Quantum chemical ab-initio calculations (SCF, 3-21G-
920
basis set. experimental geometry), were carried out for 3
and the monoanion 3a, as well as for 1 and its monoanion
l a , in order to ascertain the reason for the markedly differ-
ent acidities of the compounds 1 and 3. The deprotona-
tion energy of 1 was calculated to be 1573 kJ mol-', and
that of 3 to be only 1452 kJ mol-'. This result is under-
standable on the basis of population analyses according to
Mulliken, which show a stronger delocalization of the ad-
ditional electron in the bicyclic 3a than in l a .
The question whether measured structural data (apla-
narity of the bicyclic compound) are to be interpreted as
molecular properties or must be attributed to packing ef-
fects in the crystal, could also be settled by quantum chem-
ical calculations for 3 , the dianion 3b,["] and 8. Compari-
son of a pyramidal and a planar environment for the ni-
trogen atom shows that planarity of the central R2N-NR2
fragment is more favorable for the molecules 3, 3b, and 8 :
the relative stabilities for a planar R2N-NR2 fragment are
+ +
25.3 for 8 (folding angle as in 3), 15.5 for 3 , and 5.9
kJ mol-.' for 3b. Therefore the folding angles observed in
3 and 3b in the crystalline state can be attributed to inter-
molecular interactions and to neighboring cations, respec-
tively.
Experimental
6 : A solution of 4 (30 g, 94.4 mmol) in CHIC12 (50 mL) was cooled to
-60°C i n the absence of moisture in a three-necked flask fitted with a
cooled dropping funnel. I 1 g (155.1 mmol) of chlorine (ca. 7 mL at -60°C)
were condensed into the dropping funnel and added dropwise within I h to
the solution of 4, which turned deep red in color. All volatile components
were then removed under vacuum and the temperature slowly raised to 0 ° C
(great care must be taken here: vigorous evolution of CI2 takes place sponta-
neously at ca. -40°C); 6 separated out thereby in the form of red crystals.
Yield: 14.4 g (89Oh). UV/VIS (CHC13): A,,, [nm]= 522 ( s ) , 542 (s). 564 (s); IR
(CCI,): G(C-H)=2960 (w), 2925 (w) c m - ' , G(C=O)=1765 (vs) c m - ' ,
G(Me,Si)= 1262 (vs), 850 (vs), 725 (m), 688 (m) c m - '
7 : A solution of 6 (14.4g, 84.1 mmol) in CH2C12 (50mL) was treated with
5 mL of D M F and the mixture heated under reflux for 48 h. After removal of
volatile components under vacuum, the pale yellow residue was sublimed at
150°C and 0.01 torr: pure 7 was obtained in the form of colorless needle-
shaped crystals. M.p. 168°C: 4.6 g (34%). Correct elemental analysis.-lR
(KBr): S l c m - ' ] = 2 9 6 0 ( ~ ) , 2 9 1 0 ( v w ) 1780(vs),
, 1430(w), 1300(vs), 1250(s),
I160 (s), 1060 ( s ) , 850 (vs), 780 (s), 765 (m); '9Si-NMR (CDCI,): 6=7.69;
"C-NMR (CDCI,): 6=147.5, - 1.10.
3 : 14.4 g (84 I mmol) of 6 was allowed to stand for 48 h at room temperature
in the presence of atmospheric moisture and then 24 h at 80°C in a dry box:
the color of the substance changed from red to colorless. For purification,
the crude product was recrystallized from 50 mL of water, whereby decom-
position of 3 by hydrolysis could be essentially reduced by heating to not
more than 80°C and rapidly cooling the filtrate to 0°C. Yield: 5.6 g (67%).
Decomp. at 340°C. Correct elemental analysis.-IR (KBr): i. [cm-']=3240
(vs), 2750 (sh), 1780 (vs), 1740 ( s ) , 1480 (w). 1430 (s), 1360 (vs), I180 (s), I168
(s), I133 (s), 945 (w). 745 ( s ) ; "C-NMR ([D6]Me2SO): 6 = 159.79.
Received: November 19, 1987 [Z 2505 I€]
German version: Angew Chem. 100 (1988) 703
CAS Registry numbers:
3, 113893-26-8; 4, 113924-28-0, 6 , 113924-29-1; 7, 113924-30-4.
[ I ] a) 1. E. Herweh, R. M. Fantazier, Tetrahedron Lett. 1973, 2101; b) H.
Wamhoff, G. Kunz, Angew. Chem. 93 (1981) 832; Angew. Chem. Int. Ed.
Engl. 20 (1981) 797.
121 R. Stolle, Chem. Ber. 45 (1912) 273.
131 a ) D. W Borhani, F. D. Greene, J . Org. Chem. 51 (1986) 1563; b) Le H.
Dao, D Mackay, Can. J . Chem. 57 (1979) 2727; c) H. Wamhoff, K.
Wdld. Chem. Ber. 110 (1977) 1699; d) R. F. Smith, S . B. Kaldor, E. D.
Lagania, R. F. Oot, J . Org. Chem. 40 (1975) 1854
141 G. Faleschini, E. Nachbaur. Monath. Chem. I19 f 1988) 457. , I
151 J . Bourdais, F. Cugniet, JLC. Prin, P. Chabrier, Bull. Soc. Chim. Fr 1964,
500.
[61 R. C . H ~ r t ,R. G. Schmitt, Spectrochim. Acra 12 (1958) 127.
[7] Crystal structure data of 3 : monoclinic. P 2 , / c , a=8.2049(4),
~ samples of citronella1 and vetiver oil, and Dr B. Mauerer, Firmenich,
h=5.4172(2), c = 13.2406(8) A, 8=90.28(6)", V=588.5(1)A3, Z = 4 ,
Anqew Chem. I n t . Ed. Engl. 27(1988) No. 5 0 VCH Verlagsgesellschaft mbH. 0-6940 Weinheim. 1988
P ~ . . ~ 1.
