Abstract
Dihalobenzenes that possess directing groups such as OH, CH2OH,
NH2, NHAc, or NHBoc were subjected to ortho-selective cross-coupling
with Grignard reagents in the presence of palladium-based catalysts
to give the corresponding substituted monohalobenzenes. For the
dibromo- and dichlorophenols and anilines, hydroxylated terphenylphosphines 1 and 2 were found
to be effective ligands for palladium, whereas tricyclohexylphosphine
was preferable for the dichlorobenzyl alcohols, dichloroanilides,
and difluorobenzenes.
Key words
cross-coupling - palladium - site-selective - Grignard reagents - dihalobenzenes
References
<A NAME="RZ16608SS-1A">1a</A>
Naumann K.
J. Prakt. Chem.
1999,
341:
417
<A NAME="RZ16608SS-1B">1b</A>
Müller K.
Faeh C.
Diederich F.
Science
2007,
317:
1881
<A NAME="RZ16608SS-2">2</A>
Urch CJ. In
Comprehensive Organic Functional Group Transformations
Vol.
2:
Katritzky AR.
Taylor RJK.
Pergamon;
Cambridge:
1995.
p.605
<A NAME="RZ16608SS-3A">3a</A>
Reddy GS.
Tam W.
Organometallics
1984,
3:
630
<A NAME="RZ16608SS-3B">3b</A>
Singh R.
Just G.
J. Org. Chem.
1989,
54:
4453
<A NAME="RZ16608SS-3C">3c</A>
Dirk SM.
Price DW.
Chanteau S.
Kosynkin DV.
Tour JM.
Tetrahedron
2001,
57:
5109
<A NAME="RZ16608SS-3D">3d</A>
Ackermann L.
Althammer A.
Angew. Chem. Int. Ed.
2007,
46:
1627
<A NAME="RZ16608SS-3E">3e</A>
Houpis IN.
Hoeck J.-PV.
Tilstam U.
Synlett
2007,
2179
<A NAME="RZ16608SS-3F">3f</A>
Ishii Y.
Chatani N.
Yorimitsu S.
Murai S.
Chem. Lett.
1998,
27:
157
<A NAME="RZ16608SS-3G">3g</A>
Wang T.
Alfonso BJ.
Love JA.
Org. Lett.
2007,
9:
5629
For site-selective cross-coupling of polyhalogenated heteroarenes,
see:
<A NAME="RZ16608SS-3H">3h</A>
Schröter S.
Stock C.
Bach T.
Tetrahedron
2005,
61:
2245
<A NAME="RZ16608SS-3I">3i</A>
Fairlamb IJS.
Chem. Soc. Rev.
2007,
36:
1036
<A NAME="RZ16608SS-4A">4a</A>
Ishikawa S.
Manabe K.
Chem.
Lett.
2007,
36:
1304
<A NAME="RZ16608SS-4B">4b</A>
Ishikawa S.
Manabe K.
Org. Lett.
2007,
9:
5593
<A NAME="RZ16608SS-4C">4c</A>
Manabe K.
Ishikawa S.
Synthesis
2008,
2645
For reviews on cross-coupling with
Grignard reagents, see:
<A NAME="RZ16608SS-5A">5a</A>
Tsuji J.
Palladium Reagents and Catalysts
Wiley;
West Sussex:
2004.
p.335
<A NAME="RZ16608SS-5B">5b</A>
Cepanec I.
Synthesis of Biaryls
Elsevier;
Oxford:
2004.
p.83
<A NAME="RZ16608SS-6">6</A>
Ishikawa S.
Manabe K.
Chem. Lett.
2007,
36:
1302
<A NAME="RZ16608SS-7">7</A> The design of these terphenylphosphines
is based on biphenylphosphines developed by Buchwald et al., see:
Wolfe JP.
Buchwald SL.
Angew. Chem. Int. Ed.
1999,
38:
2413
<A NAME="RZ16608SS-8">8</A>
Phosphine 1 was
purified and stored as the HBF4 salt.
