and 23
(1984) 58; H. Werner, L. Hofmann, J. Wolf, G. Muller, J. Organomet.
Chem. 280 (1985) C55.
[4] T. J. Collins, W. R. Roper, J. Chem. Soc. Chem. Commun. 1977, 901; L.
Hofmann, H. Werner, J. Organomet. Chem. 255 (1983) C41; W. Paul, H.
Werner, Angew. Chem. 95 (1983) 333; Angew. Chem. Int. Ed. Engl. 22
(1983) 316; Angew. Chem. Suppl. 1983. 396.
[5] M. Pasquali, P. Leoni, C. Floriani, A. Chiesi-Villa, C. Guastini, Inorg.
Chem. 22 (1983) 841.
[6] See, e.g., F. A. Cotton, F. Zingales, Inorg. Chem. I(1962) 145; S. C. Tripathi, S. C. Srivastava, R. D. Pandey, J. Inorg. Nucl. Chem. 35 (1973) 457;
D. DeFilippo, A. Lai, E. F. Trogu, G. Verani, G. Preti, ibid. 36 (1974) 73;
E . Lindner, W. Nagel, Z. Narurforsch. 8 3 2 (1977) 11 16; H. tom Dieck, M.
Form, 2. Anorg. Allg. Chem. 515 (1984) 19.
[7] Binuclear complexes with RC(S)SR' bridges: A. Benoit, J. Y. LeMarouille, C. Mahe, H. Patin, J. Organomet. Chem. 218 (1981) C67; D. Seyferth, G. B. Womack, L. C. Song, M. Cowie, B. W. Hames, Organomefallics 2 (1983) 928; G. J. Kruger, L. Linford, H. G. Raubenheimer, A. A.
Chalmers, J. Organomet. Chem. 262 (1984) 69.
(81 G. Dauphin, A. Cuer, Org. Magn. Reson. I2 (1979) 557.
[9] D. Touchard, P. H. Dixneuf, R. D. Adams, B. E. Segmiiller, Organometallics 3 (1984) 640; J. Amaudrut, A. Kadmiri, J. Sala-Pala, J. E. Guerchais,
J. Organornet. Chem. 266 (1984) 53.
b: n = 3
c: n = 4
9 : A solution of 7 (1.44 g, 2.70 mmol) in acetone (20 mL) was treated at 20°C
with methyl iodide (1.0 mL, 16.0 mmol). After 24 h, the solution was filtered
and evaporated to 2 mL. Upon addition of diethyl ether (10 mL), 9 separated
as a yellow crystalline powder. Yield 0.52 g (29%), m.p. = 1 15-120°C (decamp.).
Received: June 14, 1985;
revised: July 18, 1985 [Z 1352 IE]
German version: Angew. Chem. 97 (1985) 967
a: n = 2
Table I . SDectroscooic data for some of the new comoounds la1
2b: "C-NMR (CDCI,, 20 MHz): 6=217.4 (C-carbonyl), 139.1, 127.5, 122.6
(C-arom.), 52.4 (C-1, C-4), 34.3 (C-5, C-7). 17.4 (C-6); 'H-NMR (CDCI,, 90
MHz):6=7.25 (4H, arom.), 3.37 (2H, m), 2.15-1.90 (4H, m), 1.57-0.78 (2H,
m); IR(KBr): v(C0)=1760 c m - '
3: ' T - N M R (CDC13, 100 MHz): 6=21Y.O (C-9); 140.3, 136.0, 131.5, 127.5,
126.9, 123.7 (C-arom.), 52.2 (C-4, G I ) , 41.1 (C-5, C-8); 'H-NMR (CDC13, 60
(KBr): v(CO)= 1750 c m - ' ; m.p.=153.5"C
12a: "C-NMR (CDC13, 20 MHz): 6= 146.6 (ipso-phenyl), 143.6 (C-2, C-3);
127.7, 126.7, 126.5, 122.5 (C-arom.), 82.0 (C-8), 49.2 (C-1, C-4). 24.5 (C-5,
C-7), 16.7 (C-6); 'H-NMR (CDCI,, 90 MHz): 6=7.4-7.1 (9H, arom.), 3.32
(2H, m), 2.46-2.09 (2H, m), 1.99 (1 H, s), 1.79-1.20 (3H, m), 1.02-0.5 ( I H,
m); m.p.=70"C.
