Abstract
Allylation reactions promoted by niobium pentachloride are described. Allylstannanes
were added to aromatic and aliphatic aldehydes and aromatic imines in good yields.
Excellent syn diastereoselectivities were obtained in the addition of (E )-cinnamylstannane to benzaldehyde (49:1) and in the addition of crotylstannane to
N -benzylideneaniline (46:1).
Key words
allylation - homoallylic compounds - stereoselectivity - niobium pentachloride - Lewis
acids
References
1a </A>
Yamamoto Y.
Asao N.
Chem. Rev.
1993,
93:
2207
1b </A>
Nishigaichi Y.
Takuwa A.
Naruta Y.
Maruyama K.
Tetrahedron
1993,
49:
7395
1c </A>
Marshall JA.
Chem. Rev.
1996,
96:
31
1d </A>
Bloch R.
Chem. Rev.
1998,
98:
1407
2a </A>
Suzuki K.
Hashimoto T.
Maeta H.
Matsumoto T.
Synlett
1992,
125
2b </A>
Maeta H.
Nagasawa T.
Handa Y.
Takei T.
Osamura Y.
Suzuki K.
Tetrahedron Lett.
1995,
36:
899
2c </A>
Howarth J.
Gillespie K.
Tetrahedron Lett.
1996,
37:
6011
2d </A>
Yamamoto M.
Nakazawa M.
Kishikawa K.
Kohmoto S.
Chem. Commun.
1996,
20:
2353
2e </A>
Chandrasekhar S.
Takhi M.
Reddy YR.
Mohapatra S.
Rao CR.
Reddy KV.
Tetrahedron
1997,
53:
14997
2f </A>
Kobayashi S.
Busujima T.
Nagayama S.
Chem.-Eur. J.
2000,
6:
3491
<A NAME="RC00902SS-3">3 </A>
Hagen G.
Mayr H.
J. Am. Chem. Soc.
1991,
113:
4954
<A NAME="RC00902SS-4">4 </A> For a review on niobium compounds, see:
Nowak I.
Ziolek M.
Chem. Rev.
1999,
99:
3603
5a </A>
Andrade CKZ.
Azevedo NR.
Tetrahedron Lett.
2001,
42:
6473
5b </A>
Andrade CKZ.
Oliveira GR.
Tetrahedron Lett.
2002,
43:
1935
<A NAME="RC00902SS-6">6 </A>
Yamamoto Y.
Yatagai H.
Ishihara Y.
Maeda N.
Maruyama K.
Tetrahedron
1984,
40:
2239
<A NAME="RC00902SS-7">7 </A>
Heathcock CH.
Kiyooka S.
Blumenkopf TA.
J. Org. Chem.
1984,
49:
4214
<A NAME="RC00902SS-8">8 </A>
Keck GE.
Abbott DE.
Boden EP.
Enholm EJ.
Tetrahedron Lett.
1984,
25:
3927
<A NAME="RC00902SS-9">9 </A>
Coxon JM.
van Eyk SJ.
Steel PJ.
Tetrahedron
1989,
45:
1029
10a </A>
Denmark SE.
Wilson T.
Willson TM.
J. Am. Chem. Soc.
1988,
110:
984
10b </A>
Denmark SE.
Weber EJ.
Wilson TM.
Willson TM.
Tetrahedron
1989,
45:
1053
10c </A>
Naruta Y.
Nishigaichi Y.
Maruyama K.
Tetrahedron
1989,
45:
1067
10d </A>
Keck GE.
Andrus MB.
Castellino S.
J. Am. Chem. Soc.
1989,
111:
8136
<A NAME="RC00902SS-11">11 </A> For its synthesis, see:
Carofiglio T.
Marton D.
Tagliavini G.
Organometallics
1992,
11:
2961
<A NAME="RC00902SS-12">12 </A>
Koreeda M.
Tanaka Y.
Chem. Lett.
1982,
1299
<A NAME="RC00902SS-13">13 </A> In CH2 Cl2 the reaction is syn -selective (82:18):
Yasuda M.
Sugawa Y.
Yamamoto A.
Shibata I.
Baba A.
Tetrahedron Lett.
1996,
37:
5951
<A NAME="RC00902SS-14">14 </A> The anti isomer is also obtained exclusively in the reaction of cinnamyl chloride with aldehydes
mediated by tin and aluminum. See ref. Also:
Uneyama K.