, ~ - = g cm-', STOE AED 2 four-circle diffractometer, graphite
monochromator, MoKnrA=0.71073 A, 2H<60", 1725 independent, 1372
significant reflections with F,,>3a(f,,). The structure was solved by di-
rect methods (MULTAN), the hydrogen atoms were refined isotropical-
ly, the remaining atoms anisotropically. R =0.0425, R,. =0.0387 (I372
observables, 118 parameters). Further details of the crystal structure in-
vestigation are available on request from the Director of the Cambridge
Crystallographic Data Center, University Chemical Laboratory, Lens-
field Road, Cambridge CB2 IEW (England). on quoting the names of
the authors, and the journal citation.
[8] G. Fritsch, G. Zinner, D. Mootz, M. Scherf, H. Wunderlich, Arch.
Pharm. (Weinheim, Ger.) 319 (1986) 646.
[9] An analysis of the structural data of 64 urazole derivatives from the
Cambridge Crystallographic Data File gave as mean values for these pa-
A
rameters 1.432 and 105.9" and 110.9". resp.
[lo] H. B. Biirgi, J. D. Dunitz, E. Shefter, Acta Crysrallogr. Sect. 8 3 0 (1974)
1517.
1111 An X-ray structure analysis of the dianion 3b shows that the two best
five-membered ring planes form an angle of 140.3(1)" (F. Belaj, unpub-
lished).
Stereoselective Synthesis of trans- Deca lins
+ via Intramolecular Ene Reactions;
Synthesis of the Enantiomerically Pure
Cadinane-Sesquiterpene Veticadinol**
By Lutz F. Tietze,* Uwe Beifuss, Jochen Antel, and
George M . Sheldrick
The sesquiterpenes of the cadinane or cadalane series
are widely distributed as plant constituents. They are
found, inter alia, in vetiver oil, an important olfactory. The
cadinanes contain 2,8-dimethy1-5-isopropyldecalin1 as
basic structural unit (numbering as in 2). They are classi-
tied into four groups according to the type of annulation
and the position of the isopropyl group: the true cadinanes
(cadinane) and the bulgaranes with trans-fused rings, and
the muurolanes and amorphanes with cis-fused rings."'
on
Few methods are as yet known for the stereoselective
synthesis of both the cis- and the trans-fused ring systems
of the cadinanes.[21In our studies on the synthesis of terpe-
noid natural products we developed a novel stereoselective
entry to the trans-coupled decalin system of the cadinanes
which enabled us to synthesize the sesquiterpene veticadin-
01 2.13]From the retrosynthetic analysis it followed that it
should be possible to synthesize the decalin system of 2 by
two intramolecular cyclizations. The first cyclization is the
intramolecular ene reaction of the alkylidenemalonate 5,Is1
which proceeds with high non-induced and induced dia-
and the second is the cyclization of 11
stereo~electivity,!~~
(Scheme 1). 5 already cyclizes in 92% yield at -78°C in
[*] Prof. Dr. L. F. Tietze, Dr. U. Beifuss
lnstitut fur Organische Chemie der Universitat
Tammannstrasse 2, D-3400 Gottingen (FRG)
DipLChem. J. Antel, Prof. G. M. Sheldrick
lnstilut fur Anorganische Chemie der Universitat
Tammannstrasse 4, D-3400 Gottingen (FRG)
["I This work was supported by the Deutsche Forschungsgemeinschaft and
the Fonds der Chemischen Industrie. We thank Dr. E. 1. Brunke and Dr.
K . G . Fahlbusch, Dragoco Holzminden, for kindly supplying us with
Geneva (Switzerland) for a gift of vetiver oil.
0570-0833/88/0505-0703 $ 02.80/0 703
the presence of FeCI3 on basic aluminum oxide@]to give
the trans-substituted cyclohexanes 7 and 6 in the ratio
98.8 : 1.2 (GC; i-de 97.6%, ni-de >99%). The FeCI3/AI20,
catalyst newly introduced by us for the ene reaction has
great advantages over other Lewis acids in that it is easy to
handle, can be used in catalytic amounts and affords very
good selectivities and high yields. The absence of almost
any side products in the reaction with FeCI3/AI20, is pre-
sumably due in part to the fact that this catalyst acts as a
proton scavanger, similarly to alkylalurninum halides.['I
lows the intramolecular ene reaction furnishes the mono-
ester 8 in 92% yield, which undergoes a Prinz reaction[']
with paraformaldehyde to give the alcohol 9 (81%). For
the intramolecular alkylating cy~lization,['~ 9 is converted
via the tosylate 10 into the iodide 11, which reacts with
lithium diisopropylamide (LDA) in tetrahydrofuran at
-78°C via an intermediary ester enolate to give the de-
calin derivative 12 in 92% yield. The assignment of the
structure of 12 follows from the characteristic resonance at
6=0.87 for an equatorially arranged methyl group, and
from the large coupling constants 3J&H.7.H = 3 J 7 ~ H . x . H = 12
Hz, indicating trans coupling of the rings. The equatorial
position of the methoxycarbonyl group is confirmed by the

