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1
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33746302238
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The chemistry of carbonyl compounds is virtually the backbone of synthetic organic chemistry
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Benjamin, New York
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"The chemistry of carbonyl compounds is virtually the backbone of synthetic organic chemistry": J. D. Roberts, M. C. Caserio, Basic Principles of Organic Chemistry, Benjamin, New York, 1965, p. 426.
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Basic Principles of Organic Chemistry
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Roberts, J.D.1
Caserio, M.C.2
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0000679543
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a) K. Voigt, P. von Zezschwitz, K. Rosauer, A. Lansky, A. Adams, O. Reiser, A. de Meijere, Eur. J. Org. Chem. 1998, 1521-1534;
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Voigt, K.1
Von Zezschwitz, P.2
Rosauer, K.3
Lansky, A.4
Adams, A.5
Reiser, O.6
De Meijere, A.7
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7
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0344132082
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b) S. Bräse, Synlett 1999, 1654-1656.
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Bräse, S.1
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8
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0033548113
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F. Bellina, D. Ciucci, R. Rossi, P. Vergamini, Tetrahedron 1999, 55, 2103-2112.
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Tetrahedron
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Bellina, F.1
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Rossi, R.3
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10
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0027300102
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a) J. Suffert, A. Eggers, S. W. Scheuplein, R. Brueckner, Tetrahedron Lett. 1993, 34, 4177-4180;
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Tetrahedron Lett.
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Suffert, J.1
Eggers, A.2
Scheuplein, S.W.3
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11
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0033575422
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b) T. Okauchi, T. Yano, T. Fukamachi, J. Ichikawa, T. Minami, Tetrahedron Lett. 1999, 40, 5337-5340.
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Fukamachi, T.3
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Minami, T.5
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12
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0000880894
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and references therein
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a) R. Zimmer, M. Webel, H.-U. Reissig, J. Prakt. Chem. 1998, 340, 274-277, and references therein;
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Zimmer, R.1
Webel, M.2
Reissig, H.-U.3
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16
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3843098415
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c) I. M. Lyapkalo, J. Hogermeier, H.-U. Reissig, Tetrahedron 2004, 60, 7721-7729.
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(2004)
Tetrahedron
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Lyapkalo, I.M.1
Hogermeier, J.2
Reissig, H.-U.3
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17
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The reaction results in the anticipated nonafluorobutane-1-sulfonamides: I. M. Lyapkalo, H.-U. Reissig, A. Schaefer, A. Wagner, Helv. Chim. Acta 2002, 85, 4206-4215.
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(2002)
Helv. Chim. Acta
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Lyapkalo, I.M.1
Reissig, H.-U.2
Schaefer, A.3
Wagner, A.4
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33746283365
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note
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Trialkylamines are not basic enough to promote the nonaflation, whereas DBU gives low conversions as a result of the side reaction with NfF. The results will be reported in a subsequent full account.
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33749144042
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and references therein
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2 or higher order phosphazene bases, see: R. Schwesinger, H. Schlemper, C. Hasenfratz, J. Willaredt, T. Dambacher, T. Breuer, C. Ottaway, M. Fletschinger, J. Boele, H. Fritz, D. Putzas, H. W. Rotter, F. G. Bordwell, A. V. Satish, G. Z. Ji, E. M. Peters, K. Peters, H. G. von Schnering, L. Walz, Liebigs Ann. 1996, 1055-1082 and references therein.
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Liebigs Ann.
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Schwesinger, R.1
Schlemper, H.2
Hasenfratz, C.3
Willaredt, J.4
Dambacher, T.5
Breuer, T.6
Ottaway, C.7
Fletschinger, M.8
Boele, J.9
Fritz, H.10
Putzas, D.11
Rotter, H.W.12
Bordwell, F.G.13
Satish, A.V.14
Ji, G.Z.15
Peters, E.M.16
Peters, K.17
Von Schnering, H.G.18
Walz, L.19
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21
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0035898812
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S. Chang, S. H. Yang, P. H. Lee, Tetrahedron Lett. 2001, 42, 4833-4836.
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(2001)
Tetrahedron Lett.
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Chang, S.1
Yang, S.H.2
Lee, P.H.3
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23
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0000864263
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For the relevant multistep methods known to date, see a) M. Shibasaki, Y. Torisawa, S. Ikegami, Tetrahedron Lett. 1982, 23, 4607-4610;
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(1982)
Tetrahedron Lett.
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Shibasaki, M.1
Torisawa, Y.2
Ikegami, S.3
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24
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0029156880
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b) L. A. Paquette, S. Hormuth, C. J. Lovely, J. Org. Chem. 1995, 60, 4813-4821;
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Paquette, L.A.1
Hormuth, S.2
Lovely, C.J.3
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25
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0034719711
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c) T. Matsuura, S. Yamamura, Y. Terada, Tetrahedron Lett. 2000, 41, 2189-2192.
