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Effects of Strained Bicyclic Annelation on the Benzene Nucleus The X-Ray Crystal Structures of a Triphenylene and Two Anthracene Derivatives.

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[I81 It was not possible to perform measurements under saturation conditions.
because the rates k,,, became too fast for determination by the N M R method.
The factor of about 100 between the ratios k,,,lk,,,,,, produced by 1 and 2 can
also be illustrated by the fact that. at the same malonate concentration
(10 mt.1). /cob, for 2 is about the same as that for 1 (about 260 x lo-' s C 1 ) at a
20-fold lower concentration
M for 1 versus lo-' M for 2. that IS, under
conditions much further from saturation for 2 than for 1.
[19] E. W Hansen. P. RuofT, J. Plirs. Chef??.1988. 92. 2641.
[20] CIFlhrms stable complexes with protonated polyamines (M. W. Hosseini. J. P.
Kintzmger. J. M . Lehn. A . Zahidi. Helr. C/i;m. Actu 1989, 72. 1078). Furthermore. N a + can compete %ith H + for the interaction with the polyamine [13c].
(211 This macrocycle had been synthesized in the course ofother work: A. MarquisRigault. J.-M Lehn. unpublished results; another approach has been reported
recently [22]
[21] T. Shimada. hl. Kodera. H. Okawa. S. Kida. J. Clieni. Soc. Dulrofi Puns. 1992.
[23] [2] = I 0 - j M. [miilonate] = 2.5 x
-lo-' M. Lineweaver-Burk plot
(6 points. r = 0.996).
[24] N . Kyritsaka\. J. Fischcr. H. Fenniri. .I.-M. Lehn, unpublished result.
[25] Rate acceleration for proton transfer to an enol ether catalyzed by a catalytic
antibody: J. L. Reymond. G. K. Jahangiri, C. Stoudt. R. A. Lerner, J. Am.
Chcwi Sot.. 1993. 115, 3909.
[26] J Wolf. A. C;istero. J. Rebek, Jr.. lrrrrel J. Chem. 1992. 32, 97.
[27] H. Fenniri. C Dallaire. J.-M. Lehn. unpublished results.
analyses of anti-lb, anti-lc, and anti-3. The structure of anti-3
shows significant bond length alternation within its benzene
unit. This feature is not observed in anti-lb and anti-lc.
Bond length alternation within the benzene nucleus as a result
of annelation to small rings was first postulated by Mills and
N i ~ o n . [Although
they based their work on the wrong model
of benzene, the idea that annelation to small rings could induce
bond length alternation has survived up to the currently accepted model of benzene.[51Multiple angular [a.c] and [a,c.e] annelation was expected to be more effective at promoting bond length
alternation than linear [a,d bisannelation because in the former
case the strain imposed by each of the small rings on to the
benzene nucleus would act cooperatively. However. with the
exception of compound 8,[61in which electronic factors play a
major role, the latest findings indicate that there is no significant
bond length alternation in the planar compounds 4-7."] In
Effects of Strained Bicyclic Annelation on the
Benzene Nucleus: The X-Ray Crystal Structures
of a Triphenylene and Two Anthracene
Francesca Cardullo, Daniele Giuffrida,
Franz H. Kohnke,* FranGisco M. Raymo,
J. Fraser Stoddart, and David J. Williams
In the course of our studies on the assembly of molecular
doughnuts, cages, and ribbons using repetitive Diels-Alder reactions between molecular building blocks containing endocyclic dienophilic double bonds, and exocyclic butadiene units
grafted onto either norbornane or 7-oxanorbornane skeletons,
we have synthesized the bisdienophiles 1 and 2 and the trisdienophiles 3.['l Here we report[2.31on the X-ray structural
la:X=H; Y=O
b : X = M e ; Y=CH,
c:X=Br; y=o
these compounds angular distorsion appears to lead to the formation of bent bonds instead.[7]Yet the crucial role of strained
bicyclic annelation in the induction of bond length alternation
in the benzene nucleus has recently been fully confirmed by the
results of computational and X-ray structural analysis of 9[*l
and lo['', and the interpretation of this effect in terms of the
Mills -Nixon theory has finally been rejected."]
Besides angular strain, bicyclic annelation such as that in 1-3
is recognized to introduce anomalous effects by o through-bond
coupling of the attached framework and additional coupling to
the o-linked n bonding orbitals of the ethylenic group.["]
In the X-ray crystal structure of anti-3['] (Fig. 1 ) the average
lengths of the bonds in the benzene ring endo and eso to the
annelated bicyclic systems are 1.425 and 1.353 A, respectively.
