Search

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

Reactivity Umpolung-1 Ready Reactivity Umpolung: reversal of normal polarity electrophiles become nucleophiles nucleophiles become electrophiles Outline: 1. electrophilic heteroatoms 2. acyl anions 3. homoenolates 4. the cyclopropane trick 5. sulfone chemistry Normal reactivity: X x = heteroatom d = donor (Nu-) a = acceptor (E+) d a d a d X X X X or 1 3 1 5 How to make: X X or X X 1 2 1 4 complimentary

Protecting Groups in Organic Synthesis-1 Ready Protecting groups are a sad fact of synthetic chemistry They are usually needed, but rarely desired Many syntheses have stalled because of trouble putting on or removing protecting groups 4 basic questions to address when choosing a P.G.: 1. Can I put it on where and only where I want? 2. Can I take it and only it off? 3. Will it survive all future reaction conditions? 4. Will it

Oxidations at Carbon General references March, Advanced Org Chem, 1992, 1158-1238 Trost, Comp. Org. Syn. 1991, vol 7 Carey and Sundberg, Advanced Org Chem, part B, 615-664 Smith, Org Syn, Chap 3 H CH3 C(-IV) R CH3 C(-III) R CH2 OH C(-1) R CH OH RR H2 C R C(-II) R C O R C(0) R CH O C(+I) H CH2 OH C(-II) H CH O C(0) C(II) R COR O C(+III) H COH O C(+II) O C O C(+IV) RO COR O C(+IV) alkane RCH2M RCH2SiR3 RCH2X X=halide RCH2NR2 RCH2SR RCH2PR2 Acetal: RCH(OR)2

1 R Co(CO)3(OC)3Co O O Δ (OC)3Co O R H O R H2 R H O (OC)4Co R (OC)4Co Co(CO)4 H H (CO)4CoH H2 CO R O H R CO (OC)3Co R (OC)3Co H R H2 R (OC)3Co R The Oxo process -developed in 1938 by Otto Roelen -Principle method for hydroformylation of terminal alkenes industrially -more that 4 million tons aldehyde annually -linear aldehydes more desirable Co2(CO)8 H2/CO (200-300 atm) 120-170 oC linear (normal) branched (iso) + chemical feed stocks linear alcohols

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

Cooperativity Principles in Self-Assembled Nanomedicine Yang Li,† Yiguang Wang,†,‡ Gang Huang,† and Jinming Gao*,† †Department of Pharmacology, Simmons Comprehensive Cancer Center, UT Southwestern Medical Center, 5323 Harry Hines Boulevard, Dallas, Texas 75390, United States ‡Beijing Key Laboratory of Molecular Pharmaceutics and State Key Laboratory of Natural and Biomimetic Drugs, Peking University, Beijing, 100191, China ABSTRACT: Nanomedicine is a discipline that applies nanoscience and

COMMUNICATION www.advhealthmat.de Tumor-Targeted Inhibition of Monocarboxylate Transporter  Improves T-Cell Immunotherapy of Solid Tumors Tongyi Huang, Qiang Feng, Zhaohui Wang, Wei Li, Zhichen Sun, Jonathan Wilhelm, Gang Huang, Tram Vo, Baran D. Sumer, and Jinming Gao* Export of lactic acid from glycolytic cancer cells to the extracellular tumor milieu has been reported to enhance tumor growth and suppress antitumor immunity

Meet the Wetzel Lab team.