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Graphical Abstract Angew. Chem. Int. Ed. 252004

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Contents
The following Communications are available online (in Wiley InterScience). You can find them, as
well as forthcoming Reviews, Highlights, and Essays, at www.angewandte.org, under Early View.
F. Turcu, A. Schulte, G. Hartwich, W. Schuhmann*:
Label-Free Electrochemical Recognition of DNA Hybridization by
Means of Modulation of the Feedback Current in SECM
DOI: 10.1002/anie.200454228
Published online: June 9, 2004
S. J. George, A. Ajayaghosh,* P. Jonkheijm, A. P. H. J. Schenning,
E. W. Meijer:
Coiled-Coil Gel Nanostructures of Oligo(p-phenylenevinylene)s:
Gelation-Induced Helix Transition in a Higher-Order Supramolecular Self-Assembly of a Rigid p-Conjugated System
DOI: 10.1002/anie.200453874
Published online: June 4, 2004
Articles judged by the referees or the editor as being either very important or very urgent are immediately edited, proof-read, and electronically
published once the manuscript has arrived in the editorial office in its final form. As long as there is no page number available these articles should
be cited in the following manner:
Author(s), Angew. Chem. Int. Ed., online publication date, DOI.
Meeting Reviews
Ordered Porous Nanoarchitectures with Specific Functions
3216 ? 3217
N. Hsing
Books
Bioactive Natural Products
3218
Fundamental World of Quantum
Chemistry
3219
Atta-ur-Rahman
reviewed by F. von Nussbaum
Erkki J. Br$ndas, Eugene S. Kryachko
reviewed by M. Reiher
Highlights
Protein Design
A. Tramontano*
A deeper understanding of the sequence?
structure relationship in proteins has
resulted from research in the field of
protein design. Recent success in designing a protein with a topology not yet
observed in nature (see picture) increases
our confidence in computational biology
and should open the road to the engineering of molecular machines with
specified properties and functions.
3222 ? 3223
A Brighter Future for Protein Design
Essays
Industrial Chemistry
J. M. Hawkins,*
T. J. N. Watson
Asymmetric Catalysis in the
Pharmaceutical Industry
3208
3224 ? 3228
The best catalyst from a chemical
perspective is not necessarily the best
catalyst from an overall economic
perspective. In competing approaches to
candoxatril the most selective catalyst for
the asymmetric hydrogenation (see
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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scheme) was not the one ultimately
chosen. The constraints of the pharmaceutical industry are discussed with
regard to the application of asymmetric
catalysis to the large-scale synthesis of
drug candidates and commercial drugs.
Angew. Chem. Int. Ed. 2004, 43, 3208 ? 3215
Angewandte
Chemie
Reviews
Natural Products Synthesis
The tubulin-binding alkaloid colchicine
(1), isolated from the meadow saffron, is
an antimitotic agent with a great pharmaceutical potential. Only a few other
natural products have proved to be such a
challenge to synthetic chemists for half a
century. The comparative analysis of the
often fascinating synthetic strategies
reveals why this seemingly simple structure still belongs to the ?difficult targets?.
T. Graening,
H.-G. Schmalz*
3230 ? 3256
Total Syntheses of Colchicine in
Comparison: A Journey through 50 Years
of Synthetic Organic Chemistry
Communications
Addition Reactions
R. Matsubara, Y. Nakamura,
S. Kobayashi*
3258 ? 3260
The remarkably selective addition of enecarbamates 2 to ethyl glyoxylate (1) in the
presence of a copper?diimine catalyst
(0.1 mol %) gives the corresponding
imines 3 in high yields with excellent
enantioselectivities. A concerted aza-enetype reaction mechanism was proposed to
explain the stereochemical outcome.
Highly Diastereo- and Enantioselective
Reactions of Enecarbamates with Ethyl
Glyoxylate To Give Optically Active syn and
anti a-Alkyl-b-Hydroxy Imines and
Ketones
Molecular Shuttles
J. S. Hannam, S. M. Lacy, D. A. Leigh,*
C. G. Saiz, A. M. Z. Slawin,
S. G. Stitchell
3260 ? 3264
Sew simple: How can you put a molecular
bead on a thread when no recognition
elements exist between them? A
mechanically interlocking auxiliary
assembles the macrocycle around a tem-
plate, controlled submolecular translation
moves the ring over the desired substrate
and, finally, cleavage of the auxiliary leaves
an apparently ?impossible? rotaxane (see
scheme).
