Abstract
New and recent work by the author and colleagues will be presented.
Six methods for functionalizing halogenated ethers will be presented:
(1) a new regent for halogen-exchange fluorination of chloromethyl
ethers, (2) a selective photochemical or thermal reduction of poly-chlorinated
substrates, (3) new organic sources of fluoride for antimony-pentachloride-catalyzed
halogen-exchange fluorination, (4) a chemoselective methanolysis
reaction of the trifluoromethyl group, (5) a stereoselective decarboxylation reaction,
and (6) the use of bromine trifluoride for fluorination with inversion
of configuration. The reactions are applied to the synthesis of
individual enantiomers of fluoroether anesthetics.
Key words
fluorine - halogenation - drugs - halogenated
ethers - halogen-exchange fluorination
References
<A NAME="RC05402SS-1">1 </A>
McClinton MA.
Aldrichimica
Acta
1995,
28:
31
<A NAME="RC05402SS-2">2 </A>
Rozov LA.
Lessor RA.
Kudzma LV.
Ramig K.
J. Fluorine
Chem.
1998,
88:
51
<A NAME="RC05402SS-3">3 </A>
Kudzma LV,
Lessor RA,
Rozov LA, and
Ramig K. inventors; US Patent 5886239.
<A NAME="RC05402SS-4">4 </A>
Rozov, L.; Ramig, K. unpublished results.
<A NAME="RC05402SS-5">5 </A>
van Beek HCA.
van der Stoep HJ.
van Oort H.
van Leenen J.
Ind.
Eng. Chem. Prod. Res. Dev.
1982,
21:
123
<A NAME="RC05402SS-6">6 </A>
Paleta O.
Jezek R.
Dedek V.
Collect.
Czech. Chem. Commun.
1983,
48:
766
<A NAME="RC05402SS-7">7 </A>
Paleta O.
Dadak V.
Dedek V.
Timpe H.-J.
J. Fluorine Chem.
1998,
39:
397
<A NAME="RC05402SS-8">8 </A>
Liska F.
Fikar J.
Kuzmic P.
Collect.
Czech. Chem. Commun.
1993,
58:
565
<A NAME="RC05402SS-9">9 </A>
Huang CG.
Rozov LA.
Halpern DF.
Vernice GG.
J.
Org. Chem.
1993,
58:
7382
<A NAME="RC05402SS-10">10 </A>
Ramig K.
Quiroz F.
Vernice GG.
Rozov LA.
J. Fluorine Chem.
1996,
80:
101
<A NAME="RC05402SS-11">11 </A>
Rozov LA,
Quiroz F, and
Vernice GG. inventors; US
Patent 5416244.
<A NAME="RC05402SS-12">12 </A>
Ramig K.
Krishnaswami A.
Rozov L.
Tetrahedron
1996,
52:
319
<A NAME="RC05402SS-13">13 </A>
Rozov LA.
Rafalko PW.
Evans SM.
Brockunier L.
Ramig K.
J. Org. Chem.
1995,
60:
1319
<A NAME="RC05402SS-14">14 </A>
Banks RE.
Tatlow JC. In
Organofluorine
Chemistry Principles and Commercial Applications
Banks RE.
Smart BE.
Tatlow JC.
Plenum
Press;
New York and London:
1994.
p.25
<A NAME="RC05402SS-15">15 </A>
Rozov LA.
Lessor RA.
Kudzma LV.
Ramig K.
J. Fluorine
Chem.
1998,
88:
51
<A NAME="RC05402SS-16">16 </A>
Cunningham DD.
Huang S.
Webster J.
Mayoral J.
Grabenkort RW.
Br.
J. Anaesth.
1996,
77:
537
<A NAME="RC05402SS-17">17 </A>
Knunyants IL.
Cheburkov YuA.
Bargamova MD.
Izv. Akad. Nauk., Ser. Khim.
1963,
1265 ; and references therein
<A NAME="RC05402SS-18">18 </A>
Anderson DG,
England DC, and
Milian AS. inventors; US Patent 4357282.
<A NAME="RC05402SS-19">19 </A>
England DC.
J.
Org. Chem.
1984,
49:
4007
<A NAME="RC05402SS-20">20 </A>
Hudlicky M.
J.
Fluorine Chem.
1985,
29:
349
<A NAME="RC05402SS-21">21 </A>
Nguyen T.
J.
Fluorine Chem.
1988,
38:
95
<A NAME="RC05402SS-22">22 </A>
Ramig K.
Kudzma LV.
Lessor RA.
Rozov LA.
J. Fluorine
Chem.
1999,
94:
1
<A NAME="RC05402SS-23">23 </A>
Rozov LA.
Mirzabekyants NS.
Zeifman YuV.
Cheburkov YuA.
Knunyants IL.
Russ. Chem. Bull.
1974,
1274
<A NAME="RC05402SS-24">24 </A>
Kocharyan ST.
Rokhlin EM.
Knunyants IL.
Russ. Chem. Bull.
1967,
1768
<A NAME="RC05402SS-25">25 </A>
Knunyants IL.
Kocharyan ST.
Cheburkov YuA.
Bargamova MD.
Rokhlin EM.
Dokl. Akad. Nauk.
1965,
165:
827
<A NAME="RC05402SS-26">26 </A>
Rokhlin EM.
Gambaryan NP.
Knunyants IL.
Dokl. Akad. Nauk.
1960,
135:
613
<A NAME="RC05402SS-27">27 </A>
Jeong IH.
Park TW.
Kim BT.
Synth.
Commun.
1998,
28:
1981
<A NAME="RC05402SS-28">28 </A>
Ramig, K.; Englander, M.; Kallashi,
F.; Livchits, L.; Zhou, J. Tetrahedron Lett. in
press.
<A NAME="RC05402SS-29">29 </A>
Kallashi, F.; Ramig K. unpublished
results.
<A NAME="RC05402SS-30">30 </A>
Krishnamurthy, L.; Makeyev, Y.; Ramig
K. unpublished results.
<A NAME="RC05402SS-31">31 </A>
Cram DJ.
Wingrove AS.
J. Am. Chem. Soc.
1963,
85:
1100
<A NAME="RC05402SS-32">32 </A>
Doyle TR.
Vogl O.
J. Am. Chem. Soc.
1989,
111:
8510
<A NAME="RC05402SS-33">33 </A>
Costante J.
Hecht L.
Polavarapu PL.
Collet A.
Barron LD.
Angew.
Chem., Int. Ed. Engl.
1997,
36:
885
<A NAME="RC05402SS-34">34 </A>
Rozov LA.
Ramig K.
Tetrahedron Lett.
1994,
35:
4501
<A NAME="RC05402SS-35">35 </A>
Ramig K.
Brockunier L.
Rafalko PW.
Rozov LA.
Angew. Chem., Int.
Ed. Engl.
1995,
3:
222
<A NAME="RC05402SS-36">36 </A>
Rozov LA.
Ramig K.
Chirality
1996,
8:
3
<A NAME="RC05402SS-37">37 </A>
Polavarapu PL.
Zhao C.
Ramig K.
Tetrahedron: Asymmetry
1999,
10:
1099
<A NAME="RC05402SS-38">38 </A>
Ramig K.
Halpern D. In
Enantiocontrolled
Synthesis of Fluoro-Organic Compounds: Stereochemical Challenges and
Biomedicinal Targets
Soloshonok V.
John
Wiley & Sons;
Chichester:
1999.
p.451
<A NAME="RC05402SS-39">39 </A>
Ramig K. In Asymmetric
Fluoroorganic Chemistry
Ramachandran PV.
American Chemical Society;
Washington:
2000.
p.282-292
<A NAME="RC05402SS-40">40 </A>
Rozov LA.
Huang CG.
Halpern DF.
Vernice GG.
Ramig K.
Tetrahedron: Asymmetry
1997,
8:
3023
<A NAME="RC05402SS-41">41 </A>
Rozov LA,
Huang CG,
Halpern DF, and
Vernice GG. inventors; US
Patent 5283372.
