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(a) For a review of cyclopropane amino acids, see: Stammer, C. H. Tetrahedron 1990, 46, 2231.
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Stammer, C.H.1
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(b) For a construction of 2,3- and 4,5-methanoproline, see: Hanessian, S.; Reinhold: U.; Gentile, G. Angew. Chem., Int. Ed. Engl. 1997, 36, 1881 and references therein.
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(a) Pyne, S. G.; Dong, Z.; Skelton, B. W.; White, A. H. J. Org. Chem. 1997, 62, 2337.
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15
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0344071488
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note
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H1-H2. See ref 2.
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16
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0027157785
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Piccione, E.; Case, R. D.; Domcheck, S. M.; Hu, P.; Chaudhuri, M.; Backer, J. M.; Schlessinger, J.; Shoelson, S. E. Biochemistry 1993, 32, 3197.
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Case, R.D.2
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Chaudhuri, M.5
Backer, J.M.6
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0001191123
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LaRochelle, R. W.; Trost, B. M.; Krepski, L. J. Org. Chem. 1971, 36, 1126.
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Larochelle, R.W.1
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Krepski, L.3
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18
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0344071483
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Exo denotes addition to the exo face of the bicyclic lactam, whereas anti and syn denote the cyclopropane stereochemistry
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Exo denotes addition to the exo face of the bicyclic lactam, whereas anti and syn denote the cyclopropane stereochemistry.
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19
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0344933573
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note
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The stereochemistry of the vinyl group was assigned by the presence of a positive NOE between H1 and H3 for the anti isomer and the absence of a positive NOE between H1 and H3 for the syn isomer (see Scheme 1 for numbering) or by coupling constants as described in ref 5b. All additional stereochemical assignments were accomplished in an analogous manner.
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24
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0001363277
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Johnson, C. R.; Haake, M.; Schroeck, C. W. J. Am. Chem. Soc. 1970, 92, 6594.
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Johnson, C.R.1
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Schroeck, C.W.3
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25
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0344502769
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The dimerization product is formed as a single diastereomer. We have not attempted to assign relative stereochemistry. (figure presented)
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The dimerization product is formed as a single diastereomer. We have not attempted to assign relative stereochemistry. (figure presented)
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27
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0344071481
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Although it is unusual to think of an ethyl group as smaller than a vinyl group, in this instance, a vinyl group may be considered more sterically demanding because it is coplanar with the sulfur and anionic carbon, whereas with the ethyl group, the terminal methyl may rotate away from the pyrrolidine ring
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Although it is unusual to think of an ethyl group as smaller than a vinyl group, in this instance, a vinyl group may be considered more sterically demanding because it is coplanar with the sulfur and anionic carbon, whereas with the ethyl group, the terminal methyl may rotate away from the pyrrolidine ring.
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28
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33947485650
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A possible explanation for the lack of selectivity is that following conjugate addition disproportionation scrambles the stereochemistry at the newly formed stereocenter. Products which arise from this alternate mechanistic pathway have been reported: (a) Corey, E. J.; Chaykovsky, M. J. Am. Chem. Soc. 1963, 86, 1640. (b) Tamura, Y.; Taniguchi, H.; Miyamoto, T.; Tsunekawa, M.; Ikeda, M. J. Org. Chem. 1974, 39, 3519. (figure presented)
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Corey, E.J.1
Chaykovsky, M.2
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29
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0345364997
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figure presented
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A possible explanation for the lack of selectivity is that following conjugate addition disproportionation scrambles the stereochemistry at the newly formed stereocenter. Products which arise from this alternate mechanistic pathway have been reported: (a) Corey, E. J.; Chaykovsky, M. J. Am. Chem. Soc. 1963, 86, 1640. (b) Tamura, Y.; Taniguchi, H.; Miyamoto, T.; Tsunekawa, M.; Ikeda, M. J. Org. Chem. 1974, 39, 3519. (figure presented)
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Tamura, Y.1
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Ikeda, M.5
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