Table Of ContentOrganophosphorus Chemistry
Volume 37
A Specialist Periodical Report
Organophosphorus
Chemistry
Volume 37
A Review of the Literature Published between
January 2006 and January 2007
Editors
D.W. Allen, Sheffield Hallam University, Sheffield, UK
J.C. Tebby, Staffordshire University, Stoke-on-Trent, UK
Authors
G.A. Carriedo, Universidad de Oviedo, Oviedo, Spain
A.T. Hewson, Sheffield Hallam University, Sheffield, UK
G. Keglevich, Budapest University of Technology and Economics,
Budapest, Hungary
D. Loakes, Laboratory for Molecular Biology, Cambridge, UK
K. Owsianik, Polish Academy of Sciences, Lodz, Poland
G.-V. Ro¨schenthaler, University of Bremen, Bremen, Germany
A. Skowron´ska, Polish Academy of Sciences, Lodz, Poland
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ISBN: 978-0-85404-359-0
ISSN 0306-0713
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r The Royal Society of Chemistry 2008
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Preface
David Allena and John Tebbyb
DOI: 10.1039/b717921a
This volume covers the literature of organophosphorus chemistry published in the
periodfromJanuary2006toJanuary2007,andreflectsoureffortsinrecentyearsto
provideamoreuptodatesurveyofprogressinthistopicwhichcontinuestogenerate
avastrangeofliterature.Thevolumefollowsthetraditionalapproach,apartfromthe
absenceoftheusualchapteronmononucleotidechemistry.However,somecoverage
of this area has been included in David Loake’s chapter on nucleotides and nucleic
acidsanditishopedthatthemononucleotideareawillreceiveafullsurveyinthenext
volume. We welcome new authors Professor Gabino Carriedo (Universidad de
Oviedo) who has covered phosphazenes and Professor Gerd-Volker Roeschenthaler
(InstituteofInorganic&PhysicalChemistry,UniversityofBremen)whohasreported
onadvancesinhypervalentphosphoruschemistry.
Theuseofawiderangeoftervalentphosphorusligandsinhomogeneouscatalysis
continues to be a major driver in the chemistry of both traditional P–C-bonded
phosphinesandalsothatoftervalentphosphorusacidderivatives.Itisinterestingto
note the increasing use of borane-protected metallophosphide reagents in methods
for the synthesis of new phosphines. A study of the synthesis of chiral primary
arylphosphineshasrevealed,surprisingly,thatprimaryphosphinesinwhichthearyl
substituent is involved in extended conjugation are significantly more stable to air
thanaresimplephenylanalogues.Itseemsthatmanyprimaryarylphosphinesareno
more sensitive to air than are moderately reactive aldehydes, and that these
compoundsaremuchmoreattractivesyntheticprecursorsthanpreviouslysupposed.
Considerableinteresthasalsobeenshowninstudiesofthephysicochemicalproper-
tiesofphosphines,inparticularthesolution-phaseacidityofcompoundscontaining
P–Hbondsandnewapproachesforthepredictionofthebasicityofphosphinesin
general. It has been shown that the solvent exerts a profound influence on the
basicityofphosphinesandthatitisnotvalidtousegas-phasedatatointerpretthe
solution-phasebasicityofthesecompounds.
Thechemistryofphosphinechalcogenides,phosphoniumsaltsandylideshasalso
continued to develop and activity in this area remains at a high level. Of note is a
growingliteratureontheuseofphosphonium-basedionicliquidsassolvents.
Nucleotidechemistry also continuestobeaveryactivearea. 2006sawa further
increaseinthenumberofpublicationsrelatingtomodifiedoligonucleotides.Byfar
thelargestsingleareaofresearchinthisfieldconcernsoligonucleotidescontaining
modified nucleobases, with applications ranging from duplex and triplex stabilisa-
tiontomodifiedbasepairsandanaloguespreparedtoinvestigatethemechanismof
action of a variety of enzymes. The largest sectionin the review concerns oligonu-
cleotide conjugates, a very diverse field, which includes fluorescent analogues and
theirapplications,molecularbeacons,FRETtechniquesandsinglemoleculestudies.
Alsonotedistherapidlyexpandingstudyofnanodevicesandnanostructuresanda
growing interest in the use of metal-chelating pseudonucleosides, which have
applications in novel base pairing interactions, in metal catalysis, and in the study
oftherapeuticreagentssuchascisplatin.Thestructuralstudyofoligonucleotidesis
another expanding area of research, and each year more complex structures are
solved by X-ray crystallography or by NMR. NMR techniques now allow for the
study of larger and larger biosystems that include a number of oligonucleotide-
peptidestructures.Inaddition,manynewtechniquesareemergingthatgiveglobal
aBiomedicalResearchCentre,SheffieldHallamUniversity,Sheffield,UKS11WB
bDivisionofChemistry,FacultyofSciences,StaffordshireUniversity,Stoke-on-Trent,
UKST42DE
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structures of biomolecules, such as atomic force microscopy and electron micro-
scopy.
Onceagain,therehasbeenkeeninterestinquinquevalentphosphoruschemistry.
Studies have been particularly rewarding in the field of stereoselective synthesis—
somereactionsproceedinginahighlyenantioselectivemannergivingupto99%ee.
