Ready; Catalysis Isomerization/cyclization-1 R M R' M R R' H R R' M H MH R R' H R' M M H Olefin insertion into Metal alkyl can be followed by hydride elimination or additional olefin insertions: -dimerization/oligomerization -small molecules -polymerization Recall: electron rich M (late transition metal) Keq < 1 ->dimerization, etc electron poor M (early transition metal) Keq > 1 ->polymerization P Ph2 Ni OO H C7-C14 C1-C3 HO C10-C18 C1-C3 C7-C14 Shell

Subscriber access provided by UNIV TEXAS SW MEDICAL CENTER Journal of the American Chemical Society is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Using Electrospray Ionization FTICR Mass Spectrometry To Study Competitive Binding of Inhibitors to Carbonic Anhydrase Xueheng Cheng, Ruidan Chen, James E. Bruce, Brenda L. Schwartz, Gordon A. Anderson, Steven A. Hofstadler, David C. Gale, Richard D. Smith, Jinming Gao, George B. Sigal, Mathai Mammen

1 Ready; Catalysis Hydrogenation Categories and Dichotomies: Heterogeneous or Homogeneous Neutral or Cationic Directed or Non-directed Heterolytic or Homolytic H2 Activation Racemic or Enantioselective Syn or Trans Addition Homogeneous Hydrogenation Rh Ph3P Ph3P Cl PPh3 Advantages: Mild conditions Improved selectivity Directed Hydrogenation Enantioselective Hydrogenation Mechanistically accessible Disadvantages: Purification $$$$ Often less

Subscriber access provided by UNIV TEXAS SW MEDICAL CENTER Analytical Chemistry is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Addition/Correction Using Capillary Electrophoresis To Follow the Acetylation of the Amino Groups of Insulin and To Estimate Their Basicities Jinming Gao, Milan Mrksich, Frank A. Gomez, and George M. Whitesides Anal. Chem., 1996, 68 (13), 2287-2287• DOI: 10.1021/ac9614001 • Publication Date (Web): 01 July 1996

1 P(tBu)2 P(tBu)2 CuBr P Pd P P P PBu3 Pt H Et3P Cl PEt3 Ir S R3P H PR3 H S -S PF6 - Ir S R3P H PR3 H P P Pd PF6 - Pt H Et3P Cl PEt3 Py P P Ir S R3P H PR3 H PF6 - Pt H Et3P Py PEt3 Cl Fe Pt H Et3P Py PEt3 P P Cl- Organometallic Reaction Mechanisms Ligand association/dissociation + toluene insoluble (PBu3)nCuBr soluble + active catalyst for cross coupling = NOTE: No ox. state change Ligand Exchange: Associative - common for 16e- complexes

Ready; Catalysis Intro Helpful Texts: Principles and Applications of Organotransition Metal Chemistry, Collman, Hegedus, Norton, Fink The Organometallic Chemistry of the Transition Metals, Crabtree; Prof. M-Christina White’s lecture notes: http://www.courses.fas.harvard.edu/~chem153/ (many of my notes are taken from these, with permission) Advanced Synthesis and Catalysis, Spring 2011 Or: How to make more molecules more complex more quickly with less effort/material/waste

Notes Synthesis of a Phosphonate Analog of Sialic Acid (Neu5Ac) Using Indium-Mediated Allylation of Unprotected Carbohydrates in Aqueous Media Jinming Gao, Valeri Martichonok, and George M. Whitesides* Department of Chemistry and Chemical Biology, Harvard University, 12 Oxford Street, Cambridge, Massachusetts 02138 Received October 1, 1996 Introduction Sialic acid (Neu5Ac, 1), a constituent of sialoglycopro- teins1 and gangliosides,2 mediates a number of inter- cellular and cell-virion

Advanced Synthesis and Catalysis, 2006 Unless noted, class is 9:00-10:30, mon and wed, L4.14 Date Topic Lecturer 8-22 Intro to catalysis Ready 8-24 Organometallics: structure/reactivity-1 Ready 8-29 Organometallics: structure/reactivity-2 Ready 8-31 Kinetics and mech-1 Ready 9-5 Kinetics and mech-2 Ready 9-7 Kinetic resolutions Ready 9-12 Nonlinear effects Ready 9-14 Addns to pi bonds-1 Ready 9-19 Addns to pi bonds-2 Ready 9-21 Addns to pi bonds-3 Ready 9-26 Conjugate addition-1 Ready 9-28

Noncovalent Polycationic Coatings for Capillaries in Capillary Electrophoresis of Proteins Emilio Córdova, Jinming Gao, and George M. Whitesides* Department of Chemistry and Chemical Biology, Harvard University, 12 Oxford Street, Cambridge, Massachusetts 02138 The adsorption of proteins with net positive charges (pI > pH) on the walls of fused-silica capillaries is a common problem in the analysis of proteins by capillary electro- phoresis. This paper explores the use of polycationic