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Graphical Abstract (Angew. Chem. Int. Ed. Engl. 41996)

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A Journal
of- the~
_
_
~
Gesellschaft
~Deutscher
Chemi
_
_
~ ker
1996
3514
353 464
International Edition in English
Pages
-
~~
COVER PICTURE
~~
The cover picture shows the catalytic asymmetric aminohydroxylation (AA) of alkenes in action. Methyl cinnamate can be transformed directly into a derivative of
the taxol side chain with the catalyst system K,OsO,(OH), and a phthalazine ligand; Chloraniine T serves as the nitrenoid source. Either enantiomer can be produced at will by selection of the appropriate ligand. The asymmetric aminohydroxylation (AA) follows the development of the asymmetric epoxidation (AE)
and the asymmetric dihydroxylation (AD)-three reactions whose importance for
organic synthesis cannot be overstated. Li. Chang, and Sharpless report more on the
new catalytic A A on p. 451 ff. (The cover picture was created by Michael E. Pique.
The Scripps Research Institute. La Jolla, CA, USA.)
REVIEWS-
-Contents
Two methods of making biomaterials photoswitchable ~ ~ ; ~ L 1 , , , , , ,
are presented here: the covalent linkage of photoisonierizablc components (A $ B) to biomolccules and
dthe interaction of the bjomaterials with photoswitchable microenvironments. The diagram on the
i
right iII~sti-ates
the first principle with the formation B~,.
and dissociation of. for instance, an enzyme-subSwitch -"ON"
Switch -"OFF"
strate o r antibody-antigcn assembly. In the isomer
state A the hioactive structure of the biomaterial is retained. and formation of the
complex with the substrate is activated. In the photoisomer state B the active site is
distorted. and dissociation is induced. Such modified compounds form the basis of
opto-bioelectronic devices.
\o
/$
4*r'c4
<_
I. Willner.* S. Rubin
........
......
367-385
Control of the Structure and Functions of
Biomaterials by Light
I
The willingness to undergo oxidative addition of electrophiles. the high selectivity, and
several unrxpectcd reactions are responsible for making the title compounds, which
had been disregarded or unknown for a long time. widely applicable, mild alkylating
reagents. For cxaniple. (E.Z)-~-fluorostyrenecan be converted with Me,CoLiz into
(E,Z)-l-phen)Iproprene in 92% yield. The reaction of bromophenylacetylene with
MeCo(CN)ZLi(see below) shows other possibilities.
T. Kauffmann *
. . _ _ _ _ . _ _ . . . . . . . . . . 386-403
.._.._
Nonstabilized Alkyl Complexes and AlkylCyano-Ate Complexes of Iron(ii) and
Cobalt(ii) as New Reagents i n Organic Synthesis
A prime example of applied radical chemistry is the last step of Curran's total synthesis of the antitumor agent camptothecin (below). This and other key sequences
demonstrate the importance of radical reactions in natural products chemistry.
wo
PhNC. Me3SnSnMe3
hv, 70 OC
*
63%
U. Koert * .....................................
405-407
Radical Reactions as Key. Steps
. in Natural
Product Synthesis
\.'OH
camptothecin
Very different ligands have been employed recently
for enantioselective hydrogenation. With rhodium
phospholane complexes, not only the usual. but also
highly substituted enamides such as 1 and acylhydrazones can be hydrogenated. With ruthenium
complexes containing chiral amino alcohols.
ketones can be converted into the corresponding
alcohols with high enantioselectivities.
CO,R"
J. Albrecht, U. Nagel* ............... 407--409
Enantioselective Catalytic I Iydrogenation
R
o=(H f?"'
1
COMMUNICATIONS
Crossed ring-opening metatheses (ROM) close the gap between ring-opening
metathesis polymerization (ROMP) and ring-closing metathesis (RCM). According
to this principle, easily accessible functionalized bicycles of type 1 and symmetric
olefins 2 can be converted with ruthenium catalysts into highly substituted fivemembered rings of type 3.
R
M. F. Schneider, S. Blechert*
____
411 -412
Synthesis of Highly Substituted Cyclopentane and 'Ietrahydrofuran Derivatives by
Crossed Olefin Metathesis
R
X = CH,; 0
FG = functional group
R = CZH, ; CHflCH3
1
2
FG
3
The reaction of acid N,N-dialkylamides with alkylmagnesium bromides in the presence of a stoichiometric amount of titanium tetra(2-propanolate)
produces dialkylcyclopropylamines like 1 and 2 in
moderate to good yields. Previously inaccessible
aminocyclopropane derivatives are now readily
available.
