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2242464188
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note
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Crystallographic data for the strustural analysis have been deposited with the Cambridge Crystallographic Data Center, CCDC No. 178177.
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23
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2242474110
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note
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1H NMR were found to be higher for all the minor (syn) diastereomers than the corresponding ones observed for the major (anti) diastereomers; see ref 4.
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24
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2242457868
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note
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Crystallographic data for the strustural analysis have been deposited with the Cambridge Crystallographic Data Center, CCDC No. 178048.
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26
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0000498840
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Ishiguro, M.; Ikeda, N.; Yamamoto, H. J. Org. Chem. 1982, 47, 2225-2227.
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Enders, D.; Kirchhoff, J.; Gerdes, P.; Mannes, D.; Raabe, G.; Runsink, J.; Boche, G.; Marsch, M.; Ahlbrecht, H.; Sommer, H. Eur. J. Org. Chem. 1998, 63, 3-72. Fleming, F. F., Shook, B. C. Tetrahedron 2002, 58, 1-23.
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Enders, D.; Kirchhoff, J.; Gerdes, P.; Mannes, D.; Raabe, G.; Runsink, J.; Boche, G.; Marsch, M.; Ahlbrecht, H.; Sommer, H. Eur. J. Org. Chem. 1998, 63, 3-72. Fleming, F. F., Shook, B. C. Tetrahedron 2002, 58, 1-23.
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Shook, B.C.2
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2242420202
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note
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As suggested by one of our reviewers, one may involve a transition state where the two N-substituents are roughly in the plane of the keteniminate, with the t-Bu group exo and the benzyl endo (see structure below). Such conformation would reduce steric congestion in the transition state energy, thereby negating the effect of any ground-state destabilization.
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32
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84985502354
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These two experiments were run in order to perform a pseudo-Hoffmann test due to the possible but improbable configurational stability of lithiated α-aminonitriles. Hoffmann, R.; Lanz, J.; Metternich, R.; Tarara, G.; Hoppe, D. Angew. Chem., Int. Ed. Engl. 1987, 26, 1145-1146.
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Hoffmann, R.1
Lanz, J.2
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Tarara, G.4
Hoppe, D.5
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33
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0034613348
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(a) Similar results were obtained with configurationally stable allenyl zinc reagents: Poisson, J. F.; Normant, J. F. J. Org. Chem. 2000, 65, 6553-6560.
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Poisson, J.F.1
Normant, J.F.2
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35
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2242424689
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note
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Crystallographic data for the structural analysis have been deposited with the Cambridge Crystallographic Data Center, CCDC No. 178047.
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36
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2242438273
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note
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The modest selectivity obtained with chiral aldehydes 12 and 13 is in accordance with the results generally obtained with these aldehydes. Moreover, it is possible that, due to the cyclic nature of the transition state, the attack of the lithiated ketene imine to the aldehyde does not occur in the Bürgi-Dunitz angle, which is important for the selectivity (see ref 18b).
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39
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2242418413
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The addition of Grignard reagents to the nitrile is surprising in the light of the Bruylants reaction. Such chemioselectivity is probably due to the steric effect of the t-Bu group, which prevents the formation of the immoniun intermediate. Indeed, we have observed that addition of BuMgBr to an aldol derived from 4 yielded exclusively to the Bruylants's product. Moreover, we also found that it was possible to perform the Bruylants reaction by addition of Grignard reagents to the immoniums derived from aldols 10d,e as described by Couty and Agami: Agami, C, Couty, F., Ewano, G Org. Lett. 2000, 2, 2065-2088.
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Agami, C.1
Couty, F.2
Ewano, G.3
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40
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2242490220
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note
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Crystallographic data for the structural analysis have been deposited with the Cambridge Crystallographic Data Center, CCDC No. 178176 for 16c and CCDC No. 178175 for 16d.
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42
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0000763561
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Reetz, M.T.1
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2242477727
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note
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2 protected derivative did not occur.
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45
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0001295217
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Earle, M. J.; Fairhurst, R. A.; Heaney, H.; Papageorgiou, G. Synlett 1990, 621-623.
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0001301921
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0035611042
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For the cleavage of an N-tert-butyl group on a secondary amine, see: De Kimpe, N.; Sulmon, P.; Brunet, P. J. Org. Chem. 1990, 55. 5777-5784. Bundy, G. I.; Banitt, L. S.; Dobrowolski, P. J.; Palmer, J. R.; Schwartz, T. M.; Zimmermann, D. C.; Lipton, M. F.; Mauragis, M. A.; Veley, M. F.; Appell, R. B.; Clouse, R. C.; Daug, E. D. Org. Process Dev. 2001, 5, 144-151.
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Bundy, G.I.1
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Dobrowolski, P.J.3
Palmer, J.R.4
Schwartz, T.M.5
Zimmermann, D.C.6
Lipton, M.F.7
Mauragis, M.A.8
Veley, M.F.9
Appell, R.B.10
Clouse, R.C.11
Daug, E.D.12
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