Success in the biological areas includes the synthesis of a large number of natural
and unnatural phosphates and their phosphonate, phosphinate and fluorinated
analogues as well as several inositols and phosphorus analogues of amino acids.
Highlights include the total synthesis of the antitumor fostriecin analogue, PD
113.271, cytostatin, and phostactomycin B that show antitumor, antibacterial and
antifungalactivities.Othersynthesesincludeanovelseriesofphosphorus-contain-
ingC-11-aryl-substitutedsteroidsandseveralanaloguesofaryl-substitutedfosfido-
mycin which are superior to fosfidomycin in inhibiting the growth of malaria
parasites. Mechanistic studies include phosphate ester hydrolysis and metal-cata-
lyzedreactions.Highlightsincludethegreatcatalyticpotentialofchiralphosphoric
acidshavingdifferentfunctionalizedaromaticsystems(Brønstedacids)forreactions
suchastherhodiumcatalyzedallylicalkylationofchelatedenolphosphates,andthe
allylation of iminophosphonates using various allylsilanes catalyzed by a copper
complex.
Interestinphosphazenechemistryisaskeenasever.Alargerrangeandimproved
preparativeroutestoSchwesinger’sbaseshasledtotheirwideruseinsynthesis,e.g.
as catalysts. They are now becoming commercially available. Improvements in the
stabilities of phosphazenium cations make them useful as counter cations in basic
conditions and for improving anion reactivities such as the ‘naked’ fluoride ion.
Mechanistic studies of the aza-Wittig reaction are assisting the wide use of this
reaction in organic synthesis. Staudinger ligation has also received attention
furthered by its utilization for making biologically active compounds. The role of
phosphazenes in metal catalysis is highlighted by the use of Rh and Ir complexes
withferrocenylphosphazenesinolefinhydrogenationinalmostperfectenantiomeric
excess.Bettermethodsforthegenerationofpolyphosphazeneshavebeendeveloped.
Studies of cyclo- and poly-phosphazenes have continued unabated. This has been
largelyduetotheirimmenserangeofapplicationsespeciallyasimprovedmaterials
and biological applications. These include membrane and photonic developments,
biosensors, bone composites, electrolyte additives, ion-conducting materials and
flameretardants.Theirpotentialasligandsformetalcatalysisisonlyjustbeginning
toberealised.
The interest in hypervalent phosphorus chemistry centres mainly on the bound-
ariesofacyclic,monocyclicandbicyclicphosphoruscompoundsaswellastheinter-
conversion of penta- and hexa-coordinate states. In addition to theoretical studies
there have been advances in the use of 31P NMR techniques to investigate the
structuresofmorecomplexsystems,suchasphosphoryltransferenzymes,aswellas
for investigating complex oxide structures. There have been reviews of stereogenic
phosphorussitesandthestereochemistryassociatedwithphosphoraneandoxyphos-
phoranereactionswherepentacoordinatetransitionstatesorintermediatesareoften
encountered. Consideration of apicophilic, fluxional behavior, bond parameters,
and tetra- vs. penta-coordination has shown that the familiar apicophilicity rules
give an oversimplified picture. Evidence has been presented that a number of
betainesexistinequilibriumwithisomericphosphoranes.Themechanismofligand
rearrangement (pseudorotation) has been an exciting and keenly studied area of
pentacovalent phosphorus chemistry and we acknowledge the major contribution
made byIvar K. Ugi (1930–2005) who will be especially remembered for his work
on the alternative ‘Turnstile Rotation’ mechanism to the established ‘Berry
Pseudorotation’.
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CONTENTS
Cover
Aselectionoforgano-
phosphorusmolecules.
Imagereproducedby
permissionofDrDavidLoakes.
Preface 7
David Allen and John Tebby
Phosphines and related P–C-bonded compounds 13
D. W. Allen
Introduction 13
Phosphines 13
p -Bonded phosphorus compounds 35
p
Phosphirenes, phospholes and phosphinines 38
Tervalent phosphorus acid derivatives 54
A. T. Hewson
Introduction 54
Halogenophosphorus compounds 54
Tervalent phosphorus esters 55
Tervalent phosphorus amides 63
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Phosphine chalcogenides, phosphonium salts and P-ylides 73
G. Keglevich
Phosphine chalcogenides 73
Phosphonium salts 91
Ylides (phosphoranes) 100
Quinquevalent phosphorus acids 116
A. Skowron´ska and K. Owsianik
Introduction 116
Phosphoric acids and their derivatives 116
Phosphonic and phosphinic acids 143
Nucleotides and nucleic acids; oligo- and polynucleotides 179
David Loakes
Introduction 179
Aptamers and (deoxy)ribozymes 206
Oligonucleotide conjugates 211
Nucleic acid structures 222
Pentacoordinated and hexacoordinated compounds 247
G.-V. Ro¨schenthaler
Introduction 247
Acyclic phosphoranes 248
Monocyclic phosphoranes 248
Bicyclic and polycyclic phosphoranes 249
Phosphatranes 253
Hexacoordinate phosphorus compounds 253
Biochemistry 255
10 | OrganophosphorusChem.,2008,37,9–12
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Phosphazenes 262
Gabino A. Carriedo
Introduction 262
Linear phosphazenes 262
Cyclophosphazenes 282
Polyphosphazenes 298
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