[a] All compounds gave correct elemental analyses.
Our most recent studies of the reductive alkylation of
unsaturated hydrocarbons show[31that the reaction of
dianions with difunctional alkylating agents, e.g., 1,n-dihaloalkanes 4, makes accessible a wide range of new cyHal-(CHJ-Hal
cloannelation and bridged products. In order to synthesize
2, these results suggested the reaction of the dianion 5 ,
prepared by deprotonation of 2-indanone (1. NaH, 1.2
equiv., 0°C ; 2. n-butyllithium, 1 equiv., tetrahydrofuran
(THF), - 78 'C+OoC), with 4 (both 6a and 5 were characterized by NMR spectro~copy~~~).
The central question was
New Bicyclic Ketones and the Stereochemistry of
Their Reaction with Carbanions**
By Petra Baierweck, Detlef Hoe4 and Klaus Miillen*
Dedicated to Professor Rorf C. Schulz on the occasion of
his 65th birthday
Knowledge of the reaction profile of nucleophilic attack
on carbonyl compounds is of great theoretical and practical importance."' If ketones of type 1 or 2 are allowed to
react with carbanions, the question arises whether the tranK.Miillen, DipLChem. P. Baierweck, Dipl.-Chem. D. Hoell
Institut fur Organische Chemie der Universitit
J.-J.-Becher-Weg 18-20, D-6500 Mainz I (FRG)
This work was supported by the Deutsche Forschungsgemeinschaft
6a: R = H
6b: R = - ( c H ~ ) , -Hal
[*] Prof. Dr.
0 VCH Verlagsgesellschaji mbH, 0-6940 Weinheim, 1985
0570-0833/85/111I-O972 $ 02.50/0
Angew. Chem. Ink Ed. Engl. 24 (1985) No. 11
whether the monoanion 6b, obtained by the first alkylation
in the 1-position would tend to react via C-alkylation in
position 3 (product 2), by 0-alkylation (products 7 and 8),
or-after proton migration-by C-alkylation in position 1
(product 9).
We investigated this reaction as a function of the chain
length of the alkylating agent, the halide leaving group,
and the ion-pair structure:[’’
- 1,2-dibromoethane reacts with the dianion of 2-indanone to give solely the spiroannelated product 9a; 1,3dibromopropane affords a mixture of 2b and 8b;I6]1,4dibromobutane gives a complex mixture of products,
which cannot be separated, but in which, according to
NMR, no enol ether is present.
- The ratio of C,C- to C,O-alkylation products (2b/8b) increases in going from dibromo- to diiodopropane (a
“softer” electrophile) from 2 : 1 to 5 :1.
- This product ratio, observed in T H F solution, is increased by addition of hexane and reduced by addition
of hexamethylphosphoric triamide;’” the product ratio
2b/8b is 20 : 1 if THFIhexane (6 : 4) is used as solvent.
Even in dilute solution, considerable amounts of oligomeric products are formed; in a typical experiment (1,3dibromopropane, THF), the yield of 2b/8b is 31%. The
separation of the products is achieved by column chromatography.
The variation of the alkylating agent demonstrates the
limitations of the reaction. a,a’-Dibromo-o-xylene affords
the ketone 3 (18%; side product, dispiro compound 10
(5%)), which is analogous to 2 ; no C,C-alkylation product
is formed with 1,2-bis(~-bromoethyl)benzene.When 1,2-dibromo- I ,2-dihydrobenzocyclobutene is used, an electron
transfer occurs. The trimer 11 is formed as the product of
oxidative coupling.[’]
\ /
The reaction of the ketone 2b with organometallic compounds (phenyllithium, phenylmagnesium bromide, methyllithium) exhibits pronounced diastereoselectivity: in
the alcohol formed, 12, the carbanion has always added
syn to the benzene moiety. The configuration of the alcohol 12a (Table 1) has been confirmed by an X-ray structure determination.[81These results are in marked contrast
to the results obtained for la;[21in the latter case, only a
small amount of diastereoselectivity is observed, which,
moreover, depends on the nature of the organometallic
agent. Attack of phenyllithium on 3 also affords only the
12a: R = Ph
Angew. Chem. Int. Ed. Engl. 24 (1985) No. 11
alcohol in which the phenyl group is syn to the neighboring benzene system.
