CHEM 2AO3 SUMMER 2009Reaction Summary Chart Reaction type Full hydrogenation Cis hydrogenation Trans hydrogenation Dehydrohalogenation

Reactant Alkyne Alkene Alkyne Alkyne Alkyl halide Mechanism Product Alkanes Z-Alkene E-Alkene E2: Take H+ from MS carbon (Zaitsevs) E2: Take H+ from LS carbon (Hoffmans) E1: OH2+ leaves, forms stable C+ E2: base takes H+ and OH2+ leaves Grignard R- takes H+, leaves OH H+ to LS carbon, form C+ X+ to LS carbon, XSN2 attack X+ to LS carbon, H2O SN2 attack Br to LS carbon, form stable C radical -ROH SN2 attacks, form ROPBr2+ Br- SN2 attacks, form R-Br H+ to LS carbon, form C+ BH3 attaches at LS carbon, -OH replaces Alkene/Alkyne Regiochem Syn Syn Anti

Josie Xu Catalysts/Conditions H2/Pt H2/Pt, Pd, Ni H2/Lindlars catalyst 1) Li/NH3 and 70C 2) NH4Cl Strong base: NaCH3O or NaNH2 and heat Strong bulky base: KOC(CH3)3 H2SO4, H3PO4 (concentrated acid) and heat

Dehydration (acid catalyzed)

2 and 3 alcohol alcohol Alkene ROH Alkene Alkene Alkene Alkene 1 and 2 alcohol Alkene Alkene

Alkene/Alkyne

Alkyne synthesis from alkene by double E2 Synthesis of alkane from Grignard reagent Hydrohalogenation Halogenation Halohydrin Anti-Markov addition of HBr Making Alkyl bromides with PBr3 Hydration of alkenes Hydroboration

Alkyne Alkane Alkyl halide Alkyl halide Alcohol halide Alkyl bromide Alkyl bromide Not controlled Anti Anti Not controlled HX X2

1) X2 2) 2NaNH2 1) RMgX, ether

1) X2 2) ROH ROOR, HBr PBr3

Alcohol Alcohol

Not controlled Syn

H3O+ (dilute acid) 1) BH3 or 9-BBN 2) H2O2, OHKMnO4, OH-, dilute, cold

1,2-dihydroxylation

Alkene

Cis-diol

Syn

CHEM 2AO3 SUMMER 2009Reaction Summary Chart ACID: protonate Trans-diol epoxide, attack MS carbon with H2O BASE: attack with HOat LS carbon Alcohol formation with Grignard reagent (nucleophilic reaction) Oxidation cleavage of alkenes full oxidation Ozonolysis weak oxidation cleavage Epoxidation Creating Grignard Reagent Reduction Epoxides Ketones, aldehydes Alkenes Alkenes Alkene HX Carboyxlic acid Ketone Oxidation 1 alcohols Hydride SN2 attack, forms OGrignard R- bonds to LS carbon, ring opens Grignard R- SN2 attacks, forms OCleave and oxidize at C=C Cleave and oxidize at C=C Break C=C, bond with O Alcohol Alcohol Carboxylic acids Ketones, aldehydes Epoxide RMgX Aldehyde Alcohol Alcohol Aldehyde Carboxylic acid 2 alcohols Conversation to sulfonate ester (very good leaving group) Williamson Ether Synthesis Alcohol Alkyl halide SN2 Ketone Mesylate (MsOR), Tosylate (TsOR), Triflate (RfOR) Ether

Anti

Josie Xu 1) RCO3H (peroxy acid) create epoxide Acid-catalyzed Base-catalyzed (SN1-like) (SN2) + 2) H3O 2) HO1) RMgX, Ether 2) H3O+

1) KMnO4, OH-, heat 2) H3O+ workup 1) O3 2) Zn in HOAc (Acetic acid) RCO3H (peroxy acid) dry Mg, ROR (ether) NaBH4 , H2O 1) LiAlH4 / Et2O 2) H2O/ H2SO4 NaBH4 , H2O OR 1) LiAlH4 / Et2O 2) H2O/ H2SO4 PCC / CH2Cl2 KMnO4, OH-, H2O, heat KMnO4, OH-, dilute, heat OR PCC / CH2Cl2 OR H2CrO4 OR Jones reagent (CrO3 in acetone)

Syn

RO-