H3C02C 'r COZCH3 ' h a H3C02C+

CO2CH-j
coupling pattern of the signals for 5-H,, at 6=2.24 with
coupling constants J = 12.3, 11, and 3.5 HZ.~"]Reaction of
12 with methylmagnesium iodide affords the desired enan-
tiomerically pure veticadinol 2 in 77% yield. In addition,
the methyl ketone 13 is obtained in 12% yield in an incom-
3 I 5 plete reaction, despite the use of a large excess of methyl-
magnesium iodide. Since the citronella1 used for the syn-
II b thesis is obtainable in both the R- as well as S-configura-
t tion, the enantiomer of 2 can also be prepared in the same
way. An X-ray structure analysis was carried out in order
I to establish unequivocally the relative configuration of
2.L' 11
The synthetic sequence presented here not only enabled
1
C02CH3 C02CH3
the stereoselective preparation of the interesting olfactory
veticadinol 2 for the first time,1'21but also provides a gen-
7 6 eral entry to sesquiterpenoid compounds of the decalin
type. Moreover, by variation of the aldehyde employed for
the Knoevenagel condensation in (a) and of the Grignard
reagent in (h), a large variety of compounds of interest for
the perfumery industry can be prepared.
Received: December 2, 1987 [Z 2521 IE]
German version: Angew. Chem. 100 (1988) 739

CAS Registry numbers:

CG2CH3 2, 14107-43-8; 3, 108-59-8; 4, 2385-77-5; 5, 106431-76-9; 6, 106431-82-7: 7,
106431-81-6; 8, 114032-14-3; 9, 114032-15-4; 10, 114032-16-5; 11, 114032-
9 , X = OH 17-6; 12, 114032-18-7; 13, 114129-01-0.

' 10, X z GTs

fL 11, x = I
a) G. Rucker, Angew. Chem. 85 (1973) 895; Angew. Chem. l n t . Ed. Engl.
12 (1973) 793; b) B. M. Fraga, Nut. Prod Rep. 2 (1985) 147; c) B. M.
Fraga, ibid. 3 (1986) 273; d) T. K. Devon, A. 1. Scott: Handbook of Nat-

19 urally Occurring Compounds. Vol. 11, Academic Press, London 1972; e)

