Current Fluoroorganic Chemistry. New Synthetic Directions, Technologies, Materials, and Biological Applications PDF
Preview Current Fluoroorganic Chemistry. New Synthetic Directions, Technologies, Materials, and Biological Applications
g 1 or00 09 | http://pubs.acs.1/bk-2007-0949.fw CurrenCth Felmuoisrtoroyr ganic 02 20 ber 22, oi: 10.1 od Oct7 | n 00 o2 6.64.10 ary 11, 6u 1n 2.Ja 21e: y at bD wnloaded blication Do Pu In Current Fluoroorganic Chemistry; Soloshonok, V., el al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2007. g 1 or00 s.w 09 | http://pubs.ac1/bk-2007-0949.f 02 20 ber 22, oi: 10.1 od Oct7 | n 00 o2 6.64.10 ary 11, 6u 1n 2.Ja 21e: y at bD wnloaded blication Do Pu In Current Fluoroorganic Chemistry; Soloshonok, V., el al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2007. ACS SYMPOSIUM SERIES 949 Current Fluoroorganic Chemistry New Synthetic Directions, Technologies, Materials, g 1 or00 009 | http://pubs.acs.21/bk-2007-0949.fw andV BadiiomTlh oeA Ug.n iiSvceorasloitlys ohf oAOnklopahkpo,m laEi dciatotr ions 20 ber 22, oi: 10.1 Koichi Mikami, Editor od Oct7 | Tokyo Institute of Technology n 00 o2 6.64.10 ary 11, TokyoT Uankivaesrshitiy oYf Aagmricaulztuarek ia,n dE dTeicthonro logy 6u 1n 2.Ja 21e: John T. Welch, Editor y at bD wnloaded blication StaJteo Uhnnive Frsi.t yH ofo Nnewe kY,o rEkd ati tAolbr any Do Pu The University of Waterloo Sponsored by the ACS Divisions of Fluorine Chemistry and Medicinal Chemistry American Chemical Society, Washington, DC In Current Fluoroorganic Chemistry; Soloshonok, V., el al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2007. Library of Congress Cataloging-in-Publication Data Current fluoroorganic chemistry : new synthetic directions, technologies, materials, and biological applications / Vadim Anatol'evich Soloshonok, editor... [et al.]; sponsored by the ACS divisions of fluorine chemistry and medicinal chemistry. p. cm.—(ACS symposium series ; 949) Includes bibliographical references and index. g 1 s.orw00 ISBN 13: 978-0-8412-7403-7 (alk. paper) 09 | http://pubs.ac1/bk-2007-0949.f C1hIIS.e. mOSBoNirsgl otar1syn0h.o:o f I0nlIuIo-.o8k Dr4,i n1iVve2.i -sAc7ioo.4 mnI0 Ipo3. ofA- u7Mmn d(eeasdrl.iik cc2a.i n.np aO aClp rCehgreha)mne miicc iasclto rSmyo.p coieutnyd. sD—ivSisyinotnh eosfi sF. luorine 02 20 ber 22, oi: 10.1 Q54D74'.0122—.F1dCc2872 2006 2006050085 od Oct7 | The paper used in this publication meets the minimum requirements of American n 00 National Standard for Information Sciences—Permanence of Paper for Printed Library o2 6.64.10 ary 11, CMoapteyrriiaglhst, A©N 2S0I0 Z7 3A9m.4e8r-i1ca9n8 4C.h emical Society 6u 2.1Jan Distributed by Oxford University Press 21e: by Dat All Rights Reserved. Reprographic copying beyond that permitted by Sections 107 or wnloaded blication c21h20a28p tReoro fsf eetwhee oo ofUd $ .DS3.3r iC.v0eo0,p pDylrauingsv h$et0 rA.s7,c 5Mt pAise r0a p1lla9og2we3e ,id sU pfSoaAird . itnRote etprhnueab lCl iocuaspetyi oroingn holytr ,Cr eplperoarorvadinducecedti oCtnhe anftto erar , s pIanelecr- ., Do Pu opfe rpmaigsesiso nin rtehqisu ebsotso kto i sA pCeSrm Citotepdy roignhlyt Ounffdiceer, liPcuebnlsiec aftrioomns ADCivSi.s iDonir,e c1t1 5th5e s1e6 tahn dS toretheet,r N.W., Washington, DC 20036. The citation of trade names and/or names of manufacturers in this publication is not to be construed as an endorsement or as approval by ACS of the commercial products or services referenced herein; nor should the mere reference herein to any drawing, specification, chemical process, or other data be regarded as a license or as a conveyance of any right or permission to the holder, reader, or any other person or corporation, to manufacture, reproduce, use, or sell any patented invention or copyrighted work that may in any way be related thereto. Registered names, trademarks, etc., used in this publication, even without specific indication thereof, are not to be considered unprotected by law. PRINTED IN THE UNITED STATES OF AMERICA In Current Fluoroorganic Chemistry; Soloshonok, V., el al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2007. Foreword The ACS Symposium Series was first published in 1974 to pro vide a mechanism for publishing symposia quickly in book form. The purpose of the series is to publish timely, comprehensive