orgo chem ch 7 8

H-X (Cl, Br, I)

Hydrohalogenation

Markovnikov

HBr, ROOR

hydrobromination

Antimarkovnikov

H3O+/H+/dilute acid

Acid Catalyzed Hydration

Markovnikov

rearrangements possible

1) Hg(OAc)2, H2O

2) NaBH4

oxymercuration-demercuration

markovnikov hydration

no rearrangements

1) BH3, THF

2) H2O2, NaOH

hydroboration-oxidation

antimarkovnikov hydration

no rearrangements

syn addition

H2, Pt

Hydrogenation

syn addition

Br2

Bromination

anti addition

creates a bridge in intermediate

Br2, H2O

Halohydrin formation

anti addition Br & h2o across bond

oh on more substituted position

1) RCO3H

2) H3O+

Anti dihydroxylation

epoxide then opened with acid to give trans with oh on both sides

KMnO4, NaOH cold

Syn Dihydroxylation, Treatment with an alkene gives a syn addition of OH and OH across the alkene

1) OsO4

2) NaHSO3, H2O

Syn dihydroxylation

syn addition of OH and OH

1) O3

2)DMS

Ozonolysis

cleavage of double bond with replacement of O on end

Strong base weak nucleophile

primary carbon

E2

DBU, DBN, NaH, KBuO

Strong Base Strong Nucleophile

primary carbon

Primary SN2, minor E2

NaOH, NaOCH3, NaOCH2CH3

Strong base weak nucleophile

secondary carbon

E2

DBU, DBN, NaH, KBuO

Strong base weak nucleophile

tertiary carbon

E2

DBU, DBN, NaH, KBuO

Strong Base Strong Nucleophile

primary carbon

Primary E2, Minor SN2

NaOH, NaOCH3, NaOCH2CH3

Strong Base Strong Nucleophile

tertiary carbon

only e2

NaOH, NaOCH3, NaOCH2CH3

Weak base, strong nucleophile

primary carbon

SN2

I-, Cl-, Br-

-SH

Weak base, strong nucleophile

secondary carbon

SN2

I-, Cl-, Br-

-SH

Weak base, strong nucleophile

Tertiary carbon

SN1

I-, Cl-, Br-

-SH

weak base, weak nucleophile

primary carbon

no reaction

H2O, CH3OH, etc

weak base, weak nucleophile

secondary carbon

no reaction

H2O, CH3OH, etc

weak base, weak nucleophile

tertiary carbon

SN1/E1

H2O, CH3OH, etc

Hoffman product

less substituted alkene product

Zaitsef product

more substituted alkene product

markovnikov

OH group, halogen group binds to side with more carbon substituents

antimarkovnikov

OH group, halogen group binds to side with less carbon substituents