. .
{ G
R
OH
2 G. Chiurdoglu, A. Delsernrne, Bull. Soc. Chim. Belg. 70 (1961) 5: Vetica-
Scheme 1. a) Piperidiniurn acetate, CH2C12,20"C/I h, 82%. b) FeCI3/AI2OI,
-78"C/2 h, 2OoC/2 h, 92%. c) HZO, NaCI, Me2S0, 150nC/4 h, 92%. d)
(CH,O)., (CH,),AICI, CH2C12,O"C, 20"C/4 h, 81%. e) TosCI, pyridine, O"C/
I h, 5"C/12 h, 93%. f) Nal, acetone, 20°C/12 h, 95%. g) LDA, THF, - 7 8 ° C
20"C/2 h, 92%. h) CH,MgI, Et20, 20°C/12 h, 37.S°C/12 h, 12% 13,
77% 2, chromatography on silica gel with ethyl acetate/hexane = 1/1.
R,(13)=0.44, R , ( Z ) = O 10.
The alkylidenemalonate 5 needed for the ene reaction is
accessible in 82% yield by condensation of (R)-citronella1
4 with 3.151The demethoxycarbonylatiod8I of 7 which fol-
W. Karrer: Konstiturion und Vorkommen der organischen Pflanzenstoffe.
Birkhauser, Base1 1958, 1977, 1981; f) J. S. Glasby: Encyclopaedia ofthe
Terpenoids. Wiley, Chichester 1982.
I21 a) C. H. Heathcock in J. ApSimon (Ed.): The Total Synthesis of Natural
Products, Vol. 2, Wiley, New York 1973, p. 197; b) C. H. Heathcock, S.
L. Graham, M. C. Pirrung, F. Plavac, C. T. White in J. ApSirnon (Ed.):
The Total Synthesis of Natural Products. Vol. 5. Wiley, New York 1983,
p. 1; c) J. S. Roberts, 1. Bryson, Nut. Prod Rep. I (1984) 105; d) J. S.
Roberts, ibid. 2 (1985) 97; e) M. Vandewalle. P. De Clercq, Tetrahedron
41 (1985) 1767.
dinol 2, whose structure has so far not been unequivocally confirmed,
was isolated by Chiurdogfu and Delsemrne from Congolese vetiver oil.
An attempt to detect 2 in a sample of"Bourbon" vetiver oil by CC-MS
analysis after column chromatographic purification, gave a negative re-
sult.
141 L. F. Tietze, U. Beifuss, Angew. Chem. 97 (1985) 1067; Angew. Chem.
Int. Ed. Engl. 24 (1985) 1042.
151 L. F. Tietze, U. Beifuss, Tetrahedron Lerf 27 (1986) 1767.
161 Preparation: Portionwise addition of 50 g of basic aluminum oxide
(ICN Alumina B-Super I ) to a stirred solution of anhydrous iron(ll1)
chloride in 160 mL of dichloromethane under inert atmosphere. After
one hours' stirring, removal of the solvent in a vacuum. L. F. Tietze, U.
Beifuss, Synthesis 1988. 359.
171 B. B. Snider, D. J. Rodini, T. C. Kirk, R. Cordova, J . Am. Chem. Soc. I04
(1982) 555.
181 A. P. Krapcho, Synthesis 1982. 805, 893.
191 D. A. Evans in J. D. Morrison (Ed.): Asymmetric Synthe.sis, Vol. 3. Aca-
demic Press, Orlando, FL, USA 1984, p. I.

104 0 VCH Verlagsgesellschafr mbH, 0-6940 Wernheim, 1988 0570-0833/88/0505-0704 !$ 02.50/0 Angew. Chem. Int. Ed. Engl. 27 (1988) No. 5
[lo] 1 2 ' ' H NMR (200 MHz, CDCI,): 6=0.74 (9, J = 12 Hz, I H ; 7-H.J. 0.87
(d. J = 6 . 5 Hz, 3 H : 8-CH3), 0.84-1.09 (m, I H ) , 1.19-2.03 (m. 9 H ) , 2.10
(dddm. J = 14,4.5. 3 Hz, 1 H: 3-H,,), 2.24 (ddd, J = 12.3, 1 1 , 3.5 Hz, 1 H:
5-H ,,I. 2 33-2-47 (m, I H), 3.69 ( s , 3 H : OCH,), 4.61 (mc, 1 H : H,,,,<), 4.71
(mc. I H , H,,,,, ).
[ I I ] Details of the crystal structure investigation are available on request
from the Fachinformationszentrum Energie, Physik, Mathematik
GmbH, D-75 14 Eggenstein-Leopoldshafen2 (FRG), on quoting the de-
pository number CSD-53079, the names of the authors, and the journal
citation
[I21 a) 0. P Vig, K. L. Matta, G. Singh, 1. Raj, J. Indian Chem. SOC.43 (1966)
605: h ) 0.P. Vig, G. Singh, 0. P. Chugh, K. L. Matta, Indian J . Chem. 7
(1969) 434.
pling of 617.81resulted in the isolation of 3 in 44% yield.
The physical and spectroscopic data of 3 were in accord
with the literature data.(71Bromination[" of 3 with N-bro-
mosuccinimide (NBS) in CCI, in the presence of azoisobu-
tyronitrile (AIBN) furnished the monobromide 7 in 43%
yield as a mixture of several isomers (m.p. 119-123°C).
The unpurified isomeric mixture was dehydrobrominated
with KOtBu, giving benzo[2.2]metaparacyclophan-9-ene4
in 86% yield as the only isolable product.['I Compound 4
forms colorless crystals (from hexane), which melt at 90-
91"C.'91

