Abstract
Lithiation of 2-bromo-1,1-diphenylethene (2 ) with n -butyllithium or tert -butyllithium/tetramethylethylenediamine (TMEDA) in pentane at -100 °C effects a halogen-lithium
exchange to give 2-lithio-1,1-diphenylethene (3 ) exclusively, which reacts with electrophiles to provide 2-substituted-1,1-diphenylethenes
5 -8 in high yields. Further lithiation of the monolithium derivative 3 with n -butyllithium/TMEDA results in the direct ortho -lithiation of Z -located phenyl ring to give dilithium derivative 9 , which forms disubstituted ethenes 11 -13 or heterocycles 15 -17 on treatment with electrophiles. tert -Butyllithium/TMEDA is ineffective for the second lithiation step.
Key words
halides - lithiation - organometallic reagents - complexes - regioselectivity
References <A NAME="RT08801SS-1">1 </A>
Current address: Institute of Organic Chemistry, Georg-August-Universität Göttingen,
Tammannstr.2, 37077 Göttingen, Germany. Fax: +49(551)399475; E-mail: sergei.korneev@gmx.de.
<A NAME="RT08801SS-2">2 </A>
Curtin DY.
Flynn EW.
J. Am. Chem. Soc.
1959,
81:
4714
<A NAME="RT08801SS-3A">3a </A>
Braun M. In
Houben-Weyl
4 th ed., Vol. E19d:
Hanack M.
Thieme;
Stuttgart:
1993.
p.171
<A NAME="RT08801SS-3B">3b </A>
Braun M.
Angew. Chem. Int. Ed.
1998,
37:
43 ; Angew. Chem. 1998 , 110 , 444
<A NAME="RT08801SS-4">4 </A>
Köbrich G.
Trapp H.
Akhtar A.
Chem. Ber.
1968,
101:
2644
<A NAME="RT08801SS-5">5 </A>
Köbrich G.
Trapp H.
Chem. Ber.
1966,
99:
670
<A NAME="RT08801SS-6A">6a </A>
Köbrich G.
Trapp H.
Chem. Ber.
1966,
99:
680
<A NAME="RT08801SS-6B">6b </A>
Modena G.
Scorrano G. In
The Chemistry of the Carbon-Halogen Bond
Part 1:
Patai S.
Wiley;
New York:
1973.
p.301
<A NAME="RT08801SS-7A">7a </A>
Coleman GH.
Maxwell RD.
J. Am. Chem. Soc.
1934,
56:
132
<A NAME="RT08801SS-7B">7b </A>
Jacobs TL.
Org. React.
1962,
5:
1
<A NAME="RT08801SS-7C">7c </A>
Zimmerman HE. In
Molecular Rearrangements
Part 1:
de Mayo P.
Wiley;
New York:
1963.
p.345
<A NAME="RT08801SS-7D">7d </A>
Köbrich G.
Buck P. In
Chemistry of Acetylenes
Viehe HG.
Dekker;
New York:
1969.
p.117
<A NAME="RT08801SS-8">8 </A>
Bothner-By AA.
J. Am. Chem. Soc.
1955,
77:
3293
<A NAME="RT08801SS-9">9 </A>
Curtin DY.
Richardson WH.
J. Am. Chem. Soc.
1959,
81:
4719
<A NAME="RT08801SS-10A">10a </A>
Fritsch P.
Liebigs Ann. Chem.
1894,
279:
319
<A NAME="RT08801SS-10B">10b </A>
Buttenberg WP.
Liebigs Ann. Chem.
1894,
279:
324
<A NAME="RT08801SS-10C">10c </A>
Wiechell H.
Liebigs Ann. Chem.
1894,
279:
337
<A NAME="RT08801SS-11">11 </A>
Köbrich G.
Stöber I.
Chem. Ber.
1970,
103:
2744
<A NAME="RT08801SS-12">12 </A>
Curtin DY.
Quirk RP.
Tetrahedron
1968,
24:
5791
<A NAME="RT08801SS-13">13 </A>
Curtin DY.
