Structure and Reactivity: An Introduction to Organic Chemistry Study Guide (a) (b) (c) (d) (e) (f) (i) Pd(0) (i) Pd(II) (ii) d10 (ii) d8 (iii) 14e (iii) 16e (i) Ti(IV) (i) Ti(IV) (ii) d0 (iii) 16e (iv) insertion (oxidative addn) (ii) d0 (iii) 16e (i) Pd(II) (i) Pd(II) (ii) d8 (ii) d8 (iii) 16e (iii) 14e (i) Pd(II) (i) Pd(II) (ii) d8 (ii) d8 (iii) 16e (iii) 16e (i) W(0) (i) W(0) (ii) d6 (ii) d6 (iii) 18e (iii) 18e (i) Pd(II) (i) Pd(II) (ii) d8 (ii) d8 (iii) 14e (iii) 16e (iv) (iv) (iv) (iv) (iv) additon additon substitution substitution elimination Structure and Reactivity: An Introduction to Organic Chemistry Study Guide (a) (b) (c) (d) (e) (f) (i) Ti(IV) (i) (ii) d0 (ii) d0 (iii) 16e (iii) 16e (i) Pd(II) (i) Pd(0) (ii) d8 (ii) d10 (iii) 16e (iii) 14e (i) Ru(IV) (i) Ru(IV) (ii) d4 (ii) d4 (iii) 16e (iii) 14e (i) Ti(I) (i) Ti(0) (ii) d3 (ii) d4 (iii) 15e (iii) 16e (i) Pd(II) (i) Pd(II) (ii) d8 (ii) d8 (iii) 16e (iii) 16e (i) Pd(II) (i) Pd(II) (ii) d8 (ii) d8 (iii) 16e (iii) 14e (iv) (iv) (iv) (iv) (iv) (iv) elimination reductive elimination ring closing metathesis reduction/substitution substitution addition Ti(IV) Structure and Reactivity: An Introduction to Organic Chemistry Study Guide (a) (b) (c) (d) (e) (f) (i) Rh(I) (i) (ii) d8 (ii) d6 (iii) 16e (iii) 18e (i) W(II) (i) W(II) (ii) d4 (ii) d4 (iii) 18e (iii) 18e (i) Cu(I) (i) Cu(III) (ii) d10 (ii) d8 (iii) 14e (iii) 14e (i) Rh(III) (i) Rh(III) (ii) d6 (iii) 18e (i) Pd(II) (ii) d8 (iii) 14e (i) Rh(III) (ii) d6 (iii) 18e (iv) (iv) (iv) (iv) oxidative addition ring closing metathesis substitution addition (iv) complexation/association (iv) reductive elimination Rh(III) (ii) d6 (iii) 16e (i) Pd(II) (ii) d8 (iii) 16e (i) Rh(I) (ii) d8 (iii) 16e Structure and Reactivity: An Introduction to Organic ChemistryStudy Guide (a) O H3CO H3CO Heck (donor) (b) O Ph CH3 O O Petasis (c) I H3CO O Pd(PPh3)4 KOAc Heck (EWG) (d) (e) Ph O O O H3C Stille O O CH3 Ph (f) H Grubbs O H3C (Bu3)Sn N Stille Structure and Reactivity: An Introduction to Organic Chemistry Study Guide (a) O N N H major diastereomer (92%) minor diastereomer (8%) N O N N H O N H (b) I + SnBu3 Pd(AsPh3)4 (c) OCH2Ph Br O H O O OCH2Ph O OCH2Ph Br H O O O O OCH2Ph Structure and Reactivity: An Introduction to Organic Chemistry Study Guide (a) Pd(PPh3)4 SnBu3 Br Ph CH3 N Ph Pd(PPh3)2 CH3 N SO2Ph SO2Ph Br Ph3P Pd Pd PPh3 Ph CH3 N SO2Ph Bu3SnBr (b) Pd(PPh3)4 N Ph CH3 N Pd(PPh3)2 K O Br O Ph CH3 (CH3)3COK SO2Ph SO2Ph OH Br Ph Ph3P Ph3P Pd Ph PPh3 N CH3 SO2Ph Ph Ph3P SnBu3 O Ph PPh3 CH3 N SO2Ph KBr Br O Pd PPh3 N CH3 SO2Ph K N CH3 SO2Ph Structure and Reactivity: An Introduction to Organic Chemistry Study Guide O O H H H Structure and Reactivity: An Introduction to Organic Chemistry Study Guide Zr Cl Structure and Reactivity: An Introduction to Organic Chemistry Study Guide Si Si O O N N SO2Ph SO2Ph Structure and Reactivity: An Introduction to Organic Chemistry Study Guide OCH3 Ph O OH O Ph N O O Ph OCH2CCl3 Structure and Reactivity: An Introduction to Organic Chemistry Study Guide Pd[P(tBu3)]4 Br Pd[P(tBu3)]2 N Ph3P Ph3P H Br N Pd PPh3 N Pd PPh3 (CH3)3COK KBr (CH3)3COK Ph3P H N Pd Br PPh3 Structure and Reactivity: An Introduction to Organic Chemistry Study Guide Pd(PPh)4 O Br Pd(PPh)2 Ph3P Br Pd PPh3 CO Ph3P Pd PPh3 Ph3P O Pd PPh3 C SnBu3 Ph3P Bu3SnBr Br O Br Pd O PPh3 SnBu3 Structure and Reactivity: An Introduction to Organic Chemistry Study Guide (a) (CH3CH2)3N PPh3 Ph3P H Pd OSO2CF3 Ph3P Pd(Ph3)4 OSO2CF3 OSO2CF3 Pd(Ph3)2 PPh3 (CH3CH2)3NH Pd H OSO2CF3 Ph3P Ph3P Pd OSO2CF3 OSO2CF3 PPh3 Pd H Ph3P major Ph3P Ph3P Pd Pd OSO2CF3 Ph3P OSO2CF3 Pd PPh3 OSO2CF3 OSO2CF3 Pd H minor (b) (c) The conjugated double bond is the major isomer. The regioselectivity of the b-H elimination of the Pd-H may be being driven by the resonance stabilization of the conjugated product which, if reflected in the transition state for breaking the CH bond, would lower the transition state energy and make that pathway faster. Ph3P Pd OSO2CF3 OH OH this result supports the conclusion in part (b): forming the double bond towards the OH not only creates effective delocalization stabilization (arguably the O atom is more effective than the phenyl ring, but the elimination reacting towards the OH creates an enol that can tautomerize to its keto form, driving that reaction even more sustantially in that direction. OH O

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