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Graphical Abstract (Angew. Chem. Int. Ed. Engl. 181995)

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_
__
.
International Edition in English
___
A_Journal
of the
_
GeselIschaft
_
_ --______
~
Deutscher
Chemiker
~
~
1995
34/18
Pages 1911-2066
COVER PICTURE
The cover picture shows a space-filling molecular model of the CaI + mobilizing
second messenger i>-mjo-inositol 1.4.5-trisphosphate superimposed on a sea urchin
egg that has been injected with a [Ca' +]-dependent fluorescent indicator to depict
concentrations of C a 2 + in pseudocolor. Fertilizing sperm bound to the egg at the
bottom left triggered a Ca2+-concentrationwave (green: [Ca"] low-about 1 0 0 n ~ ,
resting state; red: [Ca"] high several P M ; yellow: intermediate range). The local
increase of the Ca2 concentration at the binding site propagates as a regenerative
w;ive throughout the entire cell. Inositol 1,4,5-triphosphate is one of the intracellular
messengers that orchestrate this wave. More about inositol mediated processes is
reported o n pp. 1933 -1972 by B. V.L. Potter and D. Lampe. The authors thank
Dr. A . Galione. Oxford University, for the fluorescence imaging data, and Mr. K.
Smith m d Dr. A. S. Thompson, University of Bath, for molecular modeling.
REVIEWS
Contents
A renaissance in inositol phosphate chemistry was
0
initiated twelve years ago by the discovery of the
~ - o z ~ ~
role of wijwinositol 1.4.5-trisphosphate (1) as a sec2 - 0 ~ ~ 0
5HO
1
ond messenger. Since then, numerous methods for
the synthehis o C regiospecifically protected inositols
1
and optically active inositol phosphate regioisomers
and their nnalogues have been established with the
intent of elucidating biological roles for the some of the vast array of naturally
occurring inositol phosphates. The first pharmacological and biochemical agents are
already available for intervention in cellular signaling pathways mediated by the
hydrolysis o f polyphosphoinositide lipids.
a
With modern mass spectrometric techniques much information about reactions (pattern of reacti\ity, selectivity, intermediates) is accessible for the gas phase. Even if
the results ot. for instance. oxidations with MO' ions (isolated, charged molecules
without counterions in a highly dilute atmosphere, undergoing strictly bimolecular
reactions) arc not directly applicable to the analogous reactions in condensed phase,
a knowledge of the elementary steps obtained thus is needed for the rational design
o f such catalysts.
B. V. L. Potter,*
D.
~ Lampe
o : ._.____...___.___.._.._._.......
1933- 1972
Chemistry of Inositol Lipid Mediated
Cellular Signaling
D. Schroder, H. Schwarz*
.....
1973-1995
C - H and C--C Bond Activation by Bare
Transition-Metal Oxide Cations in the Gas
Phase
HIGHLIGHTS
Contents
From objects of speculation to manipulable compounds: Two research groups have
achieved the synthesis of the long sought metal complexes with terminal phosphido
(P”) hgdnds by independent routes, and both papers can be found in this issue of
Angewnnclre Chemie. Cummins et al. report on the synthesis of 1 on p. 2042ff,
Schrock et al. on the synthesis of 2 on p. 2044ff. Together with phosphaalkynes
R C = P these are the first compounds with a singly coordinated phosphorus and will
be of interest to theoreticians and preparative chemists alike. R = C(CD,),CH,;
Ar = 3,5-C6H,Me,; N,N = (Me,SiNCH,CH,),N; M = Mo, W).
[(NRAr),Mo-PI
1
[(N,N)M=P]
M. Scheer* ............................
1997- 1999
Terminal E, Ligands from Elements of
Group 15
2
The acylation and phosphorylation pattern determines the effectiveness of disaccharide antagonists of lipid A (lipid A from
Escherichia coli is shown on the
right), the toxic principle of
sepsis-inducing endotoxins from
Gram-negative bacteria. These
antagonists. which have not
shown toxic activity for humans,
have now been synthesized.
0. Hoist* ...............................
.O
/
0
II
2000- 2002
~
Endotoxin Antagonists: Possible
Candidates for the Treatment of
Gram-Negative Sepsis
’:‘OH
HO
CORRESPONDENCE
What’s in a name?! The letters discuss the usefulness of assigning qualitative concepts to the results of rigorous mathematical calculations. Exact definitions of the
terms d o not solve the dilemma, but pitfalls can be avoided with a knowledge of the
assumptions behind the calculations.