Prof. F. H. Kohnke. F. Cardullo. Dr. D. Giuffrida. F. M. Raymo
Dipartimento di Chimica Organica e Biologica
Universitd di Meisina
Salita Sperone 31. I-9x166 Messina (Italy)
Fax: Int. code +(90)393895
Prof J. F. Stoddart
School of Chemistry, The University of Birmingham
Edgbaatoii, GB-Birmingham B152TT (UK)
Dr. D. J. Williams
Chemical Crystallography Laboratory. Department of Chemistry
Imperial College of Science, Technology and Medicine
South Kensington. GB-London SW72AY (UK)
This work was sponsored by the Consiglio Nazionale delle Ricerche (Italy) and
the Engineering and Physicai Sciences Research Council (UK).
( / J P ~l r i i
&</,Err,?/.1996. 35,No. 3
Fig. 1. The X-ray crystal structure of an[;-3. The values of relevant dihedral angles
involving the oxygen bridges are indicated beside each associated ring system.
VCH I / r r / r ~ ~ . ~ , ~ r s ~ ~ l mhH.
/ s r / i a fD-6Y4.51
WDinhe';r??. 1996
9 10.00
+ 2'
~ ~ ~ 1 2 2 113.3"
The corresponding values observed for 9 (1.41 7
and 1.3798,) and for 10 (1.438 and 1.3498,)
1 2 3 , g m 2 3 , g *
indicate that bond length alternation in anti-3
113.3" 122.kCH2
is intermediate to those in these two hydrocarbons. This is consistent with the increasing angular distortion of the CY bonds between the
aromatic and the methine carbon atoms, which
subtend with the endo bond angles of 106.5,
104, and 102.3" in 9, anti-3, and 10, respectively. In the recently reported structure of 3 calculated at the 6-31G(d) level,["l the bond lengths
are 1.438 8, ( e x o ) and 1.340 8, (endo); the
angles formed by the CY bonds between the
arene and the methine carbon atoms and the
endo annelated bonds are 103.0".
Accompanying the pronounced bond alternation within the benzene nucleus in anri-3,
Fig. 3 . The X-ray crystal structures of A ) unri-lb and B) anli-lc. The relevant dihedral angles involving
the one-atom bridges are indicated beside each associated ring system.
there are subtle perturbations in the conformation of the molecule as a whole. The oxymethine carbon atoms all lie slightly out of the
and crystallographic Ci symmetry. In anti-lc the methine carplane of the benzene nucleus: the deviations, which are in the
bon atoms lie 0.023 and 0.041 8, out of the aromatic ring plane
range of 0.02-0.05 A, are consistent with a repulsion between
in a direction opposite to that of the bridging oxygen atoms. In
the oxygen lone pairs and the aromatic n system. Thus, C(9) and
anti-lb this effect is not observed to any significant extent. In
C(12) lie below the plane of the aromatic ring, while C(l) and
anti-lc the dihedral angles between the principal planes within
C(4), and C ( 5 ) and C(8) all lie above this plane (Fig. 1 ) . The
the bicyclic residues, that is, those containing the olefinic bond
dihedral angle between the plane containing the oxygen bridge
and the oxygen bridge, do not differ significantly from those
and the one containing the olefinic double bond is in each case
observed in anti-3. In anti-lb the replacement of the oxygen
greater than that formed by the plane containing the oxygen
atoms by methylene groups is accompanied by a reduction in the
bridge and the plane containing the pair of annelated aromatic
analogous dihedral angle (123.9" in l b , cf. 126.2' in lc , Fig. 3).
carbon atoms. Thus, the repulsive interaction of the oxygen lone
An inspection of the packing of the molecules in both these
pairs is more pronounced in the former case than in the latter.
structures does not reveal any notable intermolecular interacA study of the packing of the molecules in the crystal reveals
(Fig. 2) an elegant network of weak but cooperative C-H . . . O
In contrast with the structures observed for the linear bishydrogen bonds, involving both olefinic and methine hydrogen
dienophiles, the bond length alternations observed for the benatoms. All three oxygen atoms within each molecule are implizene rings in the crystal structures of the bisdienophiles 2b[I4]
cated in hydrogen bonding interactions.['21
confirms that the angular fusion allows the two 2,SdihydroThe structural evidence obtained previously['31 supports the
furan residues to act upon the aromatic nucleus in a cooperative
proposal that when the benzenoid ring is linearly bisannelated
manner. The relative magnitudes of the effects in 2b (average
with bicyclic units, no significant bond alternation occurs within
lengths of the endo and exo bonds are 1.422 and 1.367 A, respecthe aromatic ring. Further direct evidence for the absence of
tively) and in anti-3 are consistent with this.
bond alternation is provided by the crystal structures of anti-lb
The definitive experimental evidence for bond alternation
and anti-lc (Fig. 3). Both of these structures have molecular C,,
provided by the structure of anti-3 and support for the predicted
through-space and through-bond interactions between the aromatic
ring and the bicyclic annelated units provides an explana0
tion for the difficulties encountered['d1in the synthesis of angularly annelated systems.
