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Graphical Abstract (Angew. Chem. Int. Ed. Engl. 111996)

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~
_
A Journal of the
Gesellschaft
Deutscher
Chemiker
__ - _ _ - ~
International Edition in English
1996
35/11I
Pages
1141-1248
EDITORIAL
Science for the future-that is the slogan for the 75th anniversary
of the founding of the VCH Verlagsgesellschaft. “Future grows
from the past“. and the latter is portrayed in this quick overview.
Thc company w a s founded as “Verlag Chemie” by the Deutsche
Chemische Gesellschaft (German Chemical Society). the Verein
Ileutscher Chcmiker (Association of German Chemists) and the
Vcrein zur Wahrung der Interesscn der chemischen Industrie (Socicty for thc Protection of the Interests of the Chemical Industry).
From the beginning the traditional German chemical journals,
Ang(~ii.tmcr“c~
(’iicwrie, Clic~niischeBmicli fe, and Li(4i.s Annufen, have
been the most important products of the company. and despite the
drive for expansion in the last 15 years, little has changed in this
respect
The Gesellschaft Deutscher Chemiker (GDCh) was the successor
o f two o f the learned societies and for about 40 years, until the
beginning of thc nineties, the main owner of the publishing company. I n [his time Verlag Chemie, as i t was known until the end of
1984, underwent continual expansion. Journals were published for
othcr scientific organizations and societies (as they had been all
he long) and net+ oxs were founded, an impressive book publishing
program was cstablished, and in recent years publishing interests
beyond chemisti-) were nurtured, in particular by subsidiaries such
iis Ernst & Sohn. Akademie Verlag (both located in Berlin), and the
Academy GI-oup (London).
Aftcr more than a decade without the term “chemistry” in the
company‘s name. the interests of chemistry arc served better than
ever: the traditional journals Clzernisclw Berichir and Liebigs Airn t r h have been strengthened by a phase of reorientation; the former is now publishing inorganic and organometallic chemistry and
the latter all lields of organic chemistry. In the material sciences
. 4 c h n w d Mi/rc,rirr/.s has secured its place as a top journal; AngcI ~ . L I I I L / ~ P~ ’ l i c w i i chas
~ continued its way as a leading international
chemistry journal: the start of C‘/~einistr~~--AEuropcwn Journul
could n o t haic been more successful. VCH has become the textbook
publishers i n chemistry in Germany. Furthermore, there has been
incredible SLICCL‘SS on the German-speaking market with books such
:is the ”Chemische Kabinettstiicke” by Roesky and Mockel; an
English translation of the book (“Chemical Curiosities: Spectacular
Experiments Lind Inspired Quotes”) will appear in August, an
Italian one is in preparation. Also in the international scene. recent
new publications, for example, by Curran/Giese, Porter (“Stereochemistry of Radical Reactions”), Drauz/Waldmann (“Enzyme
Catalysis in Organic Synthesis”), Furstner (”Active Metals. Preparation-Characterization --Applications”). Lehn (“Supramolecular Chemistry. Concepts and Perspectives”), NicolaouiSorensen
(“Classics in Total Synthesis”), Schmalzried (“Chemical Kinetics of
Solids”), and Stang:Diederich (“Modern Acetylene Chemistry”)
have been extraordinarily well received. Our goal is lo continue this
path into the future.
With this background, the brand new alliance between VCH and
Wiley-- this renowned scientific publishing company founded in
1807 acquired a 90 % interest in the VCH Publishing Group in early
May offers great opportunities: the GDCh journals (which continue to be owned by the GDCh and published by VCH) will certainly profit from Wiley‘s excellent worldwide distribution network;
the same is true for the English book publishing program. The new
partnership will be extremely beneficial also in terms of developments in electronic media. On the other hand, Wiley will profit from
VCH’s competence in all areas of science, and chemistry in particular, as well as its presence in the German-speaking and continental
European market. Professor Dr. E. Winterfeldt, the President of the
GDCh, said: “. . .we have been looking for a suitable partner to
strengthen the Society’s [international] publishing interests. Wiley
has a high reputation in Germany and throughout Europe. and
o u r publishing partnership will help us effect our ambitious plans
for cooperation between all European chemical societies and
chemists.. . . In fact, in accordance with an alread) published concept the GDCh-Wiley have already given their backing -will distribute ownership rights of the new top journal C‘limzisirj,--~AEuropeun Journnl to chemical societies in Europe. Real steps towards
a European chemistry for the future”.
