D A. Evans Introduction to carbenes Carbenoids-2 Chem 206 http:/www.courses.fasharvardedu/-chem206/ Useful References to the Carbene Literature Chemistry 206 Recent Review Article Chemistry of Diazocar McKervey et al. Chem Rev. 1994, 94, 1091 Advanced Organic Chemistry Books Modern Catalytic methods for Organic Synthesis with Diazo Compounds M. P. Doyle, Wiley, 1998 Lecture Number 35 Carbenes and Nitrenes in"Reactive molecules: The neutral reactive Intermediates in Organic Chemistry, Wentrup, C W. 1984, Wiley, p. 162 Introduction to Carbenes Carbenoids-2 Rearrangements of Carbenes and Nitrenes in Rearrangements in Ground Excited States, Academic Press, DeMayo ed, Jones, W. M. 1980, p. 95 a Thermally Induced Carbene Rearrangements Carbonyl Ylides and their reactions Carbene Chemistry, 2nd ed. Academic Press, Kirmse, W, 1971 R 0⑨ Oxonium Sulfonium Ylides and their reactions The Automerization of Naphthalene(The Cume Question from Helli) Rationaliz ○Q=0Q Reading Assignment for this Lecture: 13C-labeled C,ohg is isomerized into B-13C-labeled C1oh8 at 1035.C Carey Sundberg, Advanced Organic Chemistry, 4th Ed Part B Chapter 10, "Reactiona Involving Highly Reactive L.T.scot,JAcs1991,13,9692 Electron-Deficient Intermediates".263-350 Lecture 09A Simmons-Smith Reaction: Enantioselective variants Lecture 26B Synthetic Applications of a-Diazocarbonyl Compounds Provide a mechanism for this transformation Lecture 35A The Use of Fischer Carbenes in Organic Synthesis Lecture 35B The Synthetic Applications of Carbonyl Ylides 1000°c Corannulene 10% Matthew d shair Monday, December 16. 2002 Scott, L T, et aL., JACS 113 7082(1991)D. A. Evans Chem 206 Matthew D. Shair Monday, December 16 , 2002 http://www.courses.fas.harvard.edu/~chem206/ Reading Assignment for this Lecture: Introduction to Carbenes & Carbenoids-2 Recent Review Article: Chemistry of Diazocarbonyls: McKervey et al. Chem Rev. 1994, 94, 1091. Carbenes and Nitrenes in "Reactive Molecules: The Neutral Reactive Intermediates in Organic Chemistry", Wentrup, C. W. 1984, Wiley, p. 162. Rearrangements of Carbenes and Nitrenes in Rearrangements in Ground & Excited States, Academic Press, DeMayo ed., Jones, W. M. 1980, p. 95. Carbene Chemistry, 2nd ed. Academic Press, Kirmse, W., 1971. Books: Modern Catalytic methods for Organic Synthesis with Diazo Compounds; M. P. Doyle, Wiley, 1998. Carey & Sundberg, Advanced Organic Chemistry, 4th Ed. Part B Chapter 10, "Reactiona Involving Highly Reactive Electron-Deficient Intermediates", 263-350 . Useful References to the Carbene Literature Lecture 09A Simmons-Smith Reaction: Enantioselective Variants Lecture 26B Synthetic Applications of a-Diazocarbonyl Compounds Lecture 35A The Use of Fischer Carbenes in Organic Synthesis Lecture 35B The Synthetic Applications of Carbonyl Ylides Chemistry 206 Advanced Organic Chemistry Lecture Number 35 Introduction to Carbenes & Carbenoids-2 ■ Thermally Induced Carbene Rearrangements ■ Carbonyl Ylides and their Reactions R C R R R O R O R R R R O R R R ■ Oxonium & Sulfonium Ylides and their Reactions R C R R X R R X R C R R •• •• The Automerization of Naphthalene (The Cume Question from Hell!) a– 13C-labeled C10H8 is isomerized into b– 13C-labeled C10H8 at 1035 °C D Rationalize Scott, L.T., et. al., JACS 113 7082 (1991) Corannulene 10% £ 10-4 Torr 1000° C Provide a Mechanism for this Transformation L. T. Scott, JACS 1991, 113, 9692