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(2000)
Tetrahedron Lett.
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Matsuura, T.1
Yamamura, S.2
Terada, Y.3
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26
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33746301078
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note
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Preliminary investigations show that the nonaflation/elimination protocol is applicable to a wide range of carbonyl compounds, leading to terminal or internal alkynes or allenes, depending on the stereoelectronic effects of the substituents in the carbonyl substrate. The results will be reported in due course.
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33746310030
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note
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2 base (1 equiv) and NfF under the kinetic conditions, we could detect only mixtures of the alkyne and the starting material, which clearly indicates that nonaflation is the rate-determining step.
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33746305592
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note
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3Si, under our reaction conditions.
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33746284549
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note
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2NEt in MeCN at -45°C to 5°C. The pure Z isomer was then isolated by preparative HPLC (68% yield).
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31
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85047671181
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The antimycotic agent terbinafine (Lamisil) manufactured by Novartis Pharmaceuticals is perhaps most prominent example of a widely applied drug bearing an eneyne structural motif; for other interesting bioactive compounds, see: a) L. Garlaschelli, E. Magistrali, G. Vidari, O. Zuffardi, Tetrahedron Lett. 1995, 36, 5633-5636;
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(1995)
Tetrahedron Lett.
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Garlaschelli, L.1
Magistrali, E.2
Vidari, G.3
Zuffardi, O.4
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32
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1442310136
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b) H.-J. Zhang, K. Sydara, G. T. Tan, C. Ma, B. Southavong, D. D. Soejarto, J. M. Pezzuto, H. H. S. Fong, J. Nat. Prod. 2004, 67, 194-200.
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(2004)
J. Nat. Prod.
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Zhang, H.-J.1
Sydara, K.2
Tan, G.T.3
Ma, C.4
Southavong, B.5
Soejarto, D.D.6
Pezzuto, J.M.7
Fong, H.H.S.8
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33
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0030005845
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and references therein
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J. W. Grissom, G. U. Gunawardena, D. Klingberg, D. Huang, Tetrahedron 1996, 52, 6453-6518, and references therein.
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Tetrahedron
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Grissom, J.W.1
Gunawardena, G.U.2
Klingberg, D.3
Huang, D.4
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34
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84985667633
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2] is one of the most frequently used precatalysts for the Sonogashira reaction of alkenyl sulfonates: a) S. W. Scheuplein, K. Harms, R. Brueckner, J. Suffert, Chem. Ber. 1992, 125, 271-278;
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(1992)
Chem. Ber.
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Scheuplein, S.W.1
Harms, K.2
Brueckner, R.3
Suffert, J.4
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35
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0022612688
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b) L. Castedo, A. Mourino, L. A. Sarandeses, Tetrahedron Lett. 1986, 27, 1523-1526;
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(1986)
Tetrahedron Lett.
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Castedo, L.1
Mourino, A.2
Sarandeses, L.A.3
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36
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0023884008
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c) L. Castedo, J. L. Mascarenas, A. Mourino, L. A. Sarandeses, Tetrahedron Lett. 1988, 29, 1203-1206;
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(1988)
Tetrahedron Lett.
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Castedo, L.1
Mascarenas, J.L.2
Mourino, A.3
Sarandeses, L.A.4
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37
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0028231630
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d) M. Moniatte, M. Eckhardt, K. Birckmann, R. Brueckner, J. Suffert, Tetrahedron Lett. 1994, 35, 1965-1968;
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(1994)
Tetrahedron Lett.
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Moniatte, M.1
Eckhardt, M.2
Birckmann, K.3
Brueckner, R.4
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38
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33749135452
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e) J. Suffert, E. Abraham, S. Raeppel, R. Brueckner, Liebigs Ann. 1996, 447-456;
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(1996)
Liebigs Ann.
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Suffert, J.1
Abraham, E.2
Raeppel, S.3
Brueckner, R.4
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39
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f) A. L. Braga, D. J. Emmerich, C. C. Silveira, T. L. C. Martins, O. E. D. Rodrigues, Synlett 2001, 369-370;
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(2001)
Synlett
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Braga, A.L.1
Emmerich, D.J.2
Silveira, C.C.3
Martins, T.L.C.4
Rodrigues, O.E.D.5
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g) P. E. Tessier, N. Nguyen, M. D. Clay, A. G. Fallis, Org. Lett. 2005, 7, 767-770. However, we did not carry out a specific study on the LiCl effect.
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(2005)
Org. Lett.
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Tessier, P.E.1
Nguyen, N.2
Clay, M.D.3
Fallis, A.G.4
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