Harold C. Simmons Comprehensive Cancer Center Bioinformatics Data Science Shared Resource Data Science On-Demand User Agreement SCCC-DSSR This agreement is between the DSSR client named below and the Director of SCCC-DSSR, Professor Jeon Lee. By signing this document, user acknowledges and agrees to the conditions listed below. DSSR client (Full Name

Epoxidation, Dihydroxylation, and the Utility of Epoxides and Diols Ready Outline: Epoxidation Condensation approaches Darzens condensation Sulfur ylides With organic peroxides Peroxy acids Peroxy iminic acids Dioxiranes DMDO Enantioselective versions Metal-catalyzed Approaches V(O)(acac)2 Sharpless AE Metal Oxo’s MTO Fe, Pt and Mn-based (Salen)Mn Jacobsen AE Epoxide Ring Opening Opening under acid or basic conditions Organocopper additions Reactions of epoxy alcohols Dihydroxylation

Where does the secreted protein acidic and rich in cysteine (SPARC) protein originate? What leads to its expression? SPARC is secreted from cells. Virtually any cell can produce SPARC. In fact most cells that are adherent in tissue culture produce SPARC at a detectable level. Growth of cells in culture is stressful and SPARC is a protein that is often produced by cells under stress, thus the concept of it as a ‘culture shock’ protein was established. In tissues, cells that are

Reagent/Reaction Use Ref Note DMSO/DCC (Pfitzner- Moffatt or Moffatt) Alcohol ketone/aldehyde Jacs 1963, 3027; Mech: JACS, 1965, 5561, JOC, 1967, 1926 First DMSO-based; DCC pain to remove; EDCI better DMSO/Ac2O “ Jacs 1967, 2416 DMSO/TFAA “ Jacs, 1975, 2758 DMSO/SO3-Pyridine (Parikh- Doering) “ JACS, 1967, 5505 Often under ambient conditions; best for α-chiral aldehydes/ketones (COCl)2/DMSO (swern) “ JOC, 1978, 2480; mech: Tet. 1978, 1651 Most commonly used; DMSO/Ac2O

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

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

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 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

Postdoctoral Position in Neuroimaging A postdoctoral training position is available in the BioMedical Imaging Research Lab (BiMIR) led by Dr. Jiaen Liu in the Advanced Imaging Research Center (AIRC) at UT Southwestern Medical Center to develop advanced high resolution MRI methods for neuroimaging applications. BiMIR has several exciting projects related to novel MRI acquisition and reconstruction, ultrahigh-field MRI (≥7 T), quantitative MRI (T2, T2* and MT) for myelin and iron

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