Abstract
The intramolecular Heck cyclization of N-allyl-, -aryl- or -benzyl-5-allyl-2-pyrrolidinones and N-allyl-, -aryl- or -benzyl-6-allyl-2-piperidinones (1a-f), prepared through allyltrimethylsilane addition to the corresponding cyclic N-acyliminium ions, afforded indolizidinones (3a, 5a, 5b), quinolizidinones (3b, 4b) and benzoazepinones (7a, 8a, 7b, 8b) in moderate to good yields (56-90%). Exclusive exo-trig over endo-trig mode of cyclization was observed in all examples investigated, and it was accompanied
by double bond migration, which precluded our attempts of a one-pot tandem Diels-Alder
cycloaddition with dienophiles such as maleic anhydride, methyl vinyl ketone and diethyl
azodicarboxylate. Catalytic hydrogenation of a 2:1 mixture of regioisomeric indolizidinones
5a-5b afforded the stereoisomerically enriched cis indolizidinone 6a (20:1 mixture) in quantitative yield. A similar behavior was observed in the catalytic
hydrogenation of regioisomeric benzoazepinones 7b-8b.
Key words
Heck reaction - intramolecular cylization - hydrogenation
References
<A NAME="RM00701SS-1A">1a</A>
Negishi EI.
Liu F.
In Metal-catalyzed Cross-coupling Reactions
Diederich F.
Stang PJ.
Wiley-VCH;
Weinheim:
1998.
Chap.1.
p.1
<A NAME="RM00701SS-1B">1b</A>
Negishi EI.
Coperet C.
Ma SM.
Liou SY.
Liu F.
Chem. Rev.
1996,
96:
365
<A NAME="RM00701SS-1C">1c</A>
Daves GD.
Hallberg A.
Chem. Rev.
1989,
89:
1433
<A NAME="RM00701SS-2A">2a</A>
Bräse S.
de Meijere A. In Metal-catalyzed Cross-coupling Reactions
Diederich F.
Stang PJ.
Wiley-VCH;
Weinheim:
1998.
p.99
<A NAME="RM00701SS-2B">2b</A>
Cabri W.
Cadiani I.
Acc. Chem. Res.
1995,
28:
2
<A NAME="RM00701SS-2C">2c</A>
de Meijere A.
Meyer FE.
Angew. Chem. Int. Ed. Engl.
1994,
106:
2473
<A NAME="RM00701SS-2D">2d</A>
Heck RF. In Comprehensive Organic Synthesis
Vol. 4:
Trost BM.
Fleming I.
Pergamon Press;
Oxford:
1991.
p.833
<A NAME="RM00701SS-2E">2e</A>
Heck RF. In Palladium Reagents in Organic Synthesis
Academic Press;
London:
1985.
<A NAME="RM00701SS-3A">3a</A>
Tietze LF.
Chem. Rev.
1996,
96:
115
<A NAME="RM00701SS-3B">3b</A>
Waldmann H. In
Domino Reactions in Organic Synthesis Highlights II
Waldmann H.
VCH;
Weinheim:
1995.
p.193
<A NAME="RM00701SS-3C">3c</A>
Tietze LF.
Beifuss U.
Angew. Chem. Int. Ed. Engl.
1993,
32:
131
<A NAME="RM00701SS-3D">3d</A>
Curran DP. In
Comprehensive Organic Synthesis
Vol. 4:
Trost BM.
Fleming I.
Pergamon Press;
Oxford:
1991.
p.779
<A NAME="RM00701SS-4A">4a</A>
Moreno-Manãs M.
Pleixats R.
Roglans A.
Liebigs Ann. Chem.
1995,
1807
<A NAME="RM00701SS-4B">4b</A>
Ang KH.
Bräse S.
Steinig AG.
Meyer FE.
Llebaria A.
Voigt K.
de Meijere A.
Tetrahedron
1996,
52:
11503
<A NAME="RM00701SS-4C">4c</A>
Meyer FE.
Ang KH.
Steinig GA.
de Meijere A.
Synlett
1994,
191
<A NAME="RM00701SS-5A">5a</A>
Ikeda M.
El Bialy SAA.
Yakura T.
Heterocycles
1999,
51:
1957
<A NAME="RM00701SS-5B">5b</A>
Lemaire-Audoire S.
Savignac M.
Dupuis C.
Genêt J.-P.
Tetrahedron Lett.
1996,
2003
<A NAME="RM00701SS-5C">5c</A>
Grigg R.
Stevenson PJ.
Worakun T.