_
COVER PICTURE
The cover picture shows schematically the progress of a thermally induced transformation to an ordered solid. This involves a kind of disproportionation of the
monoadduct of [60]fullerene and anthracene into the parent [60]fullerene and the
antipodal bisadduct as an ordered 1 : 1 mixture. More about this solid-state reaction,
which opens a very efficient access to the bisadduct, is reported by B. Krlutler et al.
on page 1204ff.
REVIEWS
Contents
The field of nanochemistry aspires to the synthesis of forms that exist and function
at the nanometer scale. The question is, how can this goal be achieved? Self-assembly
processes, ubiquitous in Nature, provide remarkably concise and efficient methods
for arriving at such compounds and complexes. The burgeoning field of nanochemistry must, therefore, learn lessons from Nature and transfer concepts from biology
to chemistry and apply these lessons to the synthesis of unnatural forms.
D. Philp, J. F. Stoddart ....______
1154-2196
Self-Assembly in Natural and Unnatural
Systems
HIGHLIGHTS
The potential of bioorganometallicchemistry as a new interdisciplinary research area
is illustrated impressively by organoruthenium complexes with peptide ligands.
Ruthenium-n-arene fragments are of interest both as markers for peptides that can
be readily introduced and as promoters of complex synthetic transformations such
as the preparation of cyclic peptide antibiotics and of linear oligopeptides in a
one-pot procedure.
[N,CaBa,,] clusters separated by a matrix of sodium
atoms that can alternatively be considered as stars of
octahedra (shown on the right) comprising faceshared [NCaBa,] octahedra with common Ca vertices are present in Na,,Ba,,CaN,
recently described by Simon and Steinbrenner ( A n g m ~Cl7em.
.
Int. Ed. Engl. 1996, 35, 552). This compound, the
first discrete subnitride cluster, is not only a link
between Na/Ba subnitrides and the classic Rb/Cs suboxides, but also an important
extension of the structural chemistry of this class of compounds-not least because
a “real” cation (Ca”) is present in the saltlike interior of the cluster.
R. Krlmer* . . . _ _ _ _ _ _ _ _ _ _1197-1
_ _ _ _ _199
_....____
Application of n-Arene- Ruthenium Complexes in Peptide Labeling and Peptide
Synthesis
C. Rohr* ___....._.__________.....
...... 1199-1201
From Oxides to Nitrides:
Recent Developments in the Structural
Chemistry of Alkali/Alkaline Earth Metal
Sub-Compounds
COMMUNICATIONS
B. Krlutler,* T. Miiller, J. Maynollo,
K . Gruber, C. Kratky,
P. Ochsenbein, D. Schwarzenbach,
H.-B. Biirgi ............................
1204-1206
An unprecedented solid-state reaction of a fullerene
monoadduct leads to the antipodal fullerene bisadduct 1. This regiospecific transfer of anthracene
appears to be driven by an increase in entropy.
1
“This is a substance or group of substances about which there has been much discussion” is a statement we read in an older standard textbook of inorganic chemistry
with reference to a (usually) amorphous blue material that was first mentioned by
C. W. Scheele in 1778 and discussed by J. J. Berzelius in 1826, and that today is
known as “molybdenum blue”. Now based on the knowledge of compound 1 with
an archetypal structure, the more than 200 year old mystery regarding the nature of
this multifunctional material with its interesting properties has been partly unveiled.