V. Chaplinski. A. de Meijere* .... 413-414
[tN(Rr),
2 76%
=
Novel chain extensions of [{Re*} -C C -C =C -€11
({Re*) - (r~'-C,Me,)Re(NO)(PPh,)) with alkyne
or diyne building blocks lead to rhenium-capped
oligomers of up to 20 sp carbon atoms (shown on
the right, n -- 6, 8, 10). This methodology allows.
for the first time, access to such materials with a
homogeneous chain length
A Versatile New Preparation of Cyclopropylamines from Acid Dialkylamides
-1.. Rartik, B. Bartik,
RP
ON,
I p,ph,
Re
M. Brady, R . Dembinski,
J. A. Gladysz* _ _ _ _ _ _ _ .._ ._ _ _414-417
____........._
A Step-Growth Approach to MetalCapped One-Dimensional Carbon Allotropes: Syntheses of C , , , C,,, and czopPolyynediyl Complexes
Relief of strain is the driving force for the [2+ 21 cycloaddition and subsequent [2+ 21
cycloreversioii of 1 with both open-chain and cyclic alkenes. The metathesis can even
be performed with benzene as the olefin component [Eq. (a)]. The product can be
roughly described as a ribbon- or beltlike conjugated system.
S. Kammermeier, R. Herpes* .... 417-419
Photochemically Induced Metathesis Reactions of ‘Ietradehydrodianthracene: Synthesis and Structure of Bianthraquino-
1
the rert-butyl groups of
[ ~ ~ ~ N ( ~ B U ) [ S I ( C H , ) ~ ( I(struc~)]},]
ture shown on the right) reside on the
same face of the N, plane, whereas
all SI-CH, groups are rotated
toward the periphery of the molecule. This results in E r - I I interatomic distances of 731.7-236.7 pm
for the Si-H moieties folded in toward the metal center.
All
W. S. Rees, Jr.,* 0. Just, H. Schumann.*
R. Weimann ...............................
419 -422
C31
Structural Characterization of a Tris-Agostic Lanthanoid-tI-Si Interaction
C36
cI1
Eight-coordination and identical ligand environments
have been unequivocally established in the pair of
stable iron(n) and iron(ii1) complexes shown on the
right The s) nthesis, structures and electrochemical
properties of these iron complexes are presented
here. together with some Mossbauer spectroscopic
data on the iron(i1) complex.
W. 0. Koch. A. Barbieri, M. Grodzicki.
V. Schunemann, A. X. Trautwein,
II.-J.Kruger* ............................
\/H
N
’
N‘H
Redox reactions in the initial productsformed from K,[Cr(CO),] and CI,ER (E = Al,
G a ; R = C1. alkyl) lead to the formation of aluminum(1) and gallium(1) transition
metal complexes of type 1 (shown below) that are surprisingly stable. Stoichiometric
CrGa films were prepared from 1 (E = Ga. R - CH,CH,) by MOCVD. tmeda =
N , N . N’.N’-tetramethylethylenediamine.
422 424
Eight-Coordinate Iron(ir) and Iron(ni) Ions
in Complexes with Distorted Dodecahedra1
FeN, Environments: Synthesis and Structures of Bis(2.11 -diaza[3.3)(2,6)pyridinophane)iron Complexes
M.M . Schulte, E. Herdtweck,
G. Raudaschl-Sieber,
R. A. Fischer* ...........................
424 426
Transition Metal Stabilized All and Ga’
Complexes; Structure of [(CO),Cr-Ga-
1 THF. -78 25’C
7
K2[Cr(CO)51+ C12ER
I
lmeda. CH,C:,
- 2 KCI
1
Since the porous structure iscompletely retained upon surfactant removal. Nb-TMSI,
a hexagonally packed mesoporous transition metal oxide, is an interesting molecular
sieve. The synthesis of this material was accomplished by a novel route in which the
inorganic precursor 1 and the surfactant 2 were attached by a covalent N b - N bond;
this bond is probably retained throughout the course of the synthesis.
Nb(OFr),
I
A n w i t ’ Chcm I u r Ed.
C!,H,,NH,
11. M. Antonelli, J. Y. Ying* ...... 426-430
Synthesis of a Stable Hexagonally Packed
Mesoporous Niobium Oxide Molecular
Sieve Through a Novel Ligand-Assisted
Templating Mechanism
2
Etr,d. 1996. 35. N o . 4
VCIi Verla,qsgrsrllscha/r inbH. 0-69451 Wernherm. 1996
0570-0833i9413504-0357 S I 5 00 t 2f;O
351
Enantiomeric excesses of up to 82% are obtained for the r.r-disubstituted products
4 arising from alkylation reactions of borane-amine adducts 2 and 3. which have a
chiral nitrogen atom. The structure of diastereomer 2. which can be obtained selectively in the boration of I , has been established by single-crystal X-ray analysis.
