D.A. Evans Functional Group Classification Scheme for Polar Bond Constructions Chem 206 Papers of Historical Interest http://www.courses.fasharvard.edu/-chem206/ Arthur Lapworth: The Genesis of Reaction M. Saltzman chem Ed 1972. 49. 750 Chemistry 206 A Theoretical Derivation of the Principle of Induced Altemate Polarities. A. Lapworth J. Chem. Soc. 1922, 121, 416 Advanced Organic Chemistry " The Electron Theory of Valence as Applied to Organic Compounds J. Steiglitz J. Am. Chem. Soc. 1922, 44, 1293 Lecture number 26 Monographs Hase, T. A "Umpoled Synthons. A Survey of Sources and Uses in Synthesis Ambiphilic Functional Groups ohn Wiley Sons, Inc: New York, 1987. Nitro and Diazo Groups Ho, T.-L. "Polarity Control for Synthesis", John Wiley& Sons, Inc. New York, Historical Perspective Ono, N, "The Nitro Group in Organic Synthesis", Wiley-VCH, 2001 ■ Charge Affinity Patterns a Functional Group Classification Scheme Several Interesting Problems I The Chemistry of the -NO2 Group The Chemistry of the -N2 Group Provide a mechanism for the nef reaction R Reading Assignment for this Week: Nef Reaction 2)H3O An Organizational Scheme for the Classification of Functional Groups Applications to the Construction of Difunctional Relationships D A. Evans Unpublished manuscript (Lecture 26A, pdf) Cume Question: The von Richter reaction is illustrated in the accompanying equation. Methods of Reactivity Umpolung D Seebach Angew. Chem. Int Ed Engl. 1979, 18, 239 Please provide a plausible mechanism for this transformation taking into account the following observations. (a)If5N-labeled KCN is used, the N2 formed is half labeled: (b) Nitroaliphatic Compounds-ldeal Intermediates in Organic Synthesis"Seebach, 3-bromo-benzonitrile does not form 3-bromo-benzoic acid under the reaction conditions D.et.al,chma,1979,33,1-18 Synthetic Applications of a-Diazocarbonyl Compounds Krista Beaver, Evans Group Seminar (Lecture 26B, pdf) KCN Monday, Matthew d. shair November 18. 2002 aqueous EtoH CO2Hhttp://www.courses.fas.harvard.edu/~chem206/ Br NO2 KCN N R R O O H Br CO2H N2 O R R D. A. Evans Chem 206 Matthew D. Shair Monday, November 18, 2002 Reading Assignment for this Week: Functional Group Classification Scheme for Polar Bond Constructions Chemistry 206 Advanced Organic Chemistry Lecture Number 26 Ambiphilic Functional Groups-1 Nitro and Diazo Groups ■ Historical Perspective ■ Charge Affinity Patterns ■ Functional Group Classification Scheme ■ The Chemistry of the –NO2 Group ■ The Chemistry of the –N2 Group "An Organizational Scheme for the Classification of Functional Groups. Applications to the Construction of Difunctional Relationships." D. A. Evans Unpublished manuscript (Lecture 26A, pdf) "Methods of Reactivity Umpolung." D. Seebach Angew. Chem. Int. Ed. Engl. 1979, 18, 239. "Nitroaliphatic Compounds–Ideal Intermediates in Organic Synthesis"' Seebach, D. et. al, Chimia, 1979, 33, 1-18. "Synthetic Applications of a-Diazocarbonyl Compounds" Krista Beaver, Evans Group Seminar (Lecture 26B, pdf) "Arthur Lapworth: The Genesis of Reaction Mechanism." M. Saltzman J. Chem. Ed. 1972, 49, 750. "A Theoretical Derivation of the Principle of Induced Alternate Polarities." A. Lapworth J. Chem. Soc. 1922, 121, 416. "The Electron Theory of Valence as Applied to Organic Compounds." J. Steiglitz J. Am. Chem. Soc. 1922, 44, 1293. Hase, T. A. "Umpoled Synthons. A Survey of Sources and Uses in Synthesis".; John Wiley & Sons, Inc.: New York, 1987. Ho, T.-L. "Polarity Control for Synthesis"; John Wiley & Sons, Inc.: New York, 1991. Ono, N., "The Nitro Group in Organic Synthesis", Wiley-VCH, 2001 1) HO – 2) H3O Nef Reaction + Provide a mechanism for the Nef reaction Monographs: Papers of Historical Interest: Cume Question: The von Richter reaction is illustrated in the accompanying equation. Please provide a plausible mechanism for this transformation taking into account the following observations. (a) If 15 N-labeled KCN is used, the N 2 formed is half labeled; (b) 3-bromo-benzonitrile does not form 3-bromo-benzoic acid under the reaction conditions. heat, aqueous EtOH + Several Interesting Problems