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Angew. Chem. Int. Ed. 2004, 43, 3208 ? 3215
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Controlled Submolecular Translational
Motion in Synthesis: A Mechanically
Interlocking Auxiliary
individuals who are personal members of a
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2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
3209
Contents
Folded Polymers
S. Ghosh,
S. Ramakrishnan*
Designer folds: The interplay of three
design elements (aromatic donor?
acceptor charge-transfer complexation,
solvophobic effect, and metal-ion complexation) guided the preparation of a
folded structure (see picture) in a
synthetic macromolecule. Evidence for
this is provided by UV/Vis and 1H NMR
spectroscopy.
3264 ? 3268
Aromatic Donor?Acceptor Charge-Transfer and Metal-Ion-Complexation-Assisted
Folding of a Synthetic Polymer
Microporous Materials
T. K. Maji, K. Uemura, H.-C. Chang,
R. Matsuda, S. Kitagawa*
3269 ? 3272
Expanding and Shrinking Porous
Modulation Based on Pillared-Layer
Coordination Polymers Showing
Selective Guest Adsorption
Mechanically Interlocked Compounds
J. D. Badjic?, S. J. Cantrill, R. H. Grubbs,*
E. N. Guidry, R. Orenes,
J. F. Stoddart*
3273 ? 3278
The Exclusivity of Multivalency in Dynamic
Covalent Processes
Rationally designed and synthesized, two
novel pillar-layered 3D microporous
frameworks {[Cd(pzdc)(azpy)]�H2O}n (1,
left) and {[Cd(pzdc)(bpee)]�5 H2O}n (2,
right) have high thermal stability and
highly selective adsorption properties.
Removal of guest water molecules results
in the expansion of 1 but the contraction
of 2.
Less is more: It is much less efficient to
synthesize both components of a multivalent recognition site separately than it is
to use one multivalent component to act
as a template for the catalytically orchestrated construction of the other component, as demonstrated by the formation of
the mechanically interlocked, triply
threaded molecular bundle shown. The
situation is reminiscent of nature.
Template Synthesis
M. Numata, K. Sugiyasu, T. Hasegawa,
S. Shinkai*
3279 ? 3283
Sol?Gel Reaction Using DNA as a
Template: An Attempt Toward
Transcription of DNA into Inorganic
Materials
3210
The topologically different structures in
plasmid DNA can be successfully transcribed into silica structures by using the
DNA as a template for sol?gel polycondensation of tetraethoxysilane after treat-
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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ment by two cation-exchange steps (see
scheme). These findings imply that the
different ordered silica structures can be
created from the same template through
its higher-order conformational changes.
Angew. Chem. Int. Ed. 2004, 43, 3208 ? 3215
Angewandte
Chemie
Polyfunctional gels: Thermoreversible
switchable gels with tunable magnetic,
optical, and rheological properties are
obtained from a modified spin-crossover
polymeric precursor and alkane solvents
(see picture). The iron triazole polymer
which acts as the gelator, undergoes a
spin crossover that is accompanied by a
change in the color of the gel. The transfer
of spin-crossover properties from solid
materials into gels offers a route to new
applications.
Spin Crossover in Gels
O. Roubeau, A. Colin, V. Schmitt,
R. ClTrac*
3283 ? 3286
Thermoreversible Gels as
Magneto-Optical Switches
Ab initio calculations were used for the
rational design of efficient alcohol oxidation catalysts that mimic the enzyme
galactose oxidase. Different ligand substitutions were explored based on natural
(copper, depicted) and alternative (rhodium) metal redox centers. The calculated
turnover rate for the most efficient copperbased biomimetic compound is greater
than that of the natural enzyme.
Computer Chemistry
Intercepting Carcinogens: The cancerpreventing properties of inorganic species, such as selenium and vanadium, are
well known, but mechanistic understanding is scant. It is shown that inorganic oxo
species (e.g., [SeO4]2 , [VO4]3 ) can prevent DNA alkylation as well as detoxify
alkylating agents by promoting hydrolysis
to relatively harmless alcohols (see
scheme).
Cancer Prevention
Shuttle of electrons: A redox-active bisbipyridinium cyclophane stoppered by the
enzyme glucose oxidase (GOx) in a
rotaxane configuration on a molecular
wire linked to a gold electrode (see
picture) leads to the effective electrical
contacting of the biocatalyst that oxidizes
glucose at 0.4 V (versus saturated calomel electrode).