Nanbu H.
Torii S.
Tetrahedron Lett.
1986,
27:
2395
<A NAME="RC00902SS-15">15 </A> Reaction between cinnamyl bromide and benzaldehyde, mediated by zinc in aqueous
media:
Wilson RS.
Guazzaroni ME.
J. Org. Chem.
1989,
54:
3087
<A NAME="RC00902SS-16">16 </A>
1 H NMR (CDCl3 ) anti : δ = 1.54 (br, 1 H), 3.54 (t, 1 H, J = 8.3 Hz), 5.10-5.30 (m, 3 H), 6.25 (ddd, 1 H, J = 19.1, 10.2, 8.9 Hz), 7.00-7.38 (m, 10 H). See:
Coxon JM.
Simpson GW.
Steel PJ.
Trenerry VC.
Aust. J. Chem.
1984,
37:
65
<A NAME="RC00902SS-17">17 </A>
1 H NMR (CDCl3 ) syn : δ = 1.94 (br, 1 H), 3.63 (t, 1 H, J = 8.0 Hz), 4.78-5.04 (m, 3 H), 5.89 (ddd, 1 H, J = 7.8, 10.3, 18.1 Hz), 7.01-7.38 (m, 10 H). For comparison, see ref.
[27
<A NAME="RC00902SS-18">18 </A>
Wang D.-K.
Dai L.-X.
Hou X.-L.
Tetrahedron Lett.
1995,
36:
8649
19a </A>
Bellucci C.
Cozzi PG.
Umani-Ronchi A.
Tetrahedron Lett.
1995,
36:
7289
19b </A>
Kobayashi S.
Iwamoto S.
Nagayama S.
Synlett
1997,
1099
19c </A>
Kobayashi S.
Bujima T.
Nagayama S.
Chem. Commun.
1998,
19
19d </A>
Kobayashi S.
Ishitani H.
J. Syn. Org. Chem. Jpn.
1998,
56:
357
20a </A>
Nakamura H.
Iwama H.
Yamamoto Y.
Chem. Commun.
1996,
1459
20b </A>
Nakamura H.
Iwama H.
Yamamoto Y.
J. Am. Chem. Soc.
1996,
118:
6641
20c </A>
Nakamura H.
Nakamura K.
Yamamoto Y.
J. Am. Chem. Soc.
1998,
120:
4242
20d </A>
Bao M.
Nakamura H.
Yamamoto Y.
Tetrahedron Lett.
2000,
41:
131
20e </A>
Bao M.
Nakamura H.
Yamamoto Y.
Angew. Chem. Int. Ed.
2001,
40:
3208
21 </A>
The choice for CH2 Cl2 was based on the fact that the reaction in this solvent could be run at lower temperature
(-78 °C) as compared to CH3 CN.
<A NAME="RC00902SS-22">22 </A> An example of palladium-catalyzed double-allylation reaction has recently been
reported:
Nakamura H.
Aoyagi K.
Shim J.-G.
Yamamoto Y.
J. Am. Chem. Soc.
2001,
123:
372
<A NAME="RC00902SS-23">23 </A>
Wang D.-K.
Dai L.-X.
Hou X.-L.
Tetrahedron Lett.
1995,
36:
8649
<A NAME="RC00902SS-24">24 </A>
Yamamoto Y.
Komatsu T.
Maruyama K.
J. Org. Chem.
1985,
50:
3115
<A NAME="RC00902SS-25">25 </A>
Keck GE.
Enholm EJ.
J. Org. Chem.
1984,
50:
146
<A NAME="RC00902SS-26">26 </A>
For a complete discussion of the possible transition states geometries, see ref.
[24
27a </A>
Keck GE.
Savin KA.
Cressman ENK.
Abbott DE.
J. Org. Chem.
1994,
59:
7889
27b </A>
Keck GE.
Dougherty SM.
Savin KA.
J. Am. Chem. Soc.
1995,
117:
6210
<A NAME="RC00902SS-28">28 </A> An eight-membered cyclic transition state with synclinal arrangement of the reacting C=C and C=O double bonds has been suggested for the reaction
between aldehydes and allylsilane promoted by BF3 ·Et2Ο , based on computational evidence
Bottoni A.
Costa AL.
Tommaso DD.
Rossi I.
Tagliavini E.
J. Am. Chem. Soc.
1997,
119:
12131