books devel oped from ACS sponsored symposia based on current scientific re g 1 search. Occasionally, books are developed from symposia sponsored by s.orw00 other organizations when the topic is of keen interest to the chemistry 09 | http://pubs.ac1/bk-2007-0949.f tianeuntdetrisee nsitsc eBtr.oe ev ftoiherwee eaadug drfieoeerni ncaegp. p tSrooo mpprueiba ptlieas hpane ard sb cmooomakyp, rbtheehe ee pnxrsciolvupedo escdeod vte otra abbgeleett eoarnf dcfoo fcnou rs 2002 the book; others may be added to provide comprehensiveness. When ber 22, oi: 10.1 cahpapproteprrsi aater,e opveeerrv-rieewvie wore di nptrroiodru tcoto rfiyn aclh aapccteerpsta narcee aodrd reedj.e cDtiroanf,t sa nodf od Oct7 | manuscripts are prepared in camera-ready format. on 200 As a rule, only original research papers and original review 6.64.10 ary 11, pouapsleyr sp uabreli sihnecdlu pdaepde rins athree nvootl uamcceesp.t eVde. rbatim reproductions of previ 6u 1n 2.Ja 21e: y at bD wnloaded blication ACS Books Department Do Pu In Current Fluoroorganic Chemistry; Soloshonok, V., el al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2007. Preface Selective fluorination of a lead compound can dramatically improve the performance of that material whether used in liquid crystals or g 1 cs.orpr00 pharmacologically active substances. The task confronting the synthetic s.a49. chemist is how to construct such materials: whether to employ b9 p://pu007-0 pflrueocruinrsaotre.d Tbhueil duisneg obfl oecitkhse ro rs tfrlautoergiyna itniotrno douf caes s uai tsaebcloyn dfu cnocntiuonndarliuzmed: 09 | htt1/bk-2 What are the effects of fluorination on reactivity and how can those 02 effects be employed for a desirable result? While both these topics have 20 ber 22, oi: 10.1 bhaeelfn-c ethnetu sruyb, jtehcet qouf eisntniounmse rreamblaei np.u blications and symposia over the last od Oct7 | This symposium series volume is derived from three independent n 00 o2 symposia held on organofluorine chemisty. The first of these, sponsored by 212.166.64.10 Date: January 11, jFCWohilanuestmohlyriins obtgrotyyor ngtha,a enDn dA.iC cmM. Ce(eArdhicuicaeginmun saCitls h2tCer8my ht eiohcm aeSillse dtSpr otyaec,mti e wbtthyaee rs( A21e3C,n 02tSti0th)l 0e D5Ndi) av Ntaisinoeiodnwna w slF aAosrf oC oFnrSlgut Maioenrreiiznsee tedi no fg in ed on by Vadim Soloshonok and Koichi Mikami. At the same occasion, a Download Publicati Csyumrrpaons.i uTmh ee ntthitirledd syFmlupoosriouums, hCehlde mati stthrye Iwnatesr noartigoannailz eCd hebmy icDael nnis Congress of Pacific Basin Societies, in Honolulu, Hawaii (December 15-20, 2005) focused on Fluorine-Containing Amino Acids: Preparation and Application to Biological Systems, was convened by Takashi Yamazaki, John T. Welch, and John F. Honek. Both meetings were supported by the Petroleum Research Fund of the ACS and the ACS Division of Fluorine Chemistry. Additional financial support for the Honolulu meeting came from the Japanese Society of Fluorine Chemistry. From the 55 presentations at these three symposia this volume includes 31 contributions. These chapters are organized into three groups; New Synthetic Directions, New Technologies, and New Biological Ap- xi In Current Fluoroorganic Chemistry; Soloshonok, V., el al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2007. plications. The first section describes new methods for the incorporation of fluorinated building blocks and the application of electrochemical fluorination in synthesis. The section on new technologies presents several new applications of fluorous technology or the applications of extensively fluorinated compounds in preparative reactions. The final section has a very strong emphasis on fluorinated amino acids, peptides, and proteins but also discusses fluorinated anti-cancer and antiviral com pounds in addition to carbohydrates and nucleosides. This volume, therefore, addresses in part the questions raised earlier. It is our pleasure to acknowledge the contributions of all the speak ers to the symposia and to the authors for their contributions to this volume. Organofluorine chemistry remains a challenging and exciting g 1 cs.orpr00 discipline and promises to remain so far into the future. s.a49. b9 u0 p://p007- Vadim A. Soloshonok 09 | htt1/bk-2 Department of