Abstract
Homoenolate equivalents are generated by Lewis basic N-heterocyclic carbene catalysts and then protonated to generate efficiently saturated esters from unsaturated aldehydes. This reactivity is extended to the generation of β-acylvinyl anions from alkynyl aldehydes. The asymmetric protonation of a homoenolate equivalent generated from a β,β-disubstituted aldehyde can be accomplished with a chiral N-heterocyclic carbene.
Key words
carbenes - umpolung - protonations - asymmetric catalysis - esters
References
1 Seebach D.
Angew. Chem., Int. Ed. Engl.
1979,
18:
239
2 Eisch JJ.
J. Organomet. Chem.
1995,
500:
101
3 Pohl M.
Lingen B.
Muller M.
Chem. Eur. J.
2002,
8:
5289
4 Enders D.
Niemeier O.
Henseler A.
Chem. Rev.
2007,
107:
5606
5 Marion N.
Diez-Gonzalez S.
Nolan IP.
Angew. Chem. Int. Ed.
2007,
46:
2988
6 Zeitler K.
Angew. Chem. Int. Ed.
2005,
44:
7506
7 Denmark SE.
Beutner GL.
Angew. Chem. Int. Ed.
2008,
47:
1560
8 Ugai T.
Tanaka R.
Dokawa T.
J. Pharm. Soc. Jpn.
1943,
63:
296
9 Breslow R.
J. Am. Chem. Soc.
1958,
80:
3719
10 Stetter H.
Kuhlmann H.
Chem. Ber.
1976,
109:
2890
11 Enders D.
Breuer K.
Runsink J.
Teles JH.
Helv. Chim. Acta
1996,
79:
1899
12 Sheehan JC.
Hunneman DH.
J. Am. Chem. Soc.
1966,
88:
3666
13 Enders D.
Niemeier O.
Balensiefer T.
Angew. Chem. Int. Ed.
2006,
45:
1463
14 Knight RL.
Leeper FJ.
J. Chem. Soc., Perkin Trans. 1
1998,
1891
15 Stetter H.
Lorenz G.
Chem. Ber.
1985,
118:
1115
16 Myers MC.
Bharadwaj AR.
Milgram BC.
Scheidt KA.
J. Am. Chem. Soc.
2005,
127:
14675
17 Mattson AE.
Scheidt KA.
Org. Lett.
2004,
6:
4363
18 Mattson AE.
Bharadwaj AR.
Scheidt KA.
J. Am. Chem. Soc.
2004,
126:
2314
19 Mattson AE.
Bharadwaj AR.
Zuhl AM.
Scheidt KA.
J. Org. Chem.
2006,
71:
5715
20 Our preliminary studies of generating homoenolates using N-heterocyclic carbenes and the protonation of these unusual intermediates was first described in a lecture by K.A.S. at the 2004 Natural Products Gordon Research Conference (Tilton, NH) on Thursday, July 29, 2004.
21 Burstein C.
Glorius F.
Angew. Chem. Int. Ed.
2004,
43:
6205
22 Sohn SS.
Rosen EL.
Bode JW.
J. Am. Chem. Soc.
2004,
126:
14370
23 He M.
Bode JW.
Org. Lett.
2005,
7:
3131
24 Burstein C.
Tschan S.
Xie XL.
Glorius F.
Synthesis
2006,
2418
25 Nair V.
Poonoth M.
Vellalath S.
Suresh E.
Thirumalai R.
J. Org. Chem.
2006,
71:
8964
26 Nair V.
Vellalath S.
Poonoth M.
Suresh E.
J. Am. Chem. Soc.
2006,
128:
8736
27 Chan A.
Scheidt KA.
J. Am. Chem. Soc.
2007,
129:
5334
28 Phillips EM.
Reynolds TE.
Scheidt KA.
J. Am. Chem. Soc.
2008,
130:
2416
29 Seayad J.
Patra PK.
Zhang Y.
Ying JY.
Org. Lett.
2008,
10:
953
30 Chan A.
Scheidt KA.
J. Am. Chem. Soc.
2008,
130:
2740
31 Chan A.
Scheidt KA.
Org. Lett.
2005,
7:
905
32 Sohn SS.
Bode JW.
Org. Lett.
2005,
7:
3873
33 Bordwell FG.
Mccallum RJ.
Olmstead WN.
J. Org. Chem.
1984,
49:
1424
34 Lepore SD.
Khoram A.
Bromfield DC.
Cohn P.
Jairaj V.
Silvestri MA.
