D. A. Evans The Anomeric Effect: Negative Hyperconjugation Chem 206 Useful LIterature Reviews http://www.courses.fasharvardedu/-chem206/ Kirby, A J(1982). The Anomeric Effect and Related Stereoelectronic Effects at Chemistry 206 Box, VGS(1990). The role of lone pair interactions in the chemistry of the monosaccharides. The anomeric effect "Heterocycles 31 1157 Advanced organic Chemistry Box, V.G.S(1998). The derivatives Insights from the new QVBMM molecular mechanics force field. Heterocycles 48(11 ): 2389-2417. Lecture number 2 Graczyk, P. P and M. Mikolajczyk( 1994). "Anomeric effect: origin and consequences. "Top. Stereochem. 21: 159-349 Stereoelectronic Effects-1 Juaristi, E. and G. cuevas (1992 ) "Recent studies on the anomeric effect. Tetrahedron 48 5019 Plavec, J, C Thibaudeau, et al.(1996). "How do the Energetics of the Anomeric and related Effects Stereoelectronic gauche and Anomeric Effects modulate the Conformation of (t)ides? "Pure Appl. Chem. 68: 2137- a Electrophilic& Nucleophilic Substitution Reactions Thatcher, G R I, Ed. (1993). The Anomeric Effect and Associated i Stereoelectronic Effects. Washington DC, American Chemical Society u The Sn2 Reaction: Stereoelectronic Effects Olefin Epoxidation: Stereoelectronic Effects A Problem of the Day(First hr exam, 1999) u Baeyer-Villiger Reaction: Stereoelectronic Effects The three phosphites illustrated below exhibit a 750-fold span in reactivity with a test electrophile(eq 1)(Gorenstein, JACS 1984, 106, 7831) 十 Olefin Bromination Stereoelectronic Effects (RO)3P El(+)-(RO)3P-EI (1) Hard Soft Acid and Bases(not to be covered in class OMe HSAB Discussion: Fleming Chapter 3 OMe Matthew d. shair Friday Rank the phosphites from the least to the most nucleophilic and September 20, 2002 provide a concise explanation for your predicted reactivity orderD. A. Evans The Anomeric Effect: Negative Hyperconjugation Chem 206 Chemistry 206 Advanced Organic Chemistry Lecture Number 2 Stereoelectronic Effects-1 ■ Anomeric and Related Effects ■ Electrophilic & Nucleophilic Substitution Reactions ■ The SN2 Reaction: Stereoelectronic Effects ■ Olefin Epoxidation: Stereoelectronic Effects ■ Baeyer-Villiger Reaction: Stereoelectronic Effects ■ Olefin Bromination: Stereoelectronic Effects ■ Hard & Soft Acid and Bases (Not to be covered in class) Matthew D. Shair Friday, September 20, 2002 Kirby, A. J. (1982). The Anomeric Effect and Related Stereoelectronic Effects at Oxygen. New York, Springer Verlag. Box, V. G. S. (1990). “The role of lone pair interactions in the chemistry of the monosaccharides. The anomeric effect.” Heterocycles 31: 1157. Box, V. G. S. (1998). “The anomeric effect of monosaccharides and their derivatives. Insights from the new QVBMM molecular mechanics force field.” Heterocycles 48(11): 2389-2417. Graczyk, P. P. and M. Mikolajczyk (1994). “Anomeric effect: origin and consequences.” Top. Stereochem. 21: 159-349. Juaristi, E. and G. Cuevas (1992). “Recent studies on the anomeric effect.” Tetrahedron 48: 5019. Plavec, J., C. Thibaudeau, et al. (1996). “How do the Energetics of the Stereoelectronic Gauche and Anomeric Effects Modulate the Conformation of Nucleos(t)ides?” Pure Appl. Chem. 68: 2137-44. Thatcher, G. R. J., Ed. (1993). The Anomeric Effect and Associated Stereoelectronic Effects. Washington DC, American Chemical Society. Useful LIterature Reviews ■ Problem of the Day (First hr exam, 1999) The three phosphites illustrated below exhibit a 750-fold span in reactivity with a test electrophile (eq 1) (Gorenstein, JACS 1984, 106, 7831). O P O OMe O P O OMe Rank the phosphites from the least to the most nucleophilic and provide a concise explanation for your predicted reactivity order. O P O O + El(+) (RO)3P–El (1) + A B C HSAB Discussion: Fleming Chapter 3 http://www.courses.fas.harvard.edu/~chem206/ (RO)3P