A Topochemically Controlled, Regiospecific Fullerene Bisfunctionakzdtion
A. Miiller,* J. Meyer, E. Krickemeyer,
1206-1208
E. Diemann ......____________.........
Molybdenum Blue: A 200 Year Old Mystery Unveiled
Contents
M . Albrecht,* S. Kotila
A distorted square-planar coordinated Li+ ion is located in the pocket of the triple-stranded helicate
(structure shown on the right) formed by self-assembly of three ethylene-bridged bis(catecho1ate) ligands. and two titanium(1v) ions. This unusual coordination geometry is the result of steric effects and
stabili~inghydrogen bonds between the two water
molecules bound to the Lic ion and oxygen atoms
of the ligands.
_ . . _ _ _ .1208-1210
__
Stabilization of an Unusual Coordination
Geometry at Li' in the Interior of a
Cryptand-Type Helicate
The growth of crystals of the structurally related zeolites FAU and
EMT may be characterized by layer
upon layer propagation. This previously proposed mechanism has been
confirmed by results of an investigation into the crystal growth features
in zeolite Y by atomic force microscopy. The intergrowing surfaces
of the crystal (see schematic representation on the right) are constructed by the deposition of sodalite-like
building units, leading to the formation of terraces.
M. W. Anderson,* J. R. Agger,
J.T.Thornton, N. Forsyth _... 1210-1213
Up to third-generationmetallodendrimerscan be constructed by a repetitive sequence
of reactions with building blocks that contain two coordinatively unsaturated Pd
centers ("pie" shape) and one labile, coordinating cyano group ( A ,see representation below). The key steps of assembly are the displacement of the chloro ligands
)(:.
with AgBF, and the in situ reaction with the cyano groups of the dendrimer
building blocks to give the next generation. The resulting dendrimers have molecular
masses of LIP to 25 kDa.
W. T. S. Huck, F. C. J. M. van Veggel,*
D . N. Reinhoudt* ..______...._._..
1213-1215
The calixl4larene skeleton serves both as a spacer
and as a molecular platform for preorganization in
molecular boxes such as 1 constructed from calixarene-based melamine and isocynanuric acid derivatives, which self-assemble in double-rosette structures (shown schematically on the right). These
ensembles were characterized by 2D NOESY experiments, which provide information on intramolecular H-H distances and cross relaxation rates.
R. H. Vreekamp, J. P. M. van Duynhoven,
M. Hubert, W. Verboom,
D. N. Reinhoudt* _ _ _ _ _ . . _ . _1215-1218
___._
The hydrolysis half-life is reduced from 75 years
to eight minutes for bis(pnitropheny1)phosphate (50 C, pH 7) when binuclear complexes like 1 are added; related complexes lead
to similar effects. The cleavage of plasmid
DNA is also accelerated dramatically. In these
catalyzed reactions the distance between the
metal centers plays a critical role.
Crystal Growth in Zeolite Y Revealed by
Atomic Force Microscopy
Controlled Assembly of Nanosized Metallodendrimers
Molecular Boxes Based on Calix[4]arene
Double Rosettes
qfo
K. G . Ragunathan.
H.-J. Schneider* _ _ _ _ . . _ _ _ _ _ .1219. . _ . . _1221
..
n
o
n
o
n
N
H
R
u w u
1
p
Binuclear Lanthanide Complexes as Catalysts for the Hydrolysis of Bis(p-nitropheny1)phosphate and Double-Stranded
DNA
Contents
COX and LOX inhibitors analogous to 2-arylpropanoic acids have been synthesized
(general route is shown below) and can be viewed as mimetics of arachidonic acid.
Remarkably, even medium-sized cycloalkanones reacted almost quantitatively with
zinc cuprates. Interesting differences in pharmacological activities related to ring size
were observed.
n -
B. Greve, P. Imming,"
S. Laufer ................................
1221 -1223
Efficient Synthesis of New 2-Cycloalk(en)ylpropanoic Acid Derivatives-Medium and Large Rings as Bioisosteres of
Alkylphenyl Moieties?