L. C. Allen,* J. K. Burdett ............... 2003
J. C. Schon* .....................................
2004
The Metallic Bond-Dead
A Comment and a Reply
or
Alive?
COMMUNICATIONS
A new application of chiral titanates such as 1 is the
catalysis of the asymmetric addition of boranes to a
ketocarbonyl group. Chiral alcohols are obtained in
this reaction in good enantiomeric excesses ((S):( R )
lies between 65 : 35 and 92: 8).
Po:.
‘-.x
,Ti(i-pr%
Ph Ph
1
Diastereoselective electrochemical reduction-a very promising route to heterobicycles
2. The cathodic cyclization of oxoalkylpyridinium salts 1, n = 2, in aqueous sulfuric
acid leads to the quinolizidines 2a,b (58 % yield), whereas 1, n = 1, reacts selectively
to give the indolizidine 2a in 55% yield. Pyridoazepines 2a,b, n = 3, are also
accessible.
1
1914
Za
G . Giffels, C. Dreisbach, U. Kragl,
M. Weigerding, H. Waldmann,
C. Wandrey * .........................
2005 -2006
Chiral Titanium Alkoxides as Catalysts for
the Enantioselective Reduction of Ketones
with Boranes
R. Gorny, H. J. Schafer,*
R. Frohlich ............................
2007-2009
Diastereoselective Cathodic Cyclization of
1-(4- and 1-(3-0xoalkyl)pyridiniumSalts to
Quinolizidine and Indolizidine Derivatives
2b
(c) VCH Vrrlu~.s~e.s@ll,schaft
m h H , D-6Y451 Wcinhrbn, 1995
0570-0X33:95/341X-/YI4 5’ l(J.(JlJ+ .25/0
A n g r w . Chun. Int. Ed. Ennl. 1995, 34. NCJ.18
f'nntpntc
Two previously undetected automerization processes occur among C,H, isomers. O n
irradiation at i. = 313 nm, compounds 1a.b equilibrate via 3a.b; irradiation of
compounds 2a,b a t longer wavelengths (L> 444 nm) also leads to their interconversion, perhaps via a cyclopropyne
intermediate or transition state.
. . .
. ."
H
Y
H
H
Y
d
3a
2b
Ester enolate Claisen rearrangement of the N-protected amino acid allylic esters I
affords the corresponding chiral r-allylic amino acids 2 in excellent yields and selectivities. The quinine used for the induction can be almost completely recovered in the
workup. Recrystallization with 1 -phenylethylamine gives enantiomerically pure 2.
R = alkyl, phenyl.
1
Automerizations and Isomerizations in
Propynylidene (HCCCH), Propadienylidene (H,CCC). and Cqclopropenylidene
*
2a
3b
R. A. Seburg.
R. J. McMahon* ................... 2009-2012
U. Kazmaier,* A. Krebs ........ 2012-2014
Synthesis of Chiral ;,,&Unsaturated Amino
Acids by Asymmetric Ester Enolate Claisen
Rearrangement
2
Stable to surfactant removal by calcination. Ti-TMSI is the first hexagonally packed,
mesoporous transition metal oxide. The synthesis of this new material was achieved
by ;I modified sol-gel technique from titanium alkoxides and phosphate surfactants.
The large internal surface area, narrow and controllable pore size, thermal stability,
and variablc oxidation states of the metal give this new material great potential as
a catalyst and sorbent.
D. M. Antonelli,
J. Y Ying* .............................
2014-2017
Synthesis of Hexagonally-Packed Mesoporous TiO, by a Modified Sol-Gel
Method
H. J. Bestmann,* H. P. Oechsner,
L. Kisielowski, C. Egerer-Sieber,
F. Hampel .............................. 2017-2020
The first P"-CR=PV species with a five-coordinate
and a four-coordinate phosphorus atom, the title compound 1 in which R is CH, or PhC=CHPh, for
example, were synthesized from 1,3-diphosphaallyl
cations and sodium hexamethyldisilazanide. Its
"central" C atom has ylidic character. On heating
the benmdiphospholes 1, a phosphorane-phosphane rearrangement takes place.
A Facile Access to lh5,3hs-Benzodiphospholes
1
-
Two distinct types of peripheral binding site coordinate the eight Ag' ions in the complex cation 1. The
four crown ether units each coordinate one Ag'
atom. Each of the other four Ag' ions binds in a
meso pocket that is formed by a meso N atom and
two S atoms attached to the adjacent C, positions.
