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Oxidation of Unsaturated Systems 2 general reactivity patterns: X H X Yn+2 X+ Yn ++ OH simple example O A- Me2SCl+ S+ O + S + Cl- 2 electron oxidation 1 electron oxidation Xor -1 e- or X we will focus on oxidation of aromatic rings and enol/enolate systems Couple Eo Fe(III) + e- Fe(II) 0.77 V(V) + e- V(IV) 1.00 Tl(III) + 2 e- Th(I) 1.25 Pb(IV) + 2 e- Pb(II) 1.6-1.7 Mn(III) + e- 1.56Mn(II) Ce(IV) + e- Ce(III) 1.6 Reduction potentials of oxidants we will look at (bigger number

Ready; Catalysis Conjugate Addition Topics covered 1. 1,4 addition involving copper a. stoichiometric reactions b. catalytic reactions c. allylic substitution 2. Conjugate addition without copper a. Ni-based systems b. Rh-based systems 3. Catalytic addition of heteroatoms Topics not covered: enolate conjugate additions, Friedel-Crafts-type conjugate additions Ready; Catalysis Conjugate Addition: origin 1,4 addition reactions involving

Substrate pKa's. Numbers are approximations for outside the range -2 - 16, but useful to know. For an extensive list, see http://www.chem.wisc.edu/areas/reich/pkatable/ Inorganics H2O DMSO CF3SO3H -14 HCl -8 H3O+ -2 H2O 16 NH4Cl 9 Organic X-H AcOH 5 12 O+ CH3Ph H -6 Me2OH+ -4 CH3SO3H -3 2 NH+ 5 3 N H O H 15 26 MeOH 16 28 17 29 NH3 36 38 41 EWG-CH NO2-CH3 10 17 O O 9 13 O EtO O 11 14 O EtO OEt O 13 16 O 20 27 O t-BuO 25 30 O Me2N 35 O S 3533PhOH 10 18

1 Ready; Catalysis Kinetics-1 There are only two important things in chemistry, kinetics and thermodynamics. And, exp(-ΔG/RT) = k1/k-1, so there’s really only one thing. Kinetics provides information about the transition state of a reaction. We’ll use a simple example to learn the basic tools, then look at more applications to catalysis. Crude Data [EtI] = [NaCN] 0 0.2 0.4 0.6 0.8 1 1.2 0 2 4 6 8 10 Time Co nc en tra tio n [EtI] [EtCN] 1st step

1 Ready; Catalysis Organometallics: Definitions Organometallics: Hard to define usefully and completely at the same time, but generally: Compounds containing metal-carbon bond(s). Fe Cl Ti Cl Cl ClFe NC NC CN CN CN CN K3 No question: Organometallic No question: Inorganic ???? Catalysis further complicates the issue: CH3 Br CH3 (HO)2B H3C + Me2N PCy2 PdL L H3C CH3 CH3 CH3 CH3 CH3 2% Pd(OAc)2 3% L CsF, rt L = Buchwald, JACS, 1998, 9722

Ready; Catalysis Nonlinear Effects Outline Definitions Origins of nonlinear effects in enantioselective reactions ML2 model Reservoir model Transition-state model Kinetic aspects of nonlinear effects Asymmetric amplification Cool tricks Origin of biotic asymmetry? Key reviews Kagan, ACIEE, 1998, 2922 (a pretty complete review, source of many of my figures) Kagan, Advanced Syn. Cat., 2001, 227 (an overview) Blackmond, Accts, 2000, 402 (kinetic aspects) Soai

1 Kinetic Resolutions Material outline: For the Scientist in you: Definitions Theoretical treatment For the technician in you: Practical considerations Useful KR’s Oxidative KR of allylic alcohols An extreme example Acylation/deacylation Hydrogenation olefins ketones Dynamic kinetic resolution Epoxide ring opening A very extreme example Parallel kinetic resolution General References: Vedejs, ACIEE, 2005, 3974 Jacobsen, Adv. Syn

This journal is©The Royal Society of Chemistry 2020 Mater. Horiz., 2020, 7, 477--488 | 477 Cite this:Mater. Horiz., 2020, 7, 477 An ambient-stable and stretchable ionic skin with multimodal sensation† Binbin Ying, ab Qiyang Wu, ab Jianyu Li *bc and Xinyu Liu *abd Skin serves as a physical and hygroscopic barrier to protect the inner body, and also contains sensory receptors to perceive environmental and mechanical stimuli. To recapitulate these salient features, hydrogel-based artificial

ll OPEN ACCESS iScience Review Skin-like hydrogel devices for wearable sensing, soft robotics and beyond Binbin Ying1,2,4 and Xinyu Liu1,3,* 1Department of Mechanical and Industrial Engineering, University of Toronto, 5 King’s College Road, Toronto, ON M5S 3G8, Canada 2Department of Mechanical Engineering, McGill University, 817 Sherbrooke Street West, Montreal, QC H3A 0C3, Canada 3Institute of Biomedical Engineering, University of Toronto, 164 College Street, Toronto, ON M5S 3G9, Canada

Article https://doi.org/10.1038/s41467-024-51102-5 An ingestible, battery-free, tissue-adhering robotic interface for non-invasive and chronic electrostimulation of the gut Kewang Nan 1,2,3,13 , Kiwan Wong3,13, Dengfeng Li 4,5,13, Binbin Ying2,3,13, James C. McRae2, Vivian R. Feig2,3, Shubing Wang3, Ningjie Du 6, Yuelong Liang7, Qijiang Mao7, Enjie Zhou7, Yonglin Chen3, Lei Sang8, Kuanming Yao 4, Jingkun Zhou 4,5, Jian Li 4,5, Joshua Jenkins 3, Keiko Ishida3, Johannes Kuosmanen2, Wiam Abdalla