Chemistry and Biochemistry 2002 University of Oklahoma ber 22, oi: 10.1 Norman, OK 73019-3051 od Oct7 | Koichi Mikami n 00 o2 by 212.166.64.10 Date: January 11, TDTTooeakpkkayyoraot m,sIJnheasnpitt ia tnuYo tfe aA ompf pTaliezecdah knCoih leomgyis try d n eo Download Publicati DTTooekpkayyorot mU1e5nn2itv- 8eor5fs 5Ai2tpy, poJlfai epAda gnCr ihceumltuisrter ya nd Technology John T. Welch Department of Chemistry State University of New York at Albany 1400 Washington Avenue Albany, NY 12222 John F. Honek Department of Chemistry University of Waterloo xii In Current Fluoroorganic Chemistry; Soloshonok, V., el al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2007. g 1 cs.orpr00 Current Fluoroorganic s.a49. b9 u0 p://p007- Chemistry 09 | htt1/bk-2 02 20 ber 22, oi: 10.1 od Oct7 | n 00 o2 by 212.166.64.10 Date: January 11, d n eo Download Publicati In Current Fluoroorganic Chemistry; Soloshonok, V., el al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2007. Chapter 1 Trifluoromethylation of Metal Enolates and Theoretical Guideline Koichi Mikami and Yoshimitsu Itoh Department of Applied Chemistry, Tokyo Institute of Technology, g 1 Meguro-ku, Tokyo 152-8552, Japan s.orh00 cc 09 | http://pubs.a1/bk-2007-0949. 02 20 ber 22, oi: 10.1 gTehnee radtiioffnic ulotyf maest awl eelnl olaaste sth oe f αsi-gCniFfic3-aknecteo noefs cathnen odt irbecet od easily understood by chemists unfamiliar with fluorine. In n Oct007 | sharp contrast to the great success in non-fluorine, 2.166.64.10 oJanuary 11, 2 hrosyevyanedcrtrhtsoiheocatnaidcrsaob. lwolyneH d o.c iwhmMeepmvoeeitrrsatt,arl n yett,h n oefill unaot mericsnea teraob lf o cnhce-aecnmraobrilosbatntoreyynsl chbooaomfsn pfdlolou unofnogdrr imsnb ieaanertgnee d by 21Date: carbonyl compounds have been severely limited to α-F metal d n enolates. α-CF Metal enolates have generally been wnloadeblicatio rfaeccoilgen izβe-Μd a-Fs uelni3mstainbaleti oann.d H doifwficeuvletr ,t ow per ephaarvee b edceavuelsoep eodf thae Do Pu direct generation and synthetic application of α-CF3 metal enolates. Therefore, the present results regarding the direct generation and synthetic use of metal enolates of α-CF- 3 ketones might be recognized as a paradigm shift to the general use of metal enolates in fluorine chemistry. 2 © 2007 American Chemical Society In Current Fluoroorganic Chemistry; Soloshonok, V., el al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2007. 3 Introduction Organofluorine compounds have attracted much attention because of their rapidly increasing applications in the biological and material sciences (1). In particular, CF-compounds of specific absolute configurations are employed as 3 novel lead analogues that exhibit particularly high physiological activity and remarkable physical properties (2). In sharp contrast to normal alkyl halides (Rh-X), however, perfluoroalkyl halides (RrX) can not react as a R+ reagent (eg. f nucleophilic alkylation) because the electronegativities of the perfluoroalkyl groups are higher than those of the halogens. The polarization of perfluoroalkyl halides is as Rf5"-X8+ and treatment with a nucleophile could not produce RrNu (3). g 1 Therefore, we report our research on the radical trifluoromethylation of s.orh00 metal enolates of ketones with trifluoromethyl iodide. cc 009 | http://pubs.a21/bk-2007-0949. Doti-rCeFc tm Getealn eenroaltaitoesn hoafv eT giteanneriaullmy bEeenno lraectoeg onfiz e0d1 -tCoF b3e K uensttoanblee and 20 3 ber 22, oi: 10.1 difficult to prepare because of the rapid (3-M-F elimination (Scheme 1) (4). od Oct7 | n 00 o2 2.166.64.10 January 11, 21e: ^:B(Nu) by Dat d n wnloadeblicatio ON F1 * SB<NU> » - Decomposition Do Pu highly positive Scheme 1. Decomposition of a-CF metal enolates. 3 We have already reported ( 5) that the enolate can be formed quantitatively by using TiCl and EtN (Table 1) (6). a-Deuteriated ketone (D-la) was 4 3 obtained in quantitative yield using 35 wt% DC1/D0 for quenching the enolate 2 (run 2) ( 7). This result clearly shows that TiCl-enolates can be directly 3 generated quantitatively from a-CF-ketones. In sharp contrast, the lithium 3 In Current Fluoroorganic Chemistry; Soloshonok, V., el al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2007.
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