Received: July 17, 1995
Revised version: October 5. 1995 [Z8211 IE]
German version: Angew. Chem. 1996, 108, 347-349
Keywords: bond-length alternation . Mills -Nixon effect . polycycles . strained rings . triepoxytriphenylenes
Fig. 2. The packing of anti-3 in the solid state; the elegant network of C - H " ' 0
hydrogen bonds is indicated by the dotted lines.
VCH Verlagsgesellsrhafr n?bH, 0-69451 Weinherm, 1996
[ l ] a) P. R. Ashton. G. R. Brown, N. S. Isaacs, D. Giuffrida, F. H. Kohnke. J. P.
Mathias, A . M . Z . Slawin, D. R. Smith, J. F. Stoddart, D. J. Williams, J. Am.
Chern. Soc. 1992, 144. 6330-6353; b) P. R. Ashton, U. Girreser. D. Giuffrida.
F. H. Kohnke. J. P. Mathias, F. M. Raymo, A . M . Z. Slawin, J. F. Stoddart,
D. J. Williams, ihirl. 1993. 115, 5422-5429:~) For Ibsee: H. Hart, C. Lai, G. C.
Nowkogu, S. Shamouilian, Tetrahedron 1987,43,5203-5224; d) For Ic and 3
see also: F, M. Raymo, F. H. Kohnke, F. Cardullo. U. Girreser, J. F. Stoddart,
TFtrahrdron, 1992, 48. 6827-6838 and references therein.
[2] Crystal data for anti-3: monoclinic, a =13.718(2), b = 8.661(2), c =11.178(2)
A. fl = 102.62(2)', V = 1295.9(4) A3. space group P2,ic. Z = 4, "(CuKZ)=7.8
cm- I , P . . , . ~ = 1.42 gem-'. Siemens P3IPC diffractometer, o scans, Cu,, radiation (graphite monochromator). The structure was solved by direct methods
and the non-hydrogen atoms refined anisotropically to give R = 0.061,
0570-OX33i96/3503-0340 S 10.00+ .25/0
Angew. Chem. Int. Ed. Engl. 1996, 35, No. 3
R. = 0 05.; l o i I O Y 7 independent obberved reflections [20 = 3 116 .
1 F,,,> 3n( \/;,I I] b ) Ftirther detail, of the crystal structure in\'esrigdrions cdn he
oh:,iincd Iiniii rke Direc!or of the Cdrnbridge Crvstdllogr2phic Data Centre.
; 2. Unioc R u d . GB-Cambridge CB2 IEZ ( U K ) . by quoting [he full lirerature
da:a fur (iirri-lb. rnonoclicic. 11 = 81?0(16). h - 7 36413).
637(2)A'. space group P 2 , < . Z = 2.
: O YO(?) A. p = 109.7(2) . I
/i(C:ik,l = 5 I c i n - l . ( I . . , ~=
~ 1 2 ? g c m - ' Crystdl d i m for i i r i 1 1 - 1 nirmoclinic.
' I ~ . ~ . Y % I ? ) . /I=IS.YIY?),
< =7493(2)A. [1=93?6(2). I =j900(3)AJ.
? 07 g c m
s?,icegroup 1'2, ( I . / ~ . ~ ( C U , ,-I 8 6 . 4 c n i ~ 'p.,<,,
P3 PC diIlr.:~!unierer (lor m r r - l b ) . Nicolct R 3 m E difTraclomerer (for i i i r i i Icl. 1'1 scr.n,. ('uk, rddiatioc ( g r a p h i k ~r.onochroniatur)The structures u c r e
sol\cd h! direct methods m d the Run-hydrogen dloins refined .icisorropically,
(.isiiig .ihw:?:i~wcorrected ddta fur UI
Ic) to g b e for i r i i i i l b . R = 0.051.