J. Org. Chem.
2005,
70:
7443
35 Bordwell FG.
Acc. Chem. Res.
1988,
21:
456
36 Diver ST.
Rivas FM.
Giessert AJ.
J. Org. Chem.
2002,
67:
1708
37 Zeitler K.
Org. Lett.
2006,
8:
637
38 Magill AM.
Cavell KJ.
Yates BF.
J. Am. Chem. Soc.
2004,
126:
8717
39 Wöhler F.
Liebig J.
Ann. Pharm. (Lemgo, Ger.)
1832,
3:
294
40 Adams R.
Marvel CS.
Org. Synth. Coll. Vol. I
John Wiley & Sons;
London:
1932.
p.94
41 Ide WS.
Buck JS.
Org. React.
1949,
4:
269
42 Phillips EM.
Wadamoto M.
Chan A.
Scheidt KA.
Angew. Chem. Int. Ed.
2007,
46:
3107
43 Wadamoto M.
Phillips EM.
Reynolds TE.
Scheidt KA.
J. Am. Chem. Soc.
2007,
129:
10098
44 He M.
Struble JR.
Bode JW.
J. Am. Chem. Soc.
2006,
128:
8418
45 He M.
Uc GJ.
Bode JW.
J. Am. Chem. Soc.
2006,
128:
15088
46 Reynolds NT.
Rovis T.
J. Am. Chem. Soc.
2005,
127:
16406
47 Cain CM.
Cousins RPC.
Coumbarides G.
Simpkins NS.
Tetrahedron
1990,
46:
523
48 Brunel JM.
Chem. Rev.
2005,
105:
857
49 Seebach D.
Beck AK.
Heckel A.
Angew. Chem. Int. Ed.
2001,
40:
92
50 Maki BE.
Chan A.
Phillips EM.
Scheidt KA.
Org. Lett.
2007,
9:
371
51 Chan A.
Scheidt KA.
J. Am. Chem. Soc.
2006,
128:
4558
52 Castells J.
Llitjos H.
Morenomanas M.
Tetrahedron Lett.
1977,
18:
205
53 Inoue H.
Higashiura K.
J. Chem. Soc., Chem. Commun.
1980,
549
54 Miyashita A.
Suzuki Y.
Nagasaki I.
Ishiguro C.
Iwamoto K.
Higashino T.
Chem. Pharm. Bull.
1997,
45:
1254
55 Glorius F.
Altenhoff G.
Goddard R.
Lehmann C.
Chem. Commun.
2002,
2704
56 Baskakov D.
Herrmann WA.
Herdtweck E.
Hoffmann SD.
Organometallics
2007,
26:
626
57 Pangborn AB.
Giardello MA.
Grubbs RH.
Rosen RK.
Timmers FJ.
Organometallics
1996,
15:
1518
58 Perrin DD.
Armarego WL.
Purification of Laboratory Chemicals
3rd ed.:
Pergamon Press;
Oxford:
1988.
59 Hesse S.
Kirsch G.
Synthesis
2001,
755
60 Kirsch G.
Prim D.
Leising F.
Mignani G.
J. Heterocycl. Chem.
1994,
31:
1005
61 Baldwin JE.
Mackenzie Turner SC.
Moloney MG.
Tetrahedron
1994,
50:
9411
62 Kurono N.
Sugita K.
Takasugi S.
Tokuda M.
Tetrahedron
1999,
55:
6097
63 Kopecky DJ.
Rychnovsky SD.
J. Org. Chem.
2000,
65:
191
64 Kita Y.
Akai S.
Yamamoto M.
Taniguchi M.
Tamura Y.
Synthesis
1989,
334
65 Barton P.
Laws AP.
Page MI.
J. Chem. Soc., Perkin Trans. 2
1994,
2021
66 Peterson PE.
Stepanian M.
J. Org. Chem.
1988,
53:
1903
67 Kuroda H.
Hanaki E.
Izawa H.
Kano M.
Itahashi H.
Tetrahedron
2004,
60:
1913
68 Banerjee M.
Roy S.
Org. Lett.
2004,
6:
2137
69 Waddell TG.
Rambalakos T.
Christie KR.
J. Org. Chem.
1990,
55:
4765
70 Imashiro R.
Seki M.
J. Org. Chem.
2004,
69:
4216
71 Kim N.
Kim KS.
Gupta AK.
Oh CH.
Chem. Commun.
2004,
618
72 Kerr MS.
de Alaniz JR.
Rovis T.
J. Org. Chem.
2005,
70:
5725
