Organic Mechanisms. Xiaoping Sun

      1 Chapter 1FIGURE 1.1 Reaction profiles for a concerted S_N2 reaction (a) and a stepwise...FIGURE 1.2 The changes in concentrations of the reactant (X), intermediate (...FIGURE 1.3 The effects of enthalpy and entropy on reversibility of the chemi...FIGURE 1.4 Early transition state (a) and late transition state (b).FIGURE 1.5 The S_N2 reactions that proceed via (a) an early transition state ...FIGURE 1.6 The ρ constants for various reactions of substituted benzene...FIGURE 1.7 The shapes of the s and p orbitals in the three‐dimensional space...FIGURE 1.8 Formation of the hydrogen molecule (H₂) from two hydrogen (H) ato...FIGURE 1.9 Formation of the fluorine molecule (F₂) from two fluorine (F) ato...FIGURE 1.10 Formation of (a) the C=C π bond from two equivalent p orbitals a...FIGURE 1.11 Formation of conjugate π bonds from p orbitals in (a) the allyl ...FIGURE 1.12 Resonance stabilization of benzene.FIGURE 1.13 Possible resonance structures for the carbonyl (C=O) group.FIGURE 1.14 Resonance stabilization of the anolate anion.FIGURE 1.15 Possible resonance structures for (a) hydrogen chloride (HCl) an...FIGURE 1.16 Structure of different types of carbocations.FIGURE 1.17 (a) Overlap of a C─H bond of the methyl group in the ethyl catio...FIGURE 1.18 Reaction mechanism for acid‐catalyzed hydrolysis of the oxygen‐1...FIGURE 1.19 Energetics for C─H and C─D (deuterium) bonds.FIGURE 1.20 Reaction mechanism for nitration of benzene by acetyl nitrate.FIGURE 1.21 Acid–base catalysis for enzymatic reactions. (a) Uncatalyzed con...FIGURE 1.22 (a) Mechanism for the concerted reaction of H₂O and CO₂ giving H...FIGURE 1.23 Comparison of energetics for the concerted and the enzyme (carbo...FIGURE 1.24 Hydrophobic effects on organic reactions. (a) The intermolecular...

      2 Chapter 2FIGURE 2.1 (a) Structure of and bonding in the methyl radical and (b) bondin...FIGURE 2.2 Molecular orbital model for the hyperconjugation effect in the et...FIGURE 2.3 Resonance stabilization for (a) the ethyl radical, (b) the isopro...FIGURE 2.4 Molecular orbitals in the allyl radical.FIGURE 2.5 Conjugation effect in the benzyl radical.FIGURE 2.6 Resonance stabilization for allyl (a) and benzyl radicals (b).FIGURE 2.7 Bond dissociation energies (BDEs) for HC≡C˙, C₆H₅˙, and H₂C=CH˙ r...FIGURE 2.8 Energy levels (BDE's—bond dissociation energies) for various radi...FIGURE 2.9 Mechanism for radical chlorination of methane.FIGURE 2.10 Nature of the transition states for the chain‐growth steps of ch...FIGURE 2.11 Reaction profiles for the chain‐growth steps of chlorination of ...FIGURE 2.12 Reaction profiles, transition states, and activation energies fo...FIGURE 2.13 (a) Overall mechanism for radical halogenation (substitution and...FIGURE 2.14 Thermal dissociation of (PhCOO)₂ giving the Ph˙ radical.FIGURE 2.15 Mechanism for (PhCOO)₂ initiated autoxidation of cumene (isoprop...FIGURE 2.16 The alkane C─H bond activation by transition metal complex...FIGURE 2.17 The alkane C─H bond activation by various transition metal...FIGURE 2.18 Mechanism for the methane C─H bond activation by mercury(I...FIGURE 2.19 Structure of dichloro(η‐2‐{2,2′‐bipyrimidyl})platinum(II), denot...FIGURE 2.20 Mechanism for the (bpym)PtCl₂ catalyzed functionalization of met...FIGURE 2.21 The proposed transition states for the hydrogen abstraction of t...FIGURE 2.22 Reactions of alkanes with elemental sulfur in triflic acid.FIGURE 2.23 Mechanism for the triflic acid catalyzed alkane C─H bond a...FIGURE 2.24 The protonated nitronium NO₂H²⁺ dication and its reaction with m...FIGURE 2.25 Nitration of adamantane via a three‐center, two‐electron bond ca...FIGURE 2.26 Reactions of nitronium hexafluorophosphate with (a) ethane, (b) ...FIGURE 2.27 Cytochrome P‐450 catalyzed alkane C─H bond oxidative funct...FIGURE 2.28 Structure of active site of methane monooxygenase (MMO) and mech...

      3 Chapter 3FIGURE 3.1 Mechanism and regioselectivity for electrophilic addition of hydr...FIGURE 3.2 Reaction profiles for electrophilic addition of hydrogen chloride...FIGURE 3.3 Regioselectivity for electrophilic addition of hydrogen bromide t...FIGURE 3.4 Mechanism and stereochemistry for electrophilic addition of hydro...FIGURE 3.5 Mechanism, regiochemistry, and stereochemistry for electrophilic ...FIGURE 3.6 Stereoselectivity of electrophilic addition of hydrogen iodide to...FIGURE 3.7 The acid‐catalyzed hydration of various alkenes.FIGURE 3.8 Mechanism for the acid‐catalyzed hydration of 1‐methoxycyclohexen...FIGURE 3.9 Structure of mercury(II) acetate.FIGURE 3.10 Mechanism and regioselectivity for mercury(II) acetate catalyzed...FIGURE 3.11 The acid‐catalyzed electrophilic addition of alcohols to various...FIGURE 3.12 Mechanism for toluenesulfonic acid catalyzed electrophilic addit...FIGURE 3.13 Aluminum chloride catalyzed addition of benzene to cyclohexene....FIGURE 3.14 Acid catalyzed reaction of 2‐methylpropene with isobutane effect...FIGURE 3.15 The AlCl₃‐catalyzed electrophilic addition of deuterated PhCD₂Cl...FIGURE 3.16 Electrophilic addition of hydrogen chloride to 1,3‐butadiene. (a...FIGURE 3.17 Radical initiated Non‐Markovnikov addition of hydrogen bromide t...FIGURE 3.18 Structure of and bonding in diborane and borane. The three‐cente...FIGURE 3.19 Mechanism for hydroboration of alkenes: Concerted, non‐Markovnik...FIGURE 3.20 Mechanism, regiochemistry, and stereochemistry for hydroboration...FIGURE 3.21 Synthesis of 9‐borabicyclo[3.3.1]nonane (9‐BBN).FIGURE 3.22 Hydroboration of a‐pinene by diborane (via BH₃) in THF.FIGURE 3.23 Comparison of regioselectivity for alkene hydroborations effecte...FIGURE 3.24 Stereoselectivity for hydroboration reactions of (R)‐ and (S)‐3‐...FIGURE 3.25 Mechanism for transition‐metal catalyzed heterogeneous hydrogena...FIGURE 3.26 The MO diagram for the formation of the H─M─H bonds from H₂ and ...FIGURE 3.27 Palladium catalyzed hydrogenation of 2,3‐diphenyl‐2‐butenes in (FIGURE 3.28 A hypothesized hydrogenated fat (saturated) made by transition‐m...FIGURE 3.29 Mechanism and transition states for halogenation of alkene in di...FIGURE 3.30 Mechanism and stereochemistry for bromination