I*+
J. W. Sibert, S . J. Lange, C L. Stern,
A. G. M. Barrett,*
B. M. Hoffman * ................... 2020-2022
Octathioporphyrazine Crown Ethers: An
Octanuclear Ag' Complex with Coordination In the meso Pocket
1
The specific linking of two dendrimers is
achieved by incorporating terpyridine moieties at precise locations in cascade molecules. Metal complex formation then enables
nonrandom attachment of one dendritic assembly to another (see picture). The electronic properties of the metal depend on the dendritic environment.
G. R. Newkome,* R . Giither.
C. N. Moorefield, F.Cardullo,
L. Echegoyen, E. Perez-Cordero,
H. Luftmann .........................
2023 -2026
Routes to Dendritic Networks: Bis-Dendrimers by Coupling of Cascade Macromolecules through Metal Centers
Contents
A new type of linkage between the anomeric
center of a pyranose and an amino acid is
represented by the C-glycosidic amide bond
(shown on the right). It was formed by coupling heptonic acids with a a-aminoalanine
derivative. Both the r and the P anomers were
prepared selectively.
<OR
R
O
R
~
1-1
c
o
-
'*
N
H
no
"n
,NH
?c
Much better than high temperature, which causes decomposition, high pressure accelerates the automerization (resembling a "molecular gear") of homocubyl triflate 1
[Eq. (a)] as labeling studies with [9-D]-1 showed.
- OTf
A catalytic, highly stereoselective one-pot synthesis of inositol and conduritol derivatives (2 and 3, respectively) from benzene (1) and other simple arenes has been
achieved by excitation of the charge-transfer band of the complex between the arene
and osmium tetraoxide in the presence of chlordte or broniate anions as oxygen
transfer reagents. D M A P = 4-dimethylaminopyridine.
WAC
C. Wedler, A. Kunath,
H . Schick * .............................
2028-2029
Unexpected Course of the Darzens Reaction of Phenyl Esters of cdhlorocarboxylic
Acids with Carbonyl Compounds-A
Novel One-Step Synthesis of r-Chloro-Plactones
U. P. Spitz. P. E. Eaton* ................. 2030
Fluxionality Induced by High Pressure:
[9-D]9-Homocubyl Triflate, a PressureSensing Molecule
W. B. Motherwell,*
A. S. Williams ........................
2031 -2033
Catalytic Photoinduced Charge-Transfer
Osmylation: A Novel Pathway from
Arenes to Cyclitol Derivatives
OAc
OAc
1
Stereoselective Syntheses of RetroIsomers of N-Giucoasparagine
C-glycosidic retroamide bond
,
9Ac
2026-2028
~
The use of phenyl esters in lieu of alkyl esters drasti' ' q o
cally changes the course of the Darzens reaction of
R*
r-chlorocarboxylates with carbonyl compounds. InEt CI
stead of the usual glycidic esters, cc-chloro-[Hactones 1 are formed in good yields. These lactones are useful synthetic building
blocks. R' = Me, Et. tBu, Ph, PhCH,CH,; R2 = H, Me, Et; R ' / R 2 = (CH,),,
(CH,),'
TfO,
0. Frey, M. Hoffmann,
H. Kessler* ..............................
OAc
OAc
OAc
2
3
The simultaneous activation of CO, and CH, by Ta+ ions i n the gas phase was studied
by means of FT-ICR mass spectrometry. The cationic oxides TaO' and TaO: can
be obtained by reduction of CO,, but they are inert toward CH,. In contrast. the
coupling of CO, and CH, is achieved by the complex [TaCH,O]+ and yields T a O l
and C,H20, which is probably a ketene.
The synthesis is simple, the structure very unusual.
The [Pb,,I4,IH- ion (shown on the right), as a fraction of the NaCl structure type, is the largest iodoplumbate with discrete anions reported to date. The
anion is obtained in the reaction of PbI, with NaI in
acetone as the tetrabutylammonium salt in the form
of highly refractive, yellow octahedral crystals.