Nanotechnology
Angew. Chem. Int. Ed. 2004, 43, 3208 ? 3215
L. Guidoni, K. Spiegel, M. Zumstein,
U. RUthlisberger*
3286 ? 3289
Green Oxidation Catalysts:
Computational Design of High-Efficiency
Models of Galactose Oxidase
E. E. Hamilton, J. J. Wilker*
3290 ? 3292
Inorganic Oxo Compounds React with
Alkylating Agents: Implications for DNA
Damage
E. Katz, L. Sheeney-Haj-Ichia,
I. Willner*
3292 ? 3300
Electrical Contacting of Glucose Oxidase
in a Redox-Active Rotaxane Configuration
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2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
3211
Contents
Reaction Intermediates
J. Cho, H. Furutachi, S. Fujinami,
M. Suzuki*
3300 ? 3303
A Bis(m-alkylperoxo)dinickel(ii) Complex
as a Reaction Intermediate for the
Oxidation of the Methyl Groups of the
Me2-tpa Ligand to Carboxylate and
Alkoxide Ligands
A radical approach: The reaction of
[Ni2(OH)2(Me2-tpa)2]2+ with H2O2 resulted
in the peroxidation of a methyl group of
the Me2-tpa ligand to produce a bis(malkylperoxo)dinickel(ii) complex (see
ORTEP diagram) as a reaction intermediate for further oxidation to carboxylato
and alkoxo complexes [Ni(Me1-tpaCOO)]+ and [Ni2(Me1-tpa-CH2O)2]2+.
Me2-tpa = bis[(6-methyl-2-pyridyl)methyl]
[(2-pyridyl)methyl]amine.
Supported Catalysts
C.-M. Ho, W.-Y. Yu,*
C.-M. Che*
3303 ? 3307
Ruthenium Nanoparticles Supported on
Hydroxyapatite as an Efficient and
Recyclable Catalyst for cis-Dihydroxylation
and Oxidative Cleavage of Alkenes
Impregnation of hydroxyapatite with colloidal ruthenium results in the formation
of a catalyst that effects cis-dihydroxylation
and oxidative cleavage of alkenes to their
respective cis-1,2-diols and carbonyl
products in good to excellent yields (see
scheme). The supported ruthenium catalyst can be easily recycled and reused for
consecutive reaction runs without significant deterioration of the catalytic activities. R1, R2 = H, alkyl, aryl.
Quaternary stereocenters that bear a
sulfur substituent can be created with
nearly perfect stereocontrol through an
intramolecular Michael-type process.
Lewis acids (L.A.) accelerate the intramolecular sulfur-atom transfer from the
oxazolidine-2-thione functionality to the
b carbon atom of the b,b-disubstituted
enoyl moiety, whereas the chirality of the
oxazolidine-2-thione portion controls
reaction stereochemistry (see scheme).
Asymmetric Synthesis
C. Palomo,* M. Oiarbide, F. Dias,
R. LVpez, A. Linden
3307 ? 3310
Construction of C S Bonds with a
Quaternary Stereocenter through a
Formal Michael Reaction: Asymmetric
Synthesis of Tertiary Thiols
Kinetics versus Thermodynamics
J. M. Schicks,*
J. A. Ripmeester
The unexpected coexistence of structure I
(s I) and structure II (s II) methane
hydrates under conditions where only s I
hydrates should be stable (see picture)
suggests that the initial product is determined by kinetics. The state of coexistence as well as the transformation of the
kinetic product into the thermodynamically stable s I hydrate was documented by
microscopic visual observation as well as
Raman spectroscopy.
3310 ? 3313
The Coexistence of Two Different Methane
Hydrate Phases under Moderate Pressure
and Temperature Conditions: Kinetic
versus Thermodynamic Products
3212
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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Angew. Chem. Int. Ed. 2004, 43, 3208 ? 3215
Angewandte
Chemie
Enantiomeric Synthesis
S. Arseniyadis, A. Valleix, A. Wagner,*
C. Mioskowski*
3314 ? 3317
Solvents lend a hand: Changing the
polarity of the reaction solvent from 1,3dimethyltetrahydropyrimidin-2-one
(DMPU) to toluene reverses the stereoselectivity observed in the acetylation of
amines with (1S,2S)-1 (see scheme).
Optimizing the reaction conditions led to
an unprecedented 90 % ee (S) in DMPU at
20 8C with a 33 % conversion.
Asymmetric Amplification
The evolution of homochirality from
simple organic molecules can perhaps be
modeled on the proline-mediated aminoxylation of aldehydes (see scheme). The
observed accelerating reaction rate combined with an amplification of the enantiomeric excess of the product is attributed to an autoinductive reaction mediated by an adduct of proline and the
product.