(HzcLY=o
n = 4-72, 14
The first structural analogs of the photosynthetic reaction center (1 and 2) have been
synthesized in which the electron acceptor is attached to an electron donor consisting
of a pair of porphyrin subunits held within 3 A of each other. Electrochemical
studies of the anthraquinone derivative 1 suggest that the acceptor and the bis(porphyrinato) zirconium subunit are interacting electronically.
G. S. Girolami. * C. L. Hein,
K. S. Suslick* .......... . ....._....... 1223- 1225
The n-electron density in the cavity affects the inclusion behavior of dimers, 1-1 and
2-2 as experiments with CH,, C,H,, CH,F, and CF, guests indicate.
X. Garcias, J. Rebek, Jr.* _...._1225-1228
A Zirconium Bis(porphyrinate) Sandwich
Complex with an Appended Quinone
Synthesis and Encapsulation Behavior of
New Redox-Active Dimeric Assemblies
0
1:
R = OH ; E = COz(nC4Hg)
0
2: E
An unexpectedly high affinity for guanine is shown by the rare R N A nucleobase 7,9-dimethylguanine (7,9DimeG). At pH 7 it forms a partially
protonated homo base pair (see
sketch) with its conjugated acid (7,9DimeGH'), the stability of which
greatly exceeds that of the WatsonCrick base pair between guanine and
cytosine.
= C02(n-C4Hg)
H3C
l+
H
I
H3C
N-H
S. Metzger, B. Lippert *
._ _
.....
1228- 1229
Self-Complementarity of 7,9-Dimethylguanine: A Base Pair Containing Three
Hydrogen Bonds
.... 0
I
H
CH3
Completely unprotected peptides carrying chemoselectively addressable groups react
under very mild conditions with free reducing sugars o r lipidic aldehydes to form
glycopeptides or lipopeptides (for example the somatostatin analogue 1) of any
desired structural complexity.
S. E. Cervigni, P. Dumy,
M. Mutter* _...____.._.____....____.....
1230-1232
Synthesis of Glycopeptides and Lipopeptides by Chemoselective Ligation
OH
N - 0 7
OH
f0
1
N - o A C o - ~ - ~ - ~ - ~ - ~ - ~ - ~ - ~ - ~ E - L - ~ - ~ - ~ - ~ - ~ - ~ ~ 2
'k
1146
,c>VCH V~rluils~esellsrltu~f
mbH. 0-69451 Weinhrim,1996
0570-0833/96:3511-1146 8 15 OO+ .25/0
Angeir. Chem. I n / . Ed. Engl. 1996, 35,N o . I f
Contents
An oxidative power comparable to quinonoid oxidants is a characteristic of the octakis- and tetrakis(oni0)-substituted arenes 1 and 2a,b. which are readily accessible by
Me,SiOTf-assisted poly(onio) substitution. 1 : L = 4-dimethylaminopyridine. 2a:
X = CF. 2b: X = N ; L in both cases PR,.
2 a,b
1
Complete cleavage of the phosphorus-carbon triple bond is the characteristic step in
the reaction of ter-t-butylphosphaethyne with I under mild conditions, which leads
to the formation of the p,-carbyne-p,-phosphidotricobalt cluster 2. The phosphido
ligand in 2 can be oxidized with oxygen or sulfur to give PO and PS ligands,
respectively. The phosphane arm in the starting material is evidently necessary for
the formation of cluster 2. R = CH,CH,PtBu,, R’ = tBu
R
The addition of a CH, group to the sc-carbon atom of the metallacumulene unit
Rh=C=C=C(R)Ph occurs with CH,N, (1 -+ 2) and. surprisingIy, also with CH,I
( I + 3 ) . The free butatriene H,C=C=C=C(tBu)Ph is generated from 2 (R = tBu)
and CO. Analogously, the allenes H,C=C=CRPh (R = Ph. CF,) are accessible
from the allene complexes trans-[RhCl{(l .2-r/-H2C’=C2=C3(R)Ph}(PiPr,),],
which are formed by hydrogenation of 1 (R = Ph. CF,), and CO. L = iPr,.