The newly accessible ketones and alcohols described
here are of further importance for the study of unusual
carbanion structures. For example, the alcohol 12a,
formed from 2b, can be transformed into the corresponding methyl ether. The reductive cleavage of the ether with
lithium leads to the benzyllithium system 13, which exhibits intramolecular “through-space” interaction between
the carbanion moiety and the separated benzene n-systern.”’
Received: June 3, 1985 [Z 1332 IE]
German version: Anyew. Chem. 97 (1985) 959
[I] H. B. Burgi, J. D. Dunitz, E. Shefter, J . A m . Chem. SOC.95 (1973) 5065.
[2] F. R. S. Clark, J . Warkentin, Can. J . Chem. 49 (1971) 2223.
131 W. Huber, W. Irmen, J. Lex, K. Mullen, Tetrahedron Lett. 23 (1982) 3889;
K. Miillen, Pure Appl. Chem.. in press.
[4] 6a (sodium salt, prepared from 2-indanone with sodium hydride): ”CNMR([‘H&THF, - 1O”C, 100 MHz): 6 = 182.2 (C-2); 152.6, 136.0, 126.7,
122.5, 117.8, 114.8 (C-arom.);94.3 (C-3), 42.7 (C-l).-S(’’C) values for 5 ,
see J. B. Lambert, S. M. Wharry, J . A m . Chem. Sac. 104 (1982) 5857.
[S] R. Gompper, H:H. Vogt, H.-U. Wagner, Z . Naturforsch. 8 3 6 (1981)
161 Excess sodium hydride effects the reduction of the non-enolizable ketone
2b to the alcohol.
[7] 11 exhibits stereodynamic behavior (rotation around the inter-ring single
bonds). The NMR signals are consequently broadened by exchange at
room temperature.
[XI P. Baierweck, D. Hoell, J. Lex, K. Mullen, unpublished.
191 P. R. Peoples, J. B. Grutzner, J . A m . Chem. Soc. 102 (1980) 4709; D.
Hoell, J. Lex, K. Mullen, unpublished.
Extensions of the Tricyclooctanone Concept.
A General Principle for the Synthesis of
Linearly and Angularly Annelated Triquinanes
By Martin Demuth* and Werner Hinsken
As an extension of our tricyclooctanone concept[’]for
the synthesis of enantiomerically pure cyclopentanoid natural products, we present here a variant,[‘’ which leads to
target structures that, using the original concept, would be
difficult to obtain. Applying the new strategy, the linear
anti-annelated triquinane skeleton 9I3j and its isomer 15
with angularly joined rings are accessible in only a few
steps.[41They are, in our opinion, suitable precursors for
hirsutene 10 and 5-oxosilphiperfol-6-ene 16, respectiveiY.[51
The light-induced oxadi-n-methane rearrangement of
bridged p,y-unsaturated ketones again serves as the key
step. Instead of constructing this type of chromophore via
a Diels-Alder reaction of 1,3-dienes with ketene equivalents,”] the addition of an acetylene equivalent (e.g., maleic
anhydride) to siloxy-substituted dienes (6 and 12) is
used.[‘] From the adducts (7 and 13, respectively) the photoreactive substrates (8 and 14) are obtained and subsequently undergo triplet-sensitized rearrangement to 9 and
15, respectively. The use of optically active dienes in this
new route is advantageous. Both 6 and 12 are derived
from a compound (1 in Scheme 1) whose enantiomers are
accessible in very good yields and high optical purities.”]
At first, racemic 1 was employed.
The cis-hydrindenone 518](Scheme 1, hirsutene project)
could be prepared in good yield in four steps starting from
the known compound 2 ( 1 -+ 2).19] The cis configuration is
Priv.-Doz. Dr. M. Demuth, W. Hinsken
Max-Planck-lnstitut fur Strahlenchemie
Stiftstrasse 34-36, D-4330 Miilheim a. d. Ruhr (FRG)
0 VCH Veriaysyesellscha~mbH. 0-6940 Weinheim. 1985
05?0-0833/85/1 lIl-09?3 $ 02.50/0
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thein, reaction, bicyclic, ketone, carbanion, new, stereochemistry
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