Abstract
Treatment with base of N ′-aryl
urea derivatives of het-ero- or carbocyclic amines with
benzylic nitrogen atoms promotes rearrangement with transfer of
the aryl ring from N to C, giving rise to α-arylated products.
Key words
arylation - amines - heterocycles - lithiation - ureas
References and Notes
<A NAME="RD36908ST-1A">1a </A>
Clayden J.
Organolithiums:
Selectivity for Synthesis
Pergamon;
Oxford:
2002.
<A NAME="RD36908ST-1B">1b </A>
Gawley RE.
Coldham I. In The Chemistry of Organolithium Compounds
Rappoport Z.
Marek I.
Wiley;
New
York:
2004.
p.997-1053
<A NAME="RD36908ST-1C">1c </A>
Beak P.
Johnson TA.
Kim DS.
Lim SH.
Top. Organomet. Chem.
2003,
5:
139
<A NAME="RD36908ST-2A">2a </A>
Campos KR.
Chem. Soc. Rev.
2007,
36:
1027
<A NAME="RD36908ST-2B">2b </A>
O’Brien P.
Bilke JL.
Angew.
Chem. Int. Ed.
2008,
47:
2734
<A NAME="RD36908ST-3A">3a </A>
Clayden J.
Dufour J.
Grainger D.
Helliwell M.
J.
Am. Chem. Soc.
2007,
129:
7488
<A NAME="RD36908ST-3B">3b </A>
Clayden J.
Hennecke U.
Org. Lett.
2008,
10:
3567
<A NAME="RD36908ST-4A">4a </A>
Kerrick ST.
Beak P.
J.
Am. Chem. Soc.
1991,
113:
9708
<A NAME="RD36908ST-4B">4b </A>
Beak P.
Kerrick ST.
Wu S.
Chu J.
J. Am. Chem. Soc.
1994,
116:
3231
<A NAME="RD36908ST-5A">5a </A>
Clayden J.
Dufour J.
Tetrahedron
Lett.
2006,
47:
6945
<A NAME="RD36908ST-5B">5b </A>
Clayden J.
Turner H.
Pickworth M.
Adler T.
Org. Lett.
2005,
7:
3147
<A NAME="RD36908ST-5C">5c </A>
Hassel T.
Seebach D.
Helv. Chim. Acta
1978,
61:
2237
<A NAME="RD36908ST-5D">5d </A>
Resek JE.
Beak P.
J. Am. Chem. Soc.
1994,
116:
405
<A NAME="RD36908ST-5E">5e </A>
Anderson DR.
Faibish NC.
Beak P.
J. Am. Chem. Soc.
1999,
121:
7553
<A NAME="RD36908ST-5F">5f </A>
Meigh
J.-P.
Álvarez M.
Joule JA.
J. Chem. Soc., Perkin Trans. 1
2001,
2012
<A NAME="RD36908ST-5G">5g </A>
Llopart CC.
Ferrer C.
Joule JA.
Can. J. Chem.
2004,
82:
1649
<A NAME="RD36908ST-6">6 </A> 2-Phenylpyrrolidine was made in enantiomerically
enriched form (er = 92:8 by GC) by the method of:
Verdaguer X.
Lange U.
Reding MT.
Buchwald SL.
J.
Am. Chem. Soc.
1996,
118:
6784
DMPU promotes reactions involving
dearomatising addition of organolithiums to aromatic rings. See:
<A NAME="RD36908ST-7A">7a </A>
Clayden J.
Knowles FE.
Menet CJ.
Synlett
2003,
1701
<A NAME="RD36908ST-7B">7b </A>
Clayden J.
Parris S.
Cabedo N.
Payne AH.
Angew. Chem. Int. Ed.
2008,
47:
5060
<A NAME="RD36908ST-8">8 </A>
Alongside remaining starting material,
byproducts from this reaction included those arising from ortholithiation
of the aryl ring followed by anionic ortho -Fries
rearrangement (see Sibi, M. P.; Snieckus, V. J.
Org. Chem. 1983 , 48 ,
1935). Quenching the reaction mixture with TMSCl yielded no products
of silylation α to nitrogen.