‘c..
3
1
1 ’Ph
R
$Ti
YCH,
,N
0
R = alkyl, aryl
$<
Ph
J. Foerstner. F. Olbrich,
1234- 1237
H. Butenschon* _.._.._..............
A New Mode of Reaction of tert-Butylphosphaethyne: Trinuclear Cyclopentadienylcobalt Clusters with P, PS, and PO as
p 3 Complex Ligands
H. Werner,* M. Laubender,
R . Wiedemann,
B. Windmiiller __.._..__.._..__.._.__.
1237-1239
Methyl Iodide as a Source of CH,: Two
Routes for Generating 1.1-Disubstituted
Butatrienes in the Coordination Sphere of a
Pil
Silicon makes the difference! In contrast to known imines from alkyl- or arylamines,
imines derived from C,C-bis(trimethylsily1)methylamineand enolizable aldehydes
react, as shown below, with ketenes to afford exclusively ,Mactams. Furthermore,
the reaction is highly diastereoselective when asymmetric ketenes are used.
Ph
Charge and Potential: Arenes as Oxidants
L’
L+
L’
R. Weiss,* R. May,
B. Pomrehn _............_.__.__.._.__._
1232- 1234
C. Palorno,* J. M. Aizpurua,* M. Legido,
R. Galarza, P. M. Deya, J. Dunogues,
J. P. Picard, A. Ricci.
G. Seconi __..__.__..__.__.
_ _ . _ _ _ . .1239-1241
_.__.
Imine Substituent Effects on [2 + 2JCycloadditions with Ketenes
R=CH(SiMe3)L
C
R
II
NYi
0
SiMe,
* Author to whom correspondence \hould he addressed
BOOKS
Contents
Aspects of Organic ChemistryStructure/Aspekte der Organischen Chemie.
Band 1: Struktur . G. Quinkert, E. Egert, C. Griesinger
I: Carell ..............................................
Classified 1153
1243
Keyword Index 1244
Author Index 1245
Preview 1246
The following reviews will appear in future issues:
CC-1065 and the Duocarmycins : Mechanistic Studies
Dale L. Boger and Douglas S. Johnson
What Can We Learn from Molecular Recognition in Protein-Ligand Complexes for the Design of New Drugs?
Hans-Joachim Bohm and Gerhard Klebe
Recent Developments in Molecular Chemistry for Sol-Gel Processes
Robert Corriu and Dominique Leclercq
Glycals in Organic Synthesis: The Evolution of Comprehensive and Powerful Strategies for the Assembly
of Oligosaccharides and Glycoconjugates of Biological Consequence
Samuel J. Danishefsky and Mark Bilodeau
Chemistry and Biology of the Zaragozic Acids (Squalestatins)
K. C. Nicolaou and Alan Nadin
Saccharide Sensing with Boronic Acid-Based Molecular Receptors
K. R. A. Samankumara Sandanayake, Tony D. James, and Seiji Shinkai
Polymers and the Periodic Table:
Recent Developments in Inorganic Polymer Science
Ian Manners
Enantioselective Protonation of Enolates and Enols
C. Fehr
Chiral Recognition in n Complexes of Alkenes, Aldehydes, and Ketones with Transition Metal Lewis Acids;
Development of a General Model for Enantioface Binding Selectivities
J. A. Gladysz, B. J. Boone
Structural Aspects of Nucleic Acid Analogs and Antisense Oligonucleotides
Martin Egli
1148
8 VCH
Verlagsgesellsrhaft m b H . 0-69451 Weinherm,1996
0570-083319613511-1148 $15.00+ ,2510
Angew. Chem. Inl. Ed. Engl. 1996, 35,No. 11
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