Organophosphorus Chemistry Vol. 36 PDF
Preview Organophosphorus Chemistry Vol. 36
Organophosphorus 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 Ifyoubuythistitleonstandingorder,youwillbegivenFREEaccess to the chapters online. Please contact [email protected] with proof of purchase to arrange access to be set up. Thankyou. ISBN: 978-0-85404-359-0 ISSN 0306-0713 A catalogue record for this book is available from the British Library r The Royal Society of Chemistry 2008 All rights reserved Apart from any fair dealing for the purpose of research or private study, or criticismorreviewaspermittedunderthetermsoftheUKCopyright,Designs and Patents Act, 1988, this publication may not be reproduced, stored or transmitted, in any form or by any means, without the prior permission in writing of The Royal Society of Chemistry, or in the case of reprographic reproduction only in accordance with the terms of the licences issued by the CopyrightLicensingAgencyintheUK,orinaccordancewiththetermsofthe licences issued by the appropriate Reproduction Rights Organization outside the UK. Enquiries concerning reproduction outside the terms stated here should be sent to The Royal Society of Chemistry at the address printed on this page. Published by The Royal Society of Chemistry, Thomas Graham House, Science Park, Milton Road, Cambridge CB4 0WF, UK Registered Charity Number 207890 For further information see our web site at www.rsc.org Typeset by Macmillan India Ltd, Bangalore, India Printed and bound by Henry Ling Ltd, Dorchester, UK 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 OrganophosphorusChem.,2008,37,7–8 | 7 Thisjournalis(cid:1)c TheRoyalSocietyofChemistry2008 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’. 8 | OrganophosphorusChem.,2008,37,7–8 Thisjournalis(cid:1)c TheRoyalSocietyofChemistry2008 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 OrganophosphorusChem.,2008,37,9–12 | 9 Thisjournalis(cid:1)c TheRoyalSocietyofChemistry2008 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 Thisjournalis(cid:1)c TheRoyalSocietyofChemistry2008 Phosphazenes 262 Gabino A. Carriedo Introduction 262 Linear phosphazenes 262 Cyclophosphazenes 282 Polyphosphazenes 298 OrganophosphorusChem.,2008,37,9–12 | 11 Thisjournalis(cid:1)c TheRoyalSocietyofChemistry2008
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