R. Wesendrup,
H. Schwarz* ..........................
2033 -2035
Tantalum-Mediated Coupling of Methane
and Carbon Dioxide in the Gas Phase
H. Krautscheid,* F. Vielsack . 2035 -2037
[Pb,8144]8-----An Iodoplumbate with an
Unusual Structure
At physiological temperatures (37'-C) the nonaromatic enyne allenes 2 cyclize to
provide the 3 d i h y d r o i n d e n e s 3. The high temperatures required for enediyne
cyclizations ( 1?,0--230'C) can be avoided, and a variety of functional groups should
be able t o survive the mild reaction conditions. Enediynes 1, which are accessible by
a short synthetic sequence, are converted into compounds 3 with overall yields of 52
to 70%. R 1 = H, Me; R2 = H. Me, C0,Me: R 3 = Me, OMe. C0,Me. C H 2 0 A c ;
C H D = cyclohexadiene.
J. W. Grissom,* D. Huang
.....
2037-2039
Low-Temperature Tandem Enyne Allene
Radical Cyclizations: Efficient Synthesis of
2.3-Dihydroindenes from Simple Enediynes
1,4-CHD
t
benzene
37 "C
12 h
OH
2
1
3
Substantially better initiators and therefore considerably more reactive than complexes of type A. the novel metathesis catalysts B are easily prepared by the reaction of
[RuCI,(PPh,),] with the appropriate diazoalkanes and subsequent phosphane exchange. While the PPh, derivatives are excellent catalysts for living ROMP of
norbornene. the complex with R = Cy, R' = Ph is also a very efficient catalyst for
the metathesis of acyclic alkenes.
Molybdenum complex 1 and white phosphorus react smoothly at 28 "C to give 2 with
ii terminal phosphido (P3-) ligand. The crystal structure of 2 reveals a monomer
with a M o - P triple bond (2.119(4) A). Treatment of 2 with mesityl azide gives a
complex with a terminal iminophosphenium (PNR') ligand; treatment with elemental sulfur leads to a phosphorus monosulfide (PS) complex. R = C(CD,),CH,,
Ar = 3,5-C,>H3Me,.
C. E. Laplaza, W. M. Davis.
C. C. Cummins* ............_....._ 2042-2044
A Molybdenum-Phosphorus Triple Bond:
Synthesis, Structure, and Reactivity of the
Terminal Phosphido (P3-) Complex
2
1
The chloro complex I(N,N)WCIl and the
phosphanide LiPPhH react to give the
complex [(N,N)W=P] with a terminal
phosphido (P3
- ) ligand (shown on the
right). The W - P bond length in monomeric [(N,N)W=P] is 2.162(4) A, virtually the same as the Ta-P bond length
(2.145(?) A ) in [(N,N)Ta=P(cyclohexyl)]. N,N = (Me,SiNCH,CH,),N.
N. C. Zanetti, R. R . Schrock."
W. M. Davis
2044-2046
Monomeric Molybdenum and Tungsten
Complexes That Contain a Metal-Phosphorus Triple Bond
Horner key intermediates 2 for the synthesis of trisubstituted stereochemically defined olefins 3 can be obtained easily by stereoselective alkylation of x-alkyl-pketophosphine oxides 1 with RLi. CeCI, complexes in T H F at - 78 ' C . Decomposition with K H gives trisubstituted alkenes with excellent diastereoselectivity.
o
1
A Series of Well-Defined Metathesis
Catalysts-Synthesis
of [RuC12(=CHR')(PR,),] and Its Reactions
[Mo(P)(NRAr),l
P
Fp
P. Schwab, M. B. France, J. W. Ziller,
R. H. Grubbs* ....____....___._.....
2039-2041
m
-78"C,
THF
KH. DMF
50°C
2
R1
3
G. Bartoli,* E. Marcantoni, L. Sambri,
M. Tamburini ..__.......___......__...
2046-2048
Cerium(m) Chloride Promoted Nucleophilic Addition of Orpanolithium Reagents to cc-Alkyl-p-Ketophosphine Oxides:
A New Protocol for the Synthesis of Stereochemically Defined Trisubstituted Olefins
Based on EPR, Raman, and mass spectral evidence,
the formula 1 best describes the transient intermediate which forms upon treatment of 2 with tert-butyl
hydroperoxide in the presence of alcohol. Kinetic
evidence suggests that its decomposition by oxidation of the bound alcohol proceeds via the transition
state 3. tpa = tris(2-pyridylmethy1)amine.
[Fe(tpa)(OotBu)(HOCHRR')]'+
[FeZo(tpa),(H,o),l(CF,SO,),
2+
An Alkylperoxoiron(1II) Intermediate and
Its Role in the Oxidation of Aliphatic C-H
Bonds
3
1
2
A six-membered Co,O, ring in a chair conformation is featured in the diamagnetic
dimer 2, which is in equilibrium with its Coil monomer 1(AH = - 14.5(5) kcalmol- '
and A S = - 60(3)cal K - mol- I ) . The dimerization of 1 and loss of 0, from 2 are
steps en route to dioxygen activation. Tp" = hydrotris(3-isopropyI-5-methylpyrazoly1)borate).