Flynn EW.
Nystrom RF.
J. Am. Chem. Soc.
1958,
80:
4599
<A NAME="RT08801SS-14">14 </A>
One equivalent of n -BuLi is required for the metalation of 2 to 3 . The second equivalent reacts with butyl bromide formed to turn the metalation equilibrium
to the side of products: 2 + BuLi → 3 + BuBr, BuLi + BuBr → Bu-Bu + LiBr.
<A NAME="RT08801SS-15">15 </A>
Neugebauer W.
Kos AJ.
Schleyer PvR.
J. Organomet. Chem.
1982,
228:
107
<A NAME="RT08801SS-16">16 </A>
Vogel A.
Vogel’s Textbook of Practical Organic Chemistry
4 th ed.:
Longman;
New York:
1981.
p.326
<A NAME="RT08801SS-17">17 </A>
Pouchert CJ.
The Aldrich Library of Infrared Spectra
Aldrich Chemical Co.;
Wisconsin: Milwaukee, 1970.
<A NAME="RT08801SS-18">18 </A>
Cochran JC.
Phillips HK.
Tom S.
Hurd AR.
Bronk BS.
Organometallics
1994,
13:
947
<A NAME="RT08801SS-19">19 </A>
Bremser W.
Ernst L.
Franke B.
Carbon-13 NMR Spectral Data
4 th ed.:
VCH;
Weinheim:
1987.
<A NAME="RT08801SS-20">20 </A>
Barluenga J.
Campos PJ.
Gonzalez JM.
Suarez JL.
Asensio G.
J. Org. Chem.
1991,
56:
2234
<A NAME="RT08801SS-21">21 </A>
Sokolov VI.
Bashilov VV.
Reutov OA.
J. Organomet. Chem.
1978,
162:
271
<A NAME="RT08801SS-22">22 </A>
Acetone-d
6 was used as internal standard, δ = 2.05.
<A NAME="RT08801SS-23">23 </A>
Ludvig MM.
Lagow RJ.
J. Org. Chem.
1990,
55:
4880
<A NAME="RT08801SS-24">24 </A>
Greenwald R.
Chaykovsky M.
Corey EJ.
J. Org. Chem.
1963,
28:
1128
<A NAME="RT08801SS-25">25 </A>
van der Linde R.
Korver O.
Korver PK.
van der Haak PJ.
Veenland JU.
de Boer ThJ.
Spectrochimica Acta
1965,
21:
1893
<A NAME="RT08801SS-26">26 </A>
Ni Z.-J.
Mei N.-W.
Shi X.
Tzeng Y.-L.
Wang MC.
Luh T.-Y.
J. Org. Chem.
1991,
56:
4035
<A NAME="RT08801SS-27">27 </A>
Gröbel B.-T.
Seebach D.
Chem. Ber.
1977,
110:
852
<A NAME="RT08801SS-28">28 </A>
Koerwitz FL.
Hammond GB.
Wiemer DF.
J. Org. Chem.
1989,
54:
743
<A NAME="RT08801SS-29">29 </A>
Maercker A.
Bös B.
Hajgholipour MT.
J. Organomet. Chem.
1998,
566:
143
<A NAME="RT08801SS-30">30 </A>
Kunai A.
Matsuo Y.
Ishikawa M.
Organometallics
1993,
12:
2536
<A NAME="RT08801SS-31A">31a </A>
Geneste P.
Olive J.-L.
Ung SN.
Faghi MEAE.
Easton JW.
Beierbeck H.
Saunders JK.
J. Org. Chem.
1979,
44:
2887
<A NAME="RT08801SS-31B">31b </A>
Seyferth D.
Tronich W.
Marmor RS.
Smith WE.
J. Org. Chem.
1972,
37:
1537
<A NAME="RT08801SS-32">32 </A>
Kersey ID.
Fishwick CWG.
Findlay JBC.
Ward P.
Tetrahedron
1995,
51:
6819