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To the best of our knowledge, chiral ligand based DoM reactions of secondary ferrocenylamides, are unknown. For the only case of achiral secondary ferrocenecarboxamide DoM, see: D. W. Slocum, F. E. Stonemark, J. Org. Chem. 1973, 38, 1677.
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For previous use of this concept in ferrocene chemistry see: a) C. Ganter, T. Wagner, Chem. Ber. 1995, 128, 1157; b) K. H. Ahn, C. Cho, H. Baek, J. Park, S. Lee, J. Org. Chem. 1996, 61, 4937.
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For previous use of this concept in ferrocene chemistry see: a) C. Ganter, T. Wagner, Chem. Ber. 1995, 128, 1157; b) K. H. Ahn, C. Cho, H. Baek, J. Park, S. Lee, J. Org. Chem. 1996, 61, 4937.
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0242710432
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Ph. D. Thesis, Queen's University, Kingston, Ontario, Canada
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We have observed that decreasing the steric bulk of the tertiary amide leads to erosion of the enantiomeric excess: C. Metallinos, Ph. D. Thesis, Queen's University, Kingston, Ontario, Canada, 2001.
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Metallinos, C.1
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24
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0242541484
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note
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2O, THF and PhMe) even at rt. The insolubility problem is compounded by the N-deprotonation event.
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25
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0242710434
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note
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Crystallographic data (excluding structure factors) for 6f, 7d and 11 have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication nos. CCDC-163407, 163409 and 163408, respectively. Copies of the data can be obtained free of charge on application to CCDC, 12 Union Road, Cambridge CB2 1EZ, UK [fax: (+44)1223-336-033; e-mail: deposit@ccdc.cam.ac.uk].
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26
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0000597788
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a) TMSI is known to promote carbocationic substitution in similar methyl ethers, see: G. G. A. Balavoine, J. C. Daran, G. Iftime, E. Manoury, C. Moureau-Bossuet, J. Organomet. Chem. 1998, 567, 191;
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0242457924
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note
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On the basis of this result, the same relative stereo-chemistry to all products 7a-g has been assigned.
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30
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0033588130
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For other biferrocenes with only planar chirality, see: a) A. O. Larsen, R. A. Taylor, P. S. White, M. R. Gagne, Organometallics 1999, 18, 5157; b) R. Kuwano, T. Uemura, M. Saitoh, Y. Ito, Tetrahedron Lett. 1999 40, 1327.
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For other biferrocenes with only planar chirality, see: a) A. O. Larsen, R. A. Taylor, P. S. White, M. R. Gagne, Organometallics 1999, 18, 5157; b) R. Kuwano, T. Uemura, M. Saitoh, Y. Ito, Tetrahedron Lett. 1999 40, 1327.
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Aromatic N-allylamides and carbamates are prone to deprotonation with alkyllithiums, see: a) D. Hoppe, T. Hense, Angew. Chem. Int. Ed. Engl. 1997, 36, 2282; Angew. Chem. 1997, 109, 2376; b) M. C. Whisler, L. Vaillancourt, P. Beak, Org. Lett. 2000, 2, 2655; c) L. E. Fisher, J. M. Muchowski, R. D. Clark, J. Org. Chem. 1992, 57, 2700.
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M. Ogasawara, T. Nagano, T. Hayashi, J. Am. Chem. Soc. 2002, 124, 9068.
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(2002)
J. Am. Chem. Soc.
, vol.124
, pp. 9068
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Ogasawara, M.1
Nagano, T.2
Hayashi, T.3
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45
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0242457928
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note
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The carbinol (pre-17) was purified and characterized in a separate small-scale reaction. See the Experimental Section.
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46
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0000334299
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Vinylferrocenes have served as monomers for the acid-catalyzed preparation of ferrocenyl polymers, see: C. Aso, T. Kunitake, T. Nakashima, Makromol. Chem. 1969, 124, 232.
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(1969)
Makromol. Chem.
, vol.124
, pp. 232
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Aso, C.1
Kunitake, T.2
Nakashima, T.3
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47
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0242541486
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note
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2/rt/24 h) gave alkylated products in good yield (86-94%), but low enantiocontrol (47-69% ee).
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48
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0242710436
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note
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The N,N-diethylferrocene amide corresponding to 8 may also be used to obtain the opposite enantiomers for several derivatives which, however, are much more difficult to hydrolyze and undergo partial racemization under the conditions of TBAF desilylation: U. Veith, C. Bessler, V. Snieckus, unpublished results.
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