1
J. Kim, E. Larka, E. C. Wilkinson,
L. Que, Jr.* .............................
2048-2051
2
Stripped from the solvent that effected
their aggregation, micelles (shown
on the right, for example, for the
cholic acid derivative CHAPS) were
found intact in the gas phase. Mass
spectrometric analysis provided physical evidence to verify niicelle formation.
Monomolecular lipid mono- and bilayers hdving peptide spacer groups are prepared in situ
on gold substrates By fusion with liposomes
containing ATPase, they spontaneously form
lipid bilayers Surface plasmon resonance
spectroscopy and electrochemical measurements indicate that the enzyme is incorporated into the lipid layer (depicted schematically
on the right) The dctivity of the enzyme, in
this case the translocation of protons across
the lipid layer, is detected by the current due
to the discharge of protons at the gold electrode
0. M. Reinaud, G. P. A. Yap,
A . L. Rheingold,
K. H. Theopold * ........_..... ..__.2051 -2052
Novel Binuclear Cobalt Dioxygen Complex-A Step on the Path to Dioxigen Activation
3
&'
L
I U n
0%.
G. Siuzdak,* B. Bothner ......_.2053-2055
+jso3
IN
-03s
Gas-Phase Micelles
O,NH
n 'r
R. Naumann,* A Jonczyk, R Kopp,
J van Esch, H. Ringsdorf, W Knoll,
P Graber
2056-2058
I
1
Incorporation of Membrane Proteins in
Solid-Supported Lipid Layers
+ I
I
I
I
I
-
* Author
to whom correapondznce should be addreaacd
BOOKS
Contents
The Consumer's Good Chemical Guide. A Jargon-free Guide to the Chemicals
of Everyday Life * J. Emsley
G. B. Kuujjman, L. M . Kuuffmun .... 2059
Practical Surface Analysis. A2, Vol. 1. Auger and X-Ray Photoelectron
Spectroscopy D. Briggs, M. P. Seah
H . Bubert ................................
- J. P. Glusker,
Crystal Structure Analysis for Chemists and Biologists
M. Lewis. M. Rossi
G. Miillev .........................................
Sources 1925
Events 1922
2060
Keyword Index 2062
Preview 2064
Author Index 2063
The following reviews will appear in future issues:
Carbon Dioxide as Raw Material: The Synthesis of Formic Acid and Its Derivatives from CO,
W. Leitner
Volatile Metal Oxides According to the Concept of Donor Functionality
W. A. Herrmann, N. W. Huber, 0 . Runte
Cyclopentadienyl-Free Organolanthanide Chemistry
F. T. Edelmann
Palladium-Catalyzed Synthetic Reactions of Propargylic Compounds
J. Tsuji, T. Mandai
Computer-Assisted Planning of Organic Chemical Synthesis: The Second Generation
J. Gasteiger and W.-D. Ihlenfeldt
Electronegativity and Molecular Properties
J. Hinze and D. Bergmann
Cytomimetic Organic Chemistry: Early Developments
F. M. Menger and K. D. Gabrielson
Supramolecular Inorganic Chemistry: Guests in Small and Large Hosts
A. Muller et al.
Synthetic Aspects of Metal Catalyzed Oxidations of Amines and Related Reactions
S.-I. Murahashi
Supramolecular Synthons in Crystal Engineering-The
G . R. Desirqiu
New Organic Synthesis
Copper A "Modern" Bioelement
W. Kaini and J. Rall
The Schenck Ene Reaction: Diastereoselective Oxyfunctionalization with Singlet Oxygen in Synthetic Applications
W. Adam
Metallophosphaalkenes-From
L. Weber
......... 2059
Exotics to Versatile Building Blocks in Preparative Chemistry
Electron Domains and the VSEPR Model of Molecular Geometry
R. J. Gillespie and E. A. Robinson
Protonation of Unsaturated Hydrocarbon Ligands: Regiospecificity, Stereospecificity, and Product Specificity
R. A. Henderson
Stereocontrol in Organic Synthesis Using the Diphenylphosphinoyl (Ph,PO) Group
Jonathan Clayden and Stuart Warren
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