Mini-Reviews in Organic Chemistry, Volume 1, No. 3, 2004
Contents
Recent Advances in the Synthesis of
P(III)-Chirogenic Compounds Pp.233-247
P(t-Bu)3 : A Versatile and
Efficient Ligand in Homogeneous Catalysis Pp.249-277
Jean
Michel Brunel
Generation and Reactions of Selenium
Isologues of Enolate Ions Pp.249-290
Toshiaki
Murai
Oxirene Participation in the Photochemical
Wolff Rearrangementa Pp.291-308
K.-P.
Zeller, A. Blocherb and P. Haiss
Synthesis of Stable-isotope (13C
and 15N) Labeled Nucleosides and Their Applications Pp.309-332
Etsuko
Kawashima and Kazuo Kamaike
The Chemistry and Biology of Rhazinilam and
Analogues Pp.333-341
Olivier
Baudoin, Daniel Guenard and Françoise Gueritte
Abstracts
[Back to top] Recent Advances in the Synthesis of
P(III)-Chirogenic Compounds
M.
J. Johansson and N. C. Kann
Chiral
phosphorus(III) ligands with chirality residing on the phosphorus atom have
seen a renaissance upon the discovery that coordination to boron stabilises the
phosphorus atom towards both oxidation and racemization. In this review we
describe the newer methods that are available for the preparation of
P-chirogenic ligands and discuss their advantages and limitations.
[Back to top] P(t-Bu)3 : A Versatile and
Efficient Ligand in Homogeneous Catalysis
Jean
Michel Brunel
Changing
substituents on phosphorus ligands can cause marked changes in the behaviour of
the free ligands and of their transition metal complexes. In this review, we
will describe the synthesis and the application of P(t-Bu)3,
an efficient ligand in numerous homogeneous catalytic systems and rationalise
its singular behaviour.
[Back to top] Generation and Reactions of Selenium
Isologues of Enolate Ions
Toshiaki
Murai
Characteristic
reactions of lithium eneselenolates generated from selenoamides, selenoic acid O-esters,
and selenothioic acid S-esters with carbon electrophiles are described.
Reaction and thermodynamic properties of ammonium eneselenolates of
selenothioic acid S-esters are shown. Generation of eneselenolates from
alkenyl and alkynyl metallic species is also introduced.
[Back to top] Oxirene Participation in the Photochemical
Wolff Rearrangementa
K.-P. Zeller, A. Blocherb and P. Haiss
Evidence obtained
by carbon labelling and carbene-scavenging techniques for the establishment of
an α-oxocarbene-oxirene interconversion in the photolysis of acyclic
α-diazoketones is summarised. Normalsized alicyclic α-diazoketones
and o-quinone diazides react without intervention of the oxirene route,
whereas the 12-membered ring system behaves like the acyclic counterparts. The
oxirene participation is discussed with reference to stereochemical features of
the α-diazoketones and predictions derived from high-level theory.
[Back to top] Synthesis of Stable-isotope (13C
and 15N) Labeled Nucleosides and Their Applications
Etsuko
Kawashima and Kazuo Kamaike
NMR studies of
stable-isotope labeled oligonucleotides have provided useful information
regarding nucleic acid structures, nucleic acid - drug binding, and nucleic
acid - protein interactions. For the conformational elucidation of the
sugar-phosphate backbone and/or the sugar moieties in nucleic acids, 13Clabeled
oligonucleotides are very useful, and for the transformation of nucleic acid -
drug binding sight are 15N-labeled oligonucleotides.
The present paper
has introduced the recent synthetic methods of nucleosides containing either a 13C
labeled sugar moiety or a 15N-labeled exocyclic amine, and
applications including our research work.
[Back to top] The Chemistry and Biology of Rhazinilam and
Analogues
Olivier
Baudoin, Daniel Guenard and Françoise Gueritte
Rhazinilam (1)
is a natural substance with unique tubulin-binding properties. The present
review describes the isolation and structure elucidation of (1), the
available data regarding its biological properties, its semi- and total
syntheses and its structure-activity relationships through the synthesis of
analogues.