Tetrahedron
1988,
44:
2033
<A NAME="RM00701SS-5D">5d</A>
Shi L.
Narula CK.
Mak KT.
Kao L.
Xu Y.
Heck RF.
J. Org. Chem.
1983,
48:
3894
<A NAME="RM00701SS-6">6</A>
Bhat L.
Steinig A.
Appelbe R.
de Meijere A.
Eur. J. Org. Chem.
2001,
9:
1673
<A NAME="RM00701SS-7A">7a</A>
Alves CF.
Böckelmann MA.
Mascarenhas YP.
Nery JG.
Vencato I.
Pilli RA.
Tetrahedron Lett.
1999,
40:
2891
<A NAME="RM00701SS-7B">7b</A>
Maldaner AO.
Pilli RA.
Tetrahedron
1999,
55:
13321
<A NAME="RM00701SS-7C">7c</A>
Maldaner AO.
Pilli RA.
Tetrahedron Lett.
2000,
41:
7843
<A NAME="RM00701SS-7D">7d</A>
D`Oca MGM.
Vencato I.
Pilli RA.
Tetrahedron Lett.
2000,
41:
9709
<A NAME="RM00701SS-7E">7e</A>
Santos LS.
Pilli RA.
Tetrahedron Lett.
2001,
42:
6999
<A NAME="RM00701SS-7F">7f</A>
Pilli RA.
Zanotto PR.
Böckelmann MA.
Tetrahedron Lett.
2001,
42:
7003
For recent reviews on the addition of carbon nucleophiles to N-acyliminium ions:
<A NAME="RM00701SS-8A">8a</A>
Russowsky D.
Pilli RA.
Trends Org. Chem.
1997,
6:
101
<A NAME="RM00701SS-8B">8b</A>
Moolenaar MJ.
Speckamp WN.
Tetrahedron
2000,
56:
3817
For the in situ reduction of palladium(II) to palladium(0) species, see:
<A NAME="RM00701SS-9A">9a</A>
Trost BM.
Murphy DJ.
Organometallics
1985,
4:
1143
<A NAME="RM00701SS-9B">9b</A>
McCrindle R.
Ferguson G.
Arsenault GJ.
McAlees AJ.
J. Chem. Soc., Chem. Commun.
1983,
571 ; and references cited therein
<A NAME="RM00701SS-9C">9c</A>
Amatore C.
Jutand A.
M’Barki MA.
Organometallics
1992,
11:
3009
<A NAME="RM00701SS-9D">9d</A>
Hayashi T.
Kubo A.
Ozawa F.
Pure Appl. Chem.
1992,
64:
421
<A NAME="RM00701SS-10">10</A>
Herrmann WA.
Brömer C.
Öfele K.
Reisinger C.-P.
Priermeier T.
Beller M.
Fischer H.
Angew. Chem. Int. Ed. Engl.
1995,
34:
1844
<A NAME="RM00701SS-11">11</A>
Gaussian 98, Revision A.6, Gaussian, Inc., Pittsburgh PA, 1998.
<A NAME="RM00701SS-12A">12a</A>
Melpolder JB.
Heck RF.
J. Org. Chem.
1976,
41:
265
<A NAME="RM00701SS-12B">12b</A>
Chalk AJ.
Magennis SA.
J. Org. Chem.
1976,
41:
273
<A NAME="RM00701SS-12C">12c</A>
Chalk AJ.
Magennis SA.
J. Org. Chem.
1976,
41:
1206
<A NAME="RM00701SS-13">13</A>
Kang S.-K.
Jung K.-Y.
Park C.-H.
Namkoong E.-Y.
Kim T.-H.
Tetrahedron Lett.
1995,
36:
6287
<A NAME="RM00701SS-14A">14a</A>
Jeffery T.
Tetrahedron Lett.
1985,
26:
2667
<A NAME="RM00701SS-14B">14b</A>
Jeffery T.
J. Chem. Soc., Chem. Commun.
1984,
1287
<A NAME="RM00701SS-14C">14c</A>
Jeffery T.
Tetrahedron
1996,
52:
10113
<A NAME="RM00701SS-15">15</A>
Abelman MM.
Oh T.
Overman LE.
J. Org. Chem.
1987,
52:
4130
<A NAME="RM00701SS-16">16</A>
Schuch CM.
Pilli RA.
Tetrahedron: Asymmetry
2000,
11:
753
<A NAME="RM00701SS-17">17</A>
N-2-iodophenyl succinimide was prepared from succinic anhydride, 2-iodoaniline and
acetyl chloride according to ref.
[16.]