K,,= (1 051 lor 5Y 1 icdependec! observed rcl1ectior.s ( 2 0 = 3 116 .
lc,, >4u(lF,,m I]. dcd lo r ~ i r 1 1 i - 1 ~R. = 0.03'. R , 0.041 Tor 772 independent
See ref [?h]
u h w n c d rcllcctions 120 = 3 116 . lFol >4o(i!J)i
14 H Mill\. I (; N i ~ o c .J C'/IWII .So<. 1930. 2510 252.1
J. S Sicpel. I i i y r , , i C ' h n i i 1994. /(M.I X O R . .Aii,yi>ii C/icrir Iiir GI. E i t ~ l .1994.
.I<.1 '21 l 7 ? 3 .ind references thereic
i i ~K
t . i u s r . F D Glecdcnic_e.A Streiruieser. K . P. C Vollhardt. J ,4111
C./JOII S,U 1992. / I d . 8263-8268. D ) K K Balbridge. J S Siegel. J Aui
.S,u IY92. / / . I . 9583 9587
K B{>etc.D Lllircr. u' E . Billups. M M. Hale?. A H Maulirr. D L Mohler.
1994. / 0 6 ~321 . .41i.ei,i: ('liiwi l r i l . G/ Eiigl.
K I' (' \ oilI:.irdt, . 4 1 i ~ c wChwir.
1994. L3. 31; 317
N I. Fi<icL.K K 8d;bridge. P. Gdctzel. J. S. Siegel. 7 i v r d ~ 4 i ( i i Li r v i 1995.
3n. 4 i S Y 4397
.I) H - B B u r p K K . B;ilhridgc. K Hdrdcastle. T i L. f r a n k , P Gdnrrcl. J. S .I Zillcr. 411,qw~C/rm 1995. 1 0 7 . 1S'l5-1577. A i i p ~ ,C'liiw 111i.Ed
h i p i IVYS. l 4 . I iS4 I456 b) h. L. Fr.iiih. K K . Balbridge. I . S Siegel. J .41ii
< ' / l t ' l J l .TO< 1995 117. ? l o ? 2103.
r l l J S C'r.iu. N S Hush. S Sternhell. C. W Tdnsey. J P/I:.\ Chcvii. 1992. 96.
> 7 5 3 5 7 5 % h ] hl N.Paddon-Ruu. H. K Parney. J. B Peel. G. D Willel. J
198.4. 564 566. c l M N Paddon-Row ,411
-?51 . d l K N . Houk. N . G Rondan. M. N PaddonRow C \4: Ic:'loid. P I Huh. P D Burrow. K. D Jordan. J .Am C'/riwr S o i
IY83. /fi? S i b ? 5569. e ) R Gleiter. A r i q ~ i ~C/r~~rii
1974. 86. 7 7 0 . Aii,qcii.
( ~ I i i wIui
Ld !:ti,</
1974. 13. 696 701 , f ) R Iloflmaiin. 4" C/iiwi
4. I 9
N I. t r d i i k . I Sicgel. , 4 J i w ( i , > 111 T / r ~ ~ u ~ c ~i ii i~i ~~ ri i/~/i ii i i ., L~ 1! 1 1 / ~ ~ i i I cl.i~d, 3.
( E d R P I Iiunimell. JAI. Grecii\rich (IJSA). 1995. pp 209 260 We th.ich
Prol'essoi J S Siegel lor suppl)ing 11s uirh details on the c;:lculated \true
c =
(tire t>r3
For recent
JCCUCII[S or. hydrueei: bond cetuurka i n the solid bta!e w e .!) C B
Acheio!. K R Sedduii. C/riw So< Rcr 1993. 22, iY7- 407. b) M C . Etrcr.
A < < < ' / I ~ I > I R<,\ 1990. 3, 170- 126. C) G. Dcsirdsu. i h ~ d 1991. 24. 290-796.
d ) G hl Wniiesidez. t E Siiiianek. J P Mathids. C T Sero. D.N Chin. M
Ivldiiiineii. D IGordon. i h i d 1995. 28. 37 45. The [ H
0 1 ir.~eractiocsare
0 distdnces are i c [he range 2.42o l : u o !kws . r i ~ v i g e i ones where the H
A . .]:id \$t.~LciIinkagez hctween ccctrosyrnmetricdl!). related pdirc of ~ o l \ k:icrc [ l i e H
' 0 d i \ r ~ n c t .i s 2 h l 8, The C - H
0 ~ n g l e sdie in the
r.iiipc 132 : ? I
'i) F 11. Koh::Le. _I F. Studdart. A . M 2 Slauin. D J Willidrns. A i r u C I I . \ I O / / o , ~ I .Si,<I C' 198th 44. '38
740. h ) ihirl. 1988. 44. 7 4 - 7 4 ? , C ) ihril. 1988. 44.
742 7 4 5 . ~ 1 )F 11 Kuhiike. .I P M::tkia~, J F.Studdnit. A ;M L S l a ~ i i i .D J
W!ili,irn~.h i d 1990. 40. !OJ$ 1046: e) F H Kutnhe. J P Mdtkids. .I F Stoddiirr. A M L S I . ~ u i n .D J Wa!ts. D .I WilIi:iii!s, h i / 1990. 46. 1046- 1049.
I )i/>i(/
1990. 40. ll)49-. 1051
Asymmetric Catalysis in the Complexation
of Prochiral Dienes by the Tricarbonyliron
Fragment: A Novel Methodology for the
Knantioselective Synthesis of Planar Chiral
Tricarbonyl(diene)iron Complexes**
Hans-Joachim Knolker* and Holger Herniann
Tricarbonyl(~J-1,3-diene)iron complexes are important
building blocks for organic synthesis."] l'he bulky tricarbonyliron moiety ensures in most cases a complete diastereoselectivity of reactions at these complexes. Applications of tricarbonyl(04-1.3-diene)iron complexes to asymmetric synthesis
have demonstrated that the metal fragment may also serve as a
chiral auxiliary,[21The methods available for the preparation of
enantiopure complexes include the classical separation of
raceniic complexes through diastereoisomers.131the diastereoselective complexation of enantiopure diene ligand5,l'I the separation of planar chiral complexes by enzymatic reactions.[5i and
the enantioselective complexation of prochiral 1 ..i-dienes by chiral tricarbonyliron transfer reagents.lbl We recently introduced
($-l -aza-l.3-butadiene)tricarbonylironcomplexcs as highly efficient novel tricarbonyliron transfer reagents."-'] l'he 1 -aza1Jbutadienes serve as catalysts for the complexation of 1.3-dienes with pentacarboiiyliron.['-'!
Based on these findings we investigated the possibility of
achieving a n asymmetric induction in the complexation of
prochiral 1.3-dienes with the tricarbonyliron fragment by using
chiral enantiopure I-aza-1.3-butadienes as catalysts. We describe
herein the first asymmetric catalysis of the complexation of a
prochirdl ligand by a transition metal fragment. i n which an optically active. planar chiral transition metal n complex is generated.
The reaction of 1-methoxy-1.3-cyclohcxadiene ( 1) with pentacarbonyliron [Eq. (a)]. in which the corresponding planar chiral tricarbonyliron complex was generated, was used as a model
reaction to optimize the catalytic system with respect to yield
and asymmetric induction (Table 1 ) .
Condensation of ( R ) - and (S)-1-phenylethylainine with cinnamaldehyde afforded the azadienes (S)-3and ( R)-3 shown in
Scheme 1
'l'he fact that stoichiometric complexation of these
chiral azadienes by the tricarbonyliron fragment 15 nonstereoselective is of no consequence for the present investigations, since
epimerization of the two diastereoisomers occur5 under the reaction conditions." ' ] IJnder standard reaction conditions (2
equiv Fe(CO),. 0.125 equiv of catalyst. benrene. 80 C ) . the
catalyst (S)-3provided complex 2 in 69% yield with 6 % w of
the R enantiomer. Correspondingly, complexation in presence
of catalyst ( R ) - 3 gave 2 with 6Yo et' of the S enantiomer. The
enantiomeric excess in each case was determined by separation
of the planar chiral tricarbonyliron complexes 2 on a permethylated Ikyclodextrin column by HPLC." 2 1
The axially chiral binaphthyl-substituted azadicnes (S)-4and
(S)-5 were prepared by reaction of the enantiopure ( S ) - 2 -~
Prof D r H -J. Knolkcr. Dip1.-Chern. H H e r m a e n
Inlritu! fur Orgdnische Cheniie der Uiiivcrairat
Richard-Willztatter-Allec. D 761 !I Karlsruhe (German! 1
Far In[. code +l721)698-529
e - n d i l hi:oe ochhades uhemie u i i i - i d r ~ s ~ de
Trdiicition Met.11-Dime Complexes i n Org,inic Synrkesi,. Part ?X This wurh
was supported b? the Drutsche Forschungsgerneiii~c~aI~
Forderpreis~acd the Fonds dcr ('heniischcc lndustrie h e arc grdtcful to
Priv Dor. D r P Metr. Unixcrsitit Mhcs:cr. for providing us hi, optimized
nrocedure iu[ [he svnrhcsir of cnanriupure 7-dnuno-3'-rn~,thox!-I.1'-hinaphrhpl prior to puhlication Part 27 H -J. K c d k e r . G . Baum. J - B . Pannek.
7i,1riihi~i/roii1996. .il.In
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crystals, two, anthracene, bicyclic, triphenylene, annelation, derivatives, effect, structure, nucleus, benzenes, ray, strained
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