Synthesis and Conformational Behavior of

Di benzo[2.2lmetaparacyclophanediene**
By Timothy Wong, Siu Shing Cheung, and
Henry N. C. Wong*
The preparation of [2.2]metaparacyclophane 1 was re-
ported more than two decades ago by Cram et al.[z,31Vari- 6 3
able temperature N M R studies on l l 4 l showed that, due to
conformational flipping of the molecule, the signals of the
p-phenylene protons of 1 coalesced at 146°C; this corre-
sponds to a AG,' of 87 kJ/mol.14] On the other hand,
[2.2]metaparacyclophane-1,9-diene 2 showed a coales-
cence temperature T,= -96"C, thus resulting in AG$ = 1 4
35 kJ/m01.[~'It was of interest to investigate the conforma-
tional behavior''] of compounds 3, 4, and 5 , which are
benzoannelated derivatives of 1 and 2. We report here on
the synthesis of 4 and 5 and on the results of variable tem-
perature N M R studies on these compounds.

8 0

1
8 2

10

Et,N, THP
TIC14.LIA1H& &&
o J & 13 0 '1 0
5
0 8
0 7
0
8 7
3 4 5

Benzo[2.2]metaparacyclophane 3 was first synthesized
by Vogtle et al. via several steps starting from 3,4"-bis(bro-
momethyl)-l,l':2',1"-terphenyl 6.I7l In the case of 3
T,= 116°C and AG$ = 75 k J / m ~ l . [ ' ~We were able to pre-
pare compound 3 in one step: phenyllithium-induced cou-
[*I Dr. H N. C. Wong [I], T. Wong, S . S . Cheung
Department of Chemistry, The Chinese University of Hong Kong
Shatin, New Territories (Hong Kong)
[**I Arene Synthesis by Extrusion Reaction, Part 13. The authors wish to
express their sincere thanks to Messrs. Y . H. Law. K . W. Kwong, and C .
W. Fung for their assistance in measuring the 250-MHz 'H-NMR spec-
tra and the mass spectra. S. S. C. is grateful to the Croucher Foundation
(Hong Kong) for the award of a Croucher Studentship.-Part 12: C. W.
Chan, H. N. C. Wong, J . Am. Chem. SOC I10 (1988) 462.
Treatment of 4 with bromine afforded an isomeric mix-
ture of dibromides 8 in 90% yield [MS: m / z 412 ( M @ ) 414 ,
+
( M e 2), 416 ( M e +4)]. The dibromides 8 were not sepa-
rated, but allowed to undergo direct KOtBu dehydrobrom-
ination in the presence of furan. The reaction leading to
the isomeric epoxides 10 (isolated in 53% yield) presuma-
bly proceeds via the species 9",'0.''1 containing a. C C triple
bond. The mixture of isomers 10 [m.p.>30O0C, MS: m/z
320 ( M e ) ] was not separated, but directly deoxygenated
with TiCl4-LiAlH4-Et,N in THF,"'] to give the title com-
pound dibenzo[2.2]metaparacyclophanediene 5 in 67%
yield. Compound 5 forms colorless crystals (from hexane)
which decompose at ca. 250°C. The structure of 5 was es-
tablished 'H-NMR s p e c t r o s ~ o p i c a l l y .In
~ ~[DJacetone
~ at
24"C, the protons H-5, H-6, H-7, and H-8 gave rise to only
a single extremely broad peak at Ci=6.95, which was diffi-

Angew Chrm Int. Ed Engl. 27 (1988) No. 5 0 VCH Verlagsgesellschaji mbH. 0-6940 Weinherm. I988 0~70-0833/88/0505-0705S 02.50/0 705