S. P. Mathew, H. Iwamura,
D. G. Blackmond*
3317 ? 3321
Amplification of Enantiomeric Excess in a
Proline-Mediated Reaction
Strained, ring-tilted [1]ruthenocenophanes 1 have been prepared for the first
time. Ring-opening polymerization (ROP)
of an example of 1 with a Sn bridge affords
a novel, bimetallic, high-molecular-weight
polyruthenocenylstannane 2 (R = mesityl).
Bimetallic Polymers
U. Vogel, A. J. Lough,
I. Manners*
3321 ? 3325
Isolation of [1]Ruthenocenophanes:
Synthesis of Polyruthenocenylstannanes
by Ring-Opening Polymerization
Biomimetic Synthesis
A postulated biogenesis forms the basis
for a synthetic route to the natural product
anachelin H (1). Key steps include a
tellurium-mediated, oxidative aza annulation and a Claisen condensation under
mild conditions. Experiments with a
model substrate indicate that it is likely
that a catechol oxidase-type enzyme is
involved in the biosynthesis of the anachelin chromophore.
Angew. Chem. Int. Ed. 2004, 43, 3208 ? 3215
Kinetic Resolution of Amines: A Highly
Enantioselective and Chemoselective
Acetylating Agent with a Unique SolventInduced Reversal of Stereoselectivity
K. Gademann,* Y. Bethuel
3327 ? 3329
A Biomimetic Route to the Peptide
Alkaloid Anachelin
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2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
3213
Contents
Atmospheric Chemistry
S. von Ahsen,*
J. S. Francisco
3330 ? 3333
The Trifluoromethoxy Sulfuryl Radical,
CF3OSO2C
A radical with great implications: Matrixisolated CF3O radicals interact with SO2
yielding CF3OSO2C (see picture) when the
matrix is annealed at 35 K. The new
radical was characterized spectroscopically and studied by DFT calculations.
CF3OSO2C may have significant impact on
atmospheric processes.
Grignard Reactions
A. Krasovskiy, P. Knochel*
3333 ? 3336
A LiCl-Mediated Br/Mg Exchange Reaction for the Preparation of Functionalized
Aryl- and Heteroarylmagnesium
Compounds from Organic Bromides
A wide range of aryl and heteroaryl
bromides, which are usually sluggish in
exchange reactions, are readily converted
into the corresponding Grignard reagents
DNA Modification
S. J$ger, M. Famulok*
by means of a Br/Mg exchange reaction
triggered by iPrMgCl稬iCl (see scheme).
These Grignard intermediates react with
electrophiles in good yields.
Up to eight modifications could be incorporated into a DNA heteroduplex (see
picture) by introducing different sets of 2?deoxynucleotide derivatives through DNA
polymerase mediated primer extension.
All four natural nucleobases in each
strand were substituted with different
base-modified analogues. PCR conditions
are described that allow the direct amplification of fully functionalized DNA
double strands.
3337 ? 3340
Generation and Enzymatic Amplification
of High-Density Functionalized DNA
Double Strands
Communications labeled with this symbol have been judged by two referees as being ?very important papers?.
The issues for June 2004 appeared online on the following dates
Issue 21: May 12. � Issue 22: May 19. � Issue 23: June 1. � Issue 24: June 9.
Service
3214
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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Keywords
3342
Authors
3343
Sources
A41
Preview
3345
Angew. Chem. Int. Ed. 2004, 43, 3208 ? 3215
Angewandte
Chemie
Apology
*
In the Communication ?Block-Selected
Molecular Recognition and Formation of
Polypseudorotaxanes between Poly(propylene oxide)-Poly(ethylene oxide)-Poly(propylene oxide) Triblock Copolymers
and a-Cyclodextrin? by J. Li, X. Ni, and K.
Angew. Chem. Int. Ed. 2004, 43, 3208 ? 3215
Leong (Angew. Chem. Int. Ed. 2003, 42,
69?72), the authors neglected to crossreference their thematically related full
article in J. Am. Chem. Soc. 2003, 125,
1788?1795 by J. Li, X. Ni, Z. Zhou, and K.
Leong. The later full article reported the
www.angewandte.org
strong evidence for the formation of the
triblock copolymer architectures, as well
as details of the preparation and characterization of the polypseudorotaxanes.
The authors apologize for this oversight.
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
3215
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