For recent synthesis of pyrrolidines
containing quaternary centres, see:
<A NAME="RD36908ST-9A">9a </A>
Calaza MI.
Cativiela C.
Eur. J.
Org. Chem.
2008,
3427
<A NAME="RD36908ST-9B">9b </A>
Makosza M.
Sulikowski D.
Maltsev O.
Synlett
2008,
1711
<A NAME="RD36908ST-10">10 </A>
The X-ray crystallographic data for 9d has been deposited with the Cambridge
Crystallographic Database, deposition number 706267.
For a review of the chemistry of
nicotine analogues, see:
<A NAME="RD36908ST-11A">11a </A>
Wagner F.
Comins DL.
Tetrahedron
2007,
63:
8065
Conformationally constrained analogues of nicotine are of medicinal
interest, see:
<A NAME="RD36908ST-11B">11b </A>
Papke RL.
Zheng G.
Horenstein NA.
Dwoskin LP.
Crooks PA.
Bioorg. Med. Chem.
Lett.
2005,
15:
3874
<A NAME="RD36908ST-11C">11c </A>
Luo S.
Fang F.
Zhao M.
Zhai H.
Tetrahedron
2004,
60:
5353
<A NAME="RD36908ST-11D">11d </A>
Rao
TS.
Sacaan AI.
Menzaghi FM.
Reid RT.
Adams
PB.
Correa LD.
Whelan KT.
Vernier J.-M.
Brain Res.
2004,
1003:
4
<A NAME="RD36908ST-11E">11e </A>
Sarkar TK.
Basak S.
Wainer I.
Moaddel R.
Yamaguchi R.
Jozwiak K.
Chen H.-T.
Lin C.-C.
J. Med. Chem.
2004,
47:
6691
<A NAME="RD36908ST-11F">11f </A>
Denton TT.
Zhang Xi.
Cashman JR.
J. Med. Chem.
2005,
48:
224
<A NAME="RD36908ST-11G">11g </A>
Sarkar TK.
Basak S.
Slanina Z.
Chow TJ.
J.
Org. Chem.
2003,
68:
4206
<A NAME="RD36908ST-11H">11h </A>
Zhai H.
Liu P.
Luo S.
Fang F.
Zhao M.
Org. Lett.
2002,
4:
4385
<A NAME="RD36908ST-11I">11i </A>
Ullrich T.
Krich S.
Binder D.
Mereiter K.
Anderson DJ.
Meyer MD.
Pyerin M.
J.
Med. Chem.
2002,
45:
4047
<A NAME="RD36908ST-11J">11j </A>
Xu R.
Dwoskin LP.
Grinevich V.
Sumithran SP.
Crooks
PA.
Drug Dev. Res.
2002,
55:
173
<A NAME="RD36908ST-11K">11k </A>
Ullrich T.
Binder D.
Pyerin M.
Tetrahedron
Lett.
2002,
43:
177
<A NAME="RD36908ST-11L">11l </A>
Ferretti G.
Dukat M.
Giannella M.
Piergentili A.
Pigini M.
Quaglia W.
Damaj MI.
Martin BR.
Glennon RA.
Bioorg. Med. Chem. Lett.
2000,
10:
2665
<A NAME="RD36908ST-11M">11m </A>
Kim KH.
Lin N.-H.
Anderson DJ.
Bioorg. Med. Chem.
1996,
4:
2211
<A NAME="RD36908ST-11N">11n </A>
Glennon RA.
Maarouf A.
Fahmy S.
Martin B.
Fang F.
Yousif M.
Shafik RM.
Dukat M.
Med. Chem. Res.
1993,
2:
546
<A NAME="RD36908ST-11O">11o </A>
Meyers AI.
Marra JM.
Tetrahedron
Lett.
1985,
26:
5863
<A NAME="RD36908ST-12">12 </A>
In THF, decomposition products suggest
that lithiation is followed by intra- and/or intermolecular
addition to the 2- or 4-position of the pyridyl ring, rather than
the 3-position.
<A NAME="RD36908ST-13">13 </A>
Compound 19e was
made by standard methods from commercially available material.