BH3-
I
Bn 'I'C
O
Z
M
,eN
,+
Me
I
Bn,N\/C02Me
-
M$
!
2
Me
-
Chiral Borane-Amine Adducts in Asymmetric Synthesis: Alkylation of Alanine
Derivatives
Me
I
COZMe
N
Bn'
NXC02Me
/ \
R
Me
V. Ferey, L. Toupet. T. L.e Gall,
C. Mioskowski* ___.___...__._..........
430-432
1
Me
4
A structure containing two cubes linked through a
common metal atom (1) is formed on reaction of the
novel tripodal ligand [( Re(CO), )3(011)4]- with M"
salts (M = Mn, Cu). Crystals of 1 contain extended
layers whose structures are determined by the type
of coordination sphere of MI'. 0 - Re(CO),; Counterion: NEt,' .
W. A. €krrmann.* A. Egli, E. Herdtweck.
R. Alberto. F. Baumgartner ...... 432-434
Y
1
H
A three-coordinate, cationic germanium center is
the unusual feature of this dimeric tungsten complex 1 generated by the thermolysis
[CpzW(SiMe3)(GeMe,0Tf)]. Delocalization Of
of
the charge onto only one of the tungsten centers is
suggested by structural and orbital overlap considerations.
Me. Me
OTf-
e
:
,
*\ie' '
0
w-.- +
I Ieterobimetallic Ilydroxy Complexes:
[Re3(CO),(p,-OH),(~~,-OH)]-as a Novel
Tripodal Ligand
W'"'
Me
1,. K. Figge, P. J. Carroll,
D. 11. Berry* ...__._______________.______
435-437
Synthesis and Structure of a Bridging
Germylidyne Complex: A Stable Germyl
Cation
1
.
The cassava species Munihot esculen0
OH
S. Forster. J. Roos. E Effenberger,*
1
II
(SbMNL
H . Wajant, A. Sprauer _ . . _ _ . _ _ _ 437-439
______
tu provided the first recombinant hyR/c, R1 + HCN
,p,g
R/CvcN
droxynitrile lyase (MeHNL) that beR'
came accessible by overexpression in
(S)
The First Recombinant Hydroxynitrile
Lyase and its Application in the Synthesis
E. coli. This MeHNL catalyzes the
enantioselective addition of H C N (depicted below) not only to aliphatic. aromatic,
of (S)-Cyanohydrins
and heteroaromatic aldehydes, but also to ketones to give (S)-cyanohydrins in high
optical yields. R = alkyl, aryl. heteroaryl; R' - H, CH,
-_.
.
..
.. . . . .._
All seven redox states between the tricationic dnd the
trianionic states of the decacyclenyl I ' are discernible by cyclic voltammetry The electronic ndture of the highly delocalized aromdtic n-electron
system of the neutral radical 1' and the charged species 1' ' and 1 3 - has been investigated by ESR and
NMR spectroscopy. respectively
-
1-
I Kubo, K Ydmamoto, K Ndkasuji,*
T Tdkui, I Murdta
439-441
&'
Hexd-tert-butyltribenzodecacyclenyl A SixStage Amphoteric Redox System
1'
Through formationof a contact pair. bases are capable of transferring mobile protons
from one molecular site to another. N M R experiments on a solution of diaryltriazenc 1 i n ethyl methyl ether in the presence of trimethylamine (2) [Eq. (a)] verify
that the contact pair does not dissociate in the process.
N-H'
F. Mannle, H.-I?. I,imbach* ...... 441 -442
An Intramolecular Base-Catalyzed Proton
Transfer in 1.3-Bis(4-fluorophenyl)triazene
N-CH,
2
F
1
_
~
Tertiary alcohols like 2 can prepared from 1 in two steps by palladium-catalyzed
hydrostannylation followed by an organolithium-induced ring opening. Compounds regioisomeric to those obtained with [Ni(cod),]/DIBAL-H are thus now
available.
'eH
1 . Bu,SnH. [Pd,(dba),]. PPh,
-
-
_
~
M . Lautens,* W. Klute .............. 442-445
Kegioselective Palladium-Catalyzed Hydrostannylation of Unsymmetrical Oxabicyclic Alkenes
*"
Q
OH
2 . MeLt
It,,,
2
1
.~
~
Linear pairing complexes are presumably formed by peptide nucleic
acids containing a backbone of
alanyl amino acids with alternating
configuration. The pairing of two
strands is based on recognition of the
nucleobases: however. unlike for
DNA. stable self-pairing of a hexamer from adenine-substituted alanyl
building blocks is possible for the
PNA (1) described herein.
.~
U. Diederichsen * .......................
H
445 -448
Pairing Properties of Alanyl Peptide
Nucleic Acids Containing an Amino Acid
Backbone with Alternating Configuration
1
O
H
-.
Remarkably high ee values in the asymmetric dihydroxylation reaction (AD) can be
achieved with the pseudo-enantiomcric ligand pair (DHQD),AQN and
(DIIQ)>AQN.These new ligands are superior for AD reactions of most olefins with
aliphatic substituents and show exceptionally high enantioselectivity with olefins
having heteroatoms in the allylic position [Eq. (a)]. DFIQD = dihydroquinidinyl.
o
H. Becker, K. B. Sharpless* ...... 448-451
A New Ligand Class for the Asymmetric
Dihydroxylation of Olefins
ODHQD
0.4% 0 s
~.
The stereospecific cis addition of "1sN" and H 2 0 yields 2-hydroxy-N-tosylamines
(see below). This osmium-catalyzed process, which depends on Chloramine-?' as the
nitrenoid source, is rendered asymmetric in the presence of cinchona alkaloid
ligands. The selectivities for reactions of the six olefins studied range from 33 % ee
(cis-stilbene)to 81 YOee (rrans-methylcinnamate). The active agent is presumably the
compound Os(O),NTs shown in square brackets. (I>HQ),-PHAL, = bis(dihydr0quininy1)phthalazine (see preceding communication).
I
64%. 45% ee
H
-.
G. Li, H.-T. Chang,
K. €3. Sharpless* ........................
451 -454
Catalytic Asymmetric Aminohydroxylation (AA) of Olefins
Con tents
Replacing the tosyl with a nosyl (Ns) g r o u p t h a t is the key to an improved method
for both allylic amination of olefins and 1,2-diamination of 1,3-dienes. The protecting group recently introduced by Fukuyama et al.. the o-nitrobenzenesulfonyl (nosyl) group, can be employed with diimidoselenium reagents. The resulting nosylamides can be converted into primary and secondary amines in good to excellent
yields. An example of this approach is sketched below in reaction (a) (R = Me,
CI I ,CH C €I z, (1 H ,Ph) .
M. Bruncko, T.-A. V. Kuong,
K. B. Sharpless* ........................
454-456
Allylic Amination and 1.2-Diamination
with a Modified Diimidoselenium Reagent
NsN=Se=NNs
Q -
QNHN'=
QNHR
NHNs
1
(5)-2
NHR
(t)-3
Author 10 whom correspondence should be addressed
-
BOOKS
Organosulfur Chemistry. Synthetic Aspects
P. Page
Introduction to Biocatalysis Using Enzymes and Micro-Organisms
N. J. Turner, A. J. Willetts, M. K. Turner
. S. M. Roberts,
R. Beckerl ..........................................
457
R. Csuk ..............................................
458
New Books
459
Events 361,410
Classified 362
Sources 363
Keywords 460
Author Index 461
Preview 462
The following reviews will appear in future issues:
The Total Synthesis of Brevetoxin B. A Twelve-Year Odyssey in Organic Synthesis
K. C. Nicolaou
Electrosprdy Mass Spcctrometry of Supramolecular Complexes of Biomacromolecules-New
Supramolecular Chemistry and Molecular Recognition Processes
M. Przybylski
Analytical Perspectives for
Friedrich IIund and Chemistry
W. Kutzelnigg
A First Step towards Planning of Synthesis in Solid-state Chemistry : Determination of Promising Structure Candidates IJsing a
Modular Approach
M . Jansen, J. C. Schon
Protonation of IJnsaturated IIydrocarbon Ligands: Regiospecificity, Stereospecificity, and Product Specificity
R . A. IIenderson
The Mechanism of the Claisen Rearrangement: Deja Vu All Over Again
B. Ganam
Analogues of Carbenes, Olefins, and Small Rings from Main Group Chemistry
M. DrieR. 11. Grutzmacher
What can we learn from Molecular Recognition in Protein-1.igand Complexes for the Design of New Drugs?
11.-Joachim Bohm, G. Klebe
Enzyme Mechanisms, Models and Mimics
A. J. Kirby
IJnderstanding and Manipulating Inorganic Materials IJsing Scanning Probe Microscopes
C. M. Lieber, J